KR20200132438A - Eco-friendly pump for cosmetic case comprising polyketone composition - Google Patents

Abstract

The present invention relates to an eco-friendly pump for a cosmetic container manufactured by injection molding of a polyketone composition comprising: 95.0 to 99.5 wt% of a polyketone consisting of carbon monoxide and at least one type of olefinically unsaturated hydrocarbon; and 0.5 to 5.0 wt% of a silicon master batch.

Description

Eco-friendly pump for cosmetic containers containing polyketone composition {ECO-FRIENDLY PUMP FOR COSMETIC CASE COMPRISING POLYKETONE COMPOSITION}

The present invention relates to an eco-friendly pump for cosmetic containers containing a polyketone composition.

Polyketone (PK) is a material with lower raw material and polymerization process costs compared to general engineering plastic materials such as polyamide, polyester and polycarbonate, and has excellent heat resistance, chemical resistance, impact resistance, and fuel permeability.

Polyketones with these characteristics are included in general-purpose high-performance plastics, have strengths comparable to those of conventional engineering plastics, and have good affinity with rubber. Due to the characteristics of such polyketones, polyketones may be used for tire cords or rubber materials in which conventional paraffin-based aramid fibers are exclusively used.

On the other hand, in the case of polyoxymethylene (POM), which is a representative material used as a cosmetic container, the use of formaldehyde, which is harmful to the human body, is dissolved.

Accordingly, polyketones have recently been applied as materials for cosmetic containers due to their strengths in formaldehyde-free, abrasion resistance, lubricity and chemical resistance. However, in the case of using polyketone as a material for the pump engine in the pumping structure container among cosmetic containers or pharmaceutical containers, the container contents may have various compositions, in particular, there is a problem that operation failure occurs in a liquid containing a high ethanol content. there was. Specifically, as shown in FIG. 1, in the case of a high ethanol solution, a phenomenon in which the viscosity increases due to hydrogen bonding between ethanol and water occurs, especially in the section of ethanol 50 vol%, and a defect that does not operate during pumping occurs. There can be.

Accordingly, there is a need for a technology development of a pump material that can be stably implemented even in a specific liquid, particularly a liquid with a high ethanol content.

It is an object of the present invention to provide an eco-friendly pump for cosmetic containers comprising a polyketone composition having improved surface tension that does not elute formaldehyde.

An eco-friendly pump for a cosmetic container according to an embodiment of the present invention includes 95.0 to 99.5% by weight of a polyketone consisting of carbon monoxide and at least one olefin-based unsaturated hydrocarbon; And it may be prepared by injection molding a polyketone composition comprising 0.5 to 5.0 weight of a silicone master batch (master batch).

In this case, the silicone master batch may include 40 to 60% by weight of a silicone compound and 40 to 60% by weight of a carrier resin.

The silicone-based compound may be one selected from the group consisting of ultra-high molecular weight siloxane-based compounds, polydimethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane.

The carrier resin may be one selected from the group consisting of polyamide, acrylate, and polyethylene.

In addition, the polyketone composition may have a contact angle of 68 to 77° with water and a contact angle of 0 to 55° with an aqueous solution containing 50 vol% of ethanol.

According to an embodiment of the present invention, the eco-friendly pump for a cosmetic container may improve surface tension by including the polyketone composition of the present invention, and a similar contact angle under water and high ethanol content compared to the existing pump material, polyoxymethylene. Can have For this reason, the pump operation can be stably implemented even in the cosmetic container contents, especially the contents liquid with a high ethanol content. In addition, it is eco-friendly because it does not elute formaldehyde at all compared to existing polyoxymethylene materials.

Accordingly, the polyketone composition can be environmentally and easily applied to the cosmetic container pump regardless of the composition of the liquid due to the improved surface tension along with the formaldehyde-free characteristics, abrasion resistance, and chemical resistance of the polyketone itself.

1 is a graph showing the viscosity of an aqueous solution according to vol% of ethanol.

