(19)
(11)EP 1 709 110 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
18.03.2020 Bulletin 2020/12

(21)Application number: 04706883.8

(22)Date of filing:  30.01.2004
(51)Int. Cl.: 
C08J 9/16  (2006.01)
(86)International application number:
PCT/KR2004/000182
(87)International publication number:
WO 2005/073301 (11.08.2005 Gazette  2005/32)

(54)

EXPANDED POLYSTYRENE BEAD HAVING FUNCTIONAL SKIN LAYER, MANUFACTURING PROCESS THEREOF, AND FUNCTIONAL EPS PRODUCT AND MANUFACTURING PROCESS THEREOF USING THE SAME

EXPANDIERTES POLYSTYROLKÜGELCHEN MIT FUNKTIONELLER DECKSCHICHT, HERSTELLUNGSVERFAHREN DAFÜR UND FUNKTIONELLES EPS-PRODUKT UND HERSTELLUNGSVERFAHREN DAVON DAMIT

PERLE DE POLYSTYRENE EXPANSE A PEAU FONCTIONNELLE, PROCEDE DE FABRICATION CORRESPONDANT, ET PRODUIT EN POLYSTYRENE EXPANSE FONCTIONNEL AINSI QUE PROCEDE DE FABRICATION CORRESPONDANT


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

(43)Date of publication of application:
11.10.2006 Bulletin 2006/41

(73)Proprietor: Synbra Propor B.V.
4871 NM Etten-Leur (NL)

(72)Inventor:
  • Park, Bong-Kuk
    Gyeongsan-Si, Gyeongbuk 712-190 (KR)

(74)Representative: Algemeen Octrooi- en Merkenbureau B.V. 
P.O. Box 645
5600 AP Eindhoven
5600 AP Eindhoven (NL)


(56)References cited: : 
WO-A2-91/14724
JP-A- 55 029 533
US-A- 5 786 398
JP-A- 1 264 979
US-A- 3 428 579
US-B1- 6 384 094
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to expanded polystyrene molded products having various functions, including flame-retardation, antibacterial properties, coloration properties, etc. More particularly, the present invention relates to (pre-) expanded polystyrene particles having a functional skin layer produced by coating the surface of (pre-) expanded polystyrene particles with a functional coating composition, a process for producing the expanded polystyrene particles, functional expanded polystyrene molded products manufactured using the expanded polystyrene particles with a functional skin layer, and a process for manufacturing the polystyrene molded products.

    Background Art



    [0002] Expanded polystyrene is a polymer resin obtained by heating and curing the expandable polystyrene resin including expanding agent, such as pentane (C5H12) or butane (C4H10) in polystyrene resin or its copolymer resins, to generate foams therein. Expanded polystyrene is white in color, light in weight, and is superior in water resistance, thermal insulation properties, sound absorption and buffering properties. Due to these advantages, expanded polystyrene resin is widely used as a packaging material, a construction material, a material for floats, life jackets, decorative articles, insulators, living products, such as food containers and disposable products, and the like.

    [0003] More detailed explanation regarding a molding process of expanded polystyrene products will be described below. A polystyrene or styrene copolymer resin containing an expanding agent in the shape of a bead having a diameter 0.2∼0.3 mm or a pellet having a length of about 2.5 mm is pre-expanded to produce expanded particles (usually in the forms of beads). Thereafter, the expanded particles are aged and dried. The aged expanded particles are placed in a mold, heated with a high-pressure steam, and thus molded into a desired shape.

    [0004] The expanded polystyrene thus produced contains 98 vol% of air and only about 2 vol% of the polymer resin. Further, the expanded polystyrene has a unique expanded structure in which air is enclosed by plastic foams. Based on this structure, since the expanded polystyrene is lightweight and shows superior buffering properties, thermal insulation properties, and sound absorption, it can be widely utilized in many applications.

    [0005] However, since the expanded structure makes the expanded polystyrene more susceptible to some chemicals than the chemical resistance inherent to the polystyrene resin, the expanded structure is an obstacle in imparting a variety of functions upon the expanded polystyrene particles.

    [0006] That is, the addition of functional components to expanded polystyrenes in order to impart additional functions to expanded polystyrene products presents difficulties that water resistance and heat resistance of the functional components, and moldability and chemical resistance of the expanded polystyrene must be comprehensively taken into account. Accordingly, functional expanded polystyrene molded products hitherto developed are very limited in the selection of the amount and kind of functional components within the range that does not affect physical and chemical properties during preparation of polystyrene.

    [0007] Particularly, since expanded polystyrenes have relatively low melting point, and the molten polystyrene has low viscosity, molded products made of expanded polystyrene lose their structure and are melted easily by fire, thus being converted to a combustible liquid material. Under these circumstances, regulations including the Fire Services Act, in most