In the present invention, various modifications may be made and various forms may be applied, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In describing each drawing, similar reference numerals have been used for similar elements. In the accompanying drawings, the dimensions of the structures are shown to be enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance the possibility of the presence or addition. Further, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when a part such as a layer, film, region, plate, etc. is said to be "under" another part, this includes not only the case where the other part is "directly below", but also the case where there is another part in the middle. In addition, in the present application, the term "above" may include a case where it is disposed not only above but also below.

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

The eco-friendly pump for a cosmetic container according to an embodiment may be manufactured by injection-molding a polyketone composition comprising a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and a silicone master batch.

First, the polyketone of the present invention is a linear alternating structure, and substantially contains carbon monoxide per molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins, such as propene, 1-butene, iso-butene, 1-hexene, and 1-octene. ), or an aryl aliphatic containing an aryl substituent on another aliphatic molecule, and particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons among ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene, or a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms with carbon monoxide and ethene, especially α-olefins such as propene. It is a terpolymer of the family.

When the polyketone terpolymer is used as the main polymer component of the composition according to the present invention, with respect to each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing an ethylene moiety. It is preferable that there are 10 to 100 units containing the second hydrocarbon moiety.

The polymer ring of the preferred polyketone polymer in the present invention can be represented by the following structural formula 1.

[Structural Formula 1]

-[CO-(-CH2-CH2-)-]x-[CO-(G)]y-

In the above Structural Formula 1, G is an ethylenically unsaturated hydrocarbon, particularly a moiety obtained from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and x:y is preferably at least 1:0.01.

In another embodiment, the polyketone polymer is a copolymer composed of repeating units represented by general formulas (1) and (2), and y/x is preferably 0.03 to 0.3. When the value of the y/x value is less than 0.03, there is a limit to inferior meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. Further, y/x is more preferably 0.03 to 0.1.

-[-CH2CH2-CO]x- (1)

-[-CH2-CH(CH3)-CO]y- (2)

In addition, the melting point of the polymer can be controlled by adjusting the ratio of ethylene and propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46:4:50, the melting point is about 220℃, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235℃.

Polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000 as measured by gel permeation chromatography, are particularly preferred. The physical properties of the polymer are determined according to the molecular weight, depending on the polymer being a copolymer or terpolymer, and in the case of a terpolymer, depending on the properties of the second hydrocarbon moiety present. The melting point of the polymer used in the present invention is 175°C to 300°C, and generally 210°C to 270°C. The intrinsic viscosity (IV) of the polymer measured at 60°C with HFIP (Hexafluoroisopropylalcohol) using a standard customs viscosity measuring device is 0.5dl/g to 10dl/g, preferably 0.8dl/g to 4dl/g, and more Preferably, it is 1.0dl/g-1.4dl/g. At this time, if the number of intrinsic viscosity is less than 1.0 dl/g, mechanical properties deteriorate, and if it exceeds 1.4 dl/g, processability deteriorates.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. If it is less than 1.5, the polymerization yield is lowered, and if it is more than 2.5, there is a problem that the moldability is lowered. In order to control the molecular weight distribution, it can be adjusted in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100°C or higher, the molecular weight distribution increases.

As a method for producing a polyketone polymer, a liquid phase polymerization carried out in an alcohol solvent through a catalyst composition consisting of a palladium compound, an acid having a PKa of 6 or less, and a di-di ligand compound of phosphorus may be employed. The polymerization reaction temperature is preferably 50 to 100 °C and the reaction pressure is 40 to 60 bar. The polymer is recovered through filtration and purification after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

Here, the palladium compound is preferably palladium acetate, and the amount used is preferably 10 ^-3 to 10 ^-1 mole. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid was used, and the amount used is preferably 6 to 20 equivalents compared to palladium. In addition, 1,3-bis[di(2-methoxyphenylphosphino)]propane is preferable as the compound of phosphorus bidentate coordination, and the amount is preferably 1 to 1.2 equivalents compared to palladium.

Hereinafter, the polymerization process of the polyketone polymer will be described in detail.

Carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, especially repeating units derived from carbon monoxide and ethylenically unsaturated compounds, and repeating units derived from propylene-based unsaturated compounds are substantially Polyketones of alternatingly connected structures have excellent mechanical and thermal properties, excellent processability, and high wear resistance, chemical resistance, and gas barrier properties, making them useful materials for various purposes. The high molecular weight substance of this ternary or higher copolymerized polyketone has higher processability and thermal properties, and is considered to be useful as an engineering plastic material having excellent economical efficiency. In particular, it can be used for parts such as gears of automobiles due to its high wear resistance, linings for chemical transport pipes, etc. due to its high chemical resistance, and lightweight gasoline tanks due to its high gas barrier properties. In addition, when an ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fiber, it is possible to draw a high magnification, and as a fiber with high strength and high modulus of elasticity oriented in the drawing direction, it is a reinforcing material for belts, rubber hoses, tire cords, concrete reinforcing materials. It becomes a very suitable material for building materials or industrial materials.

The polyketone production method includes carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst consisting of (a) a group 9, group 10 or group 11 transition metal compound, and (b) a ligand having an element of group 15. In the method for producing a polyketone by ternary copolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, the mixing As a solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, ketals are formed, the thermal stability may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

Here, the catalyst is composed of (a) a Group 9, Group 10, or Group 11 transition metal compound of the Periodic Table (IUPAC Nomenclature Revised Edition, 1989), and (b) a ligand having an element of Group 15.

Examples of the Group 9 transition metal compound among the Group 9, 10 or 11 transition metal compounds (a) include cobalt or ruthenium complexes, carbohydrates, phosphates, carbamates, sulfonates, and the like, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, ruthenium trifluoromethane sulfonate, and the like.

Examples of the Group 10 transition metal compound include a complex of nickel or palladium, a carbonate, a phosphate, a carbamate, a sulfonate, etc., and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate. , Palladium acetylacetate, palladium chloride, bis(N,N-diethylcarbamate)bis(diethylamine)palladium, palladium sulfate, and the like.

Examples of the Group 11 transition metal compound include a complex of copper or silver, a carbonate, a phosphate, a carbamate, a sulfonate, and the like, and specific examples thereof include copper acetate, trifluoro copper acetate, copper acetylacetate, silver acetate, tri Silver fluoroacetic acid, silver acetylacetate, silver trifluoromethane sulfonic acid, etc. are mentioned.

Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferable transition metal compounds (a) in terms of the yield and molecular weight of polyketones are palladium compounds, and improvement in catalytic activity and intrinsic viscosity It is most preferable to use palladium acetate.

Examples of the ligand (b) having an atom of Group 15 include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , Nitrogen ligands such as 2,2'-bikinoline, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Butane, 1,3-bis[di(2-methyl)phosphino]propane, 1,3-bis[di(2-isopropyl)phosphino]propane, 1,3-bis[di(2-methoxyphenyl) )Phosphino]propane, 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis(diphenylphosphino)cyclohexane, 1,2-bis (Diphenylphosphino)benzene, 1,2-bis[(diphenylphosphino)methyl]benzene, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, 1,2- Bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]methyl]benzene, 1,1'-bis(diphenylphosphino)ferrocene, 2-hydroxy-1,3-bis[di (2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-di Phosphorus ligands such as oxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), (cyclohexane-1,1-diylbis(methylene))bis(bis( 2-methoxyphenyl)phosphine, and the like.

Among them, the preferred ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly preferred in terms of the yield of polyketone is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis[ It is di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and it does not require an organic solvent and is safe. Water-soluble 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino] ]Methyl]benzene, which is easy to synthesize, can be obtained in large quantities, and is preferably 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane in terms of economy. The preferred ligand (b) having an atom of Group 15 is 1,3-bis[di(2-methoxyphenyl)phosphino]propane or 1,3-bis(diphenylphosphino)propane, most preferably 1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -Methoxyphenyl)phosphine) or (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine.

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of Formula 1 is a polyketone introduced so far. Expression equivalent to 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to exhibit the highest activity among polymerization catalysts It is a material with a simpler structure and a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art and further reducing its manufacturing cost and cost. The preparation method of the ligand for polyketone polymerization catalyst is as follows. Using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained. A method for preparing a ligand for a polyketone polymerization catalyst is provided. . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventional 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-) through an easy process in a safe environment where lithium is not used, Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.

On the other hand, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine as the ligand used in the polymerization catalyst. The method for synthesizing the ligand is as follows. Same as the reaction equation.

[Reaction Scheme]

The (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine ligand can be synthesized through the following four steps: First, diethylmalonate and 1, 5-dibromopentane is boiled under sodium ethoxide and ethanol, then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and reacted under tosyl chloride and pyridine to obtain release By reacting this ligand with 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide, the ligand can be obtained, and each step undergoes purification steps such as column chromatography and recrystallization. The purity can be confirmed through nuclear magnetic resonance analysis.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises (a) adding bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under nitrogen atmosphere and hydrogenating at room temperature. Stirring after adding sodium; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethyl sulfoxide to the obtained mixture, followed by stirring to react; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after layer separation, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) It can be carried out through the step of obtaining.

The amount of the transition metal compound (a) used in the Group 9, 10 or 11 transition metal compound (a) varies according to the selected ethylenic and propylene unsaturated compounds or other polymerization conditions. Although it cannot be limited, it is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol per 1 liter of the capacity of the reaction band. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 moles, preferably 1 to 3 moles, per 1 mole of the transition metal compound (a).

In addition, it is another feature that benzophenone is added during polymerization of the polyketone. In the present invention, the intrinsic viscosity of the polyketone can be improved by adding benzophenone during polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10, or Group 11 transition metal compound and benzophenone is 1:5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal and benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the prepared polyketone is not satisfactory, and if the molar ratio of the transition metal and benzophenone exceeds 1:100, the catalytic activity of the polyketone produced is rather It is not desirable because it tends to decrease

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins, such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic acid esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The three-way copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex consisting of the group 9, 10 or 11 transition metal compound (a), and a ligand (b) having an element of group 15 It is caused by a catalyst, and the catalyst is produced by contacting the two components. Any method can be adopted as a method of contacting. That is, in a suitable solvent, the two components may be premixed and used, or the two components may be separately supplied to the polymerization system and brought into contact within the polymerization system.

In the present invention, conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, release agents, colorants, and other materials may additionally be included in order to improve the processability or physical properties of the polymer.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, and a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution are used. The polymerization may be a batch type or a continuous type. As the reactor used for polymerization, a known reactor can be used as it is or processed. The polymerization temperature is not particularly limited, and is generally 40 to 180°C, preferably 50 to 120°C. There is also no restriction on the pressure during polymerization, but it is generally normal pressure to 20 MPa, preferably 4 to 15 MPa.

Alternating linear polyketones are formed by the polymerization method as described above.

The content of the polyketone may be a residual amount such that the total weight of the polyketone composition is 100% by weight, preferably 95.0 to 99.5% by weight. When the content of polyketone is less than 95.0% by weight, mechanical properties, thermal stability, and fluidity may be reduced, and when it exceeds 99.5% by weight, the content of specific substances added to the composition is relatively small, resulting in an effect of improving surface tension. It can be insignificant.

These polyketones can be applied as an eco-friendly pump material among cosmetic containers due to their strengths in formaldehyde-free, abrasion resistance, lubricity and chemical resistance. However, in the case of using polyketone as a material for the pump engine in the pumping structure container among cosmetic containers or pharmaceutical containers, the container contents may have various compositions, in particular, there is a problem that operation failure occurs in a liquid containing high ethanol content. there was. Specifically, as shown in FIG. 1, in the case of a high ethanol solution, a phenomenon in which the viscosity increases due to hydrogen bonding between ethanol and water occurs, especially in the section of ethanol 50 vol%, and a defect that does not operate during pumping occurs. There can be.

Thus, the polyketone composition of the present invention is characterized in that it comprises a silicone master batch. By including the silicone master batch, the surface tension may be improved, and a similar contact angle may be obtained under water and high ethanol content compared to polyoxymethylene (POM), which is a conventional pump material. For this reason, the pump operation can be stably implemented even in the cosmetic container contents, especially the contents liquid with a high ethanol content.

Accordingly, the polyketone composition can be environmentally and easily applied to the cosmetic container pump regardless of the composition of the liquid due to the improved surface tension along with the formaldehyde-free characteristics, abrasion resistance, and chemical resistance of the polyketone itself.

The polyketone composition according to the present invention may contain 0.5 to 5.0% by weight of the silicone master batch, preferably 1 to 4% by weight, and more preferably 2 to 3% by weight. When the content of the master batch is less than 0.5% by weight, it is difficult to express the desired effect of improving surface tension, and when it exceeds 5% by weight, problems such as deterioration in processability may occur.

Such a silicone master batch may include 40 to 60% by weight of a silicone compound and 40 to 60% by weight of a carrier resin, and there is an excellent advantage in improving the surface tension of the final polyketone composition within the above range. More preferably, the master batch may include 50% by weight of a silicone compound and 50% by weight of a carrier resin, and in this case, it is possible to improve surface tension while having excellent processability and moldability of the composition. Here, the silicone-based compound is a component for improving surface tension, and the carrier resin is a component used for mixing and commercialization to impart compatibility.

Non-limiting examples of the silicone-based compound may be one selected from the group consisting of ultra-high molecular weight siloxane-based compounds, polydimethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane.

In addition, various polymers such as polyamide (PA), acrylate, polyethylene (PE), etc. may be used as the carrier resin in accordance with the silicone-based compound as a matrix polymer. At this time, it is preferable to use low-density polyethylene (LDPE) among polyethylene as the carrier resin, and in this case, it is excellent in terms of price competitiveness.

In addition, the polyketone composition of the present invention may further contain conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, release agents, colorants, and other materials in order to improve the processability or physical properties of the polymer.

On the other hand, the manufacturing method of the polyketone composition of the present invention is as follows.

The method for preparing a polyketone composition of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a phosphorus 2 ligand compound; Preparing a mixed solvent (polymerization solvent) containing alcohol (eg, methanol) and water; Conducting polymerization in the presence of the catalyst composition and a mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the catalyst composition remaining from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And injection-molding the polyketone and the silicon master batch; but is not limited thereto.

The carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, and a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used as the mixed solvent. If the content of water in the mixed solvent is less than 2 parts by weight, the ketal is formed, and heat resistance may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is in the range of 40 ~ 60bar is appropriate. The resulting polymer is recovered through filtration and purification after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone composition is extruded with an extruder to finally obtain a polyketone composition. The polyketone composition may be prepared by melt-kneading and extruding into a twin screw extruder.

At this time, the extrusion temperature is preferably 230 ~ 260 ℃, the screw rotation speed is in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230°C, kneading may not occur properly, and if it exceeds 260°C, problems related to heat resistance of the resin may occur. In addition, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur, and if it exceeds 300 rpm, mechanical properties may deteriorate.

A composition may be prepared in the same manner as described above, and a sheet, a film, a plate, and a molded article may be manufactured by extrusion or injection molding the composition. In particular, the polyketone composition of the present invention can be environmentally and easily applied to a cosmetic container pump regardless of the composition of the liquid due to the improved surface tension along with the formaldehyde-free properties, abrasion resistance, and chemical resistance of the polyketone itself, The pump operation can be stably implemented even in the cosmetic container contents, especially the contents liquid with a high ethanol content.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.

[Examples 1 to 4]

The linearly alternating polyketones consisting of carbon monoxide, ethylene and propene are palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( It was prepared in the presence of a catalyst composition produced from 2-methoxyphenyl)phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first step of the polymerization temperature of 78°C and the second step of 84°C are performed. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. Further, the polyketone had a melting point of 220°C and a viscosity (I.V) of 1.4 dl/g measured at 25°C with HFIP (hexa-fluoroisopropano).

A master batch in which 50% by weight of the prepared polyketone and the ultra-high molecular weight siloxane compound is dispersed in 50% by weight of PA6 (dow corning MB50-011) was added in the amount shown in Table 1 to prepare a composition, and the prepared composition was injection-molded. Thus, a specimen of a pump for a cosmetic container was prepared.

[Examples 5 to 8]

A master batch in which 50% by weight of the polyketone and the silicone compound prepared in Example 1 were dispersed in 50% by weight of polyamide was added in the amount shown in Table 1 to prepare a composition, and the prepared composition was operated at 250 rpm with a diameter of 40 cm. And, using a twin-screw screw of L/D=32, a pellet was prepared on an extruder, and then injection-molded to prepare a specimen of a pump for a cosmetic container.

[Examples 9 and 10]

A master batch in which 50% by weight of a silicone compound was dispersed in 50% by weight of PA6 was used, and the samples were prepared through the same procedure as in Example 5, except that the contents of the polyketone and the master batch were adjusted as described in Table 1 below. Each was prepared.

[Examples 11 and 12]

A master batch in which 50% by weight of a silicone compound was dispersed in 50% by weight of acrylate was used, and the contents of the polyketone and the master batch were adjusted as described in Table 1 below. Were prepared respectively.

[Examples 13 to 16]

A master batch in which 50% by weight of a silicone compound was dispersed in 50% by weight of low-density polyethylene was used, and the contents of the polyketone and the master batch were adjusted as described in Table 1 below. Were prepared respectively.

[Comparative Examples 1 to 4]

The polymer or composition described in Table 1 below is manufactured into pellets on an extruder using a twin screw screw with a diameter of 40 cm operating at 250 rpm and L/D = 32, and then injection-molded to a specimen of a cosmetic container pump. (Rod type within 10mm in diameter and within 30mm in length) was prepared respectively.

[Experimental Example]

(1) Surface tension evaluation

For each of the specimens prepared in Examples and Comparative Examples, a contact angle with water and an aqueous solution of 50 vol% ethanol were measured, and the results are shown in Table 1 below.

(2) Evaluation of yellowness and color difference

The yellow index and color difference dE of the specimen were measured using a color difference meter (manufactured by Datacolor). The color difference can be calculated as follows using the L, a, and b values of the CIE LAB system.

ingredient ISO bending specimen (contact angle, °) water Ethanol 50 vol% Example 1 POK 99% by weight Si MB 1% by weight 72.0 45.2 Example 2 98% by weight of POK Si MB 2% by weight 76.2 45.4 Example 3 97% by weight of POK Si MB 3% by weight 71.2 45.4 Example 4 POK 96% by weight Si MB 4% by weight 73.0 43.6 Example 5 POK 99.5% by weight Si MB 0.5% by weight 71.9 43.0 Example 6 POK 99% by weight Si MB 1% by weight 71.6 48.3 Example 7 98% by weight of POK Si MB 2% by weight 68.9 45.9 Example 8 POK 96% by weight Si MB 4% by weight 72.5 48.6 Example 9 97% by weight of POK Si MB 3% by weight 71.1 48.4 Example 10 POK 96% by weight Si MB 4% by weight 72.5 45.8 Example 11 98% by weight of POK Si MB 2% by weight 74.0 47.5 Example 12 POK 96% by weight Si MB 4% by weight 72.0 44.0 Example 13 POK 99% by weight Si MB 1% by weight 73.2 40.3 Example 14 98% by weight of POK Si MB 2% by weight 71.1 45.8 Example 15 97% by weight of POK Si MB 3% by weight 71.3 53.3 Example 16 POK 96% by weight Si MB 4% by weight 73.3 54.4 Comparative Example 1 100% by weight of POK 62.8 36.8 Comparative Example 2 97% by weight of POK 3% by weight of talc 63.6 30.4 Comparative Example 3 100% by weight of POM 79.5 49.7 Comparative Example 4 LDPE 100% by weight 88.7 48.5

ingredient YI dE Example 2 98% by weight of POK Si MB 2% by weight 14.85 1.38 Example 4 POK 96% by weight Si MB 4% by weight 16.63 2.89 Example 7 98% by weight of POK Si MB 2% by weight 30.49 6.25 Example 8 POK 96% by weight Si MB 4% by weight 42.72 11.05 Example 11 98% by weight of POK Si MB 2% by weight 16.30 1.88 Example 12 POK 96% by weight Si MB 4% by weight 17.53 3.99 Example 14 98% by weight of POK Si MB 2% by weight 19.82 1.34 Example 16 POK 96% by weight Si MB 4% by weight 22.66 8.05 Comparative Example 1 100% by weight of POK 9.73 6.18 Comparative Example 3 100% by weight of POM -12.62 15.11 Comparative Example 4 LDPE 100% by weight 88.7 48.5

Referring to Table 1, a pump for a cosmetic container using a polyketone composition prepared according to the Example was shown to have a similar contact angle under water and high ethanol content compared to polyoxymethylene, which is a conventional pump material, and a pump using only polyketone ( It can be seen that the surface tension is improved compared to Comparative Example 1). In addition, the polyketone composition prepared according to the Examples showed a larger contact angle compared to the composition (Comparative Example 2) containing polyketone and talc.

In addition, when described with reference to Table 2, it can be seen that the color difference is also small in the examples compared to the comparative examples, and in particular, when 2% by weight of the silicone master batch is added while using polyamide or low density polyethylene as the carrier resin of the silicone master batch In addition, it can be seen that it is superior in terms of color difference. On the other hand, in the case of low-density polyethylene compared to polyamide, it would be preferable to use low-density polyethylene when demanding the same effect as it is excellent in terms of price competitiveness.

For this reason, as a result of testing the pump for a cosmetic container manufactured according to the Examples, it was confirmed that the pump operates normally even in the cosmetic container contents, especially the contents liquid with a high ethanol content.

Therefore, the polyketone composition of the present invention can be environmentally and easily applied to a cosmetic container pump regardless of the composition of the liquid due to the improved surface tension along with the formaldehyde-free properties, abrasion resistance, and chemical resistance of the polyketone itself.

Although the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art or those of ordinary skill in the art will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be understood that various modifications and changes can be made to the present invention within the scope of the invention.

Therefore, the technical scope of the present invention should not be limited to the content described in the detailed description of the specification, but should be determined by the claims.

Claims (5)

95.0 to 99.5% by weight of a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; And
An eco-friendly pump for cosmetic containers manufactured by injection molding a polyketone composition containing 0.5 to 5.0% by weight of a silicone master batch. The method of claim 1,
The silicone master batch is an eco-friendly pump for a cosmetic container comprising 40 to 60% by weight of a silicone compound and 40 to 60% by weight of a carrier resin. The method of claim 2,
The silicone-based compound is one kind selected from the group consisting of ultra-high molecular weight siloxane-based compounds, polydimethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane. Eco-friendly pump for cosmetic containers. The method of claim 2,
The carrier resin is one kind selected from the group consisting of polyamide, acrylate and polyethylene eco-friendly pump for cosmetic containers. The method of claim 1,
The specimen of the cosmetic container pump is an eco-friendly pump for cosmetic containers having a contact angle of 68 to 77° with water and a contact angle of 0 to 55° with an aqueous solution of ethanol 50 vol%.

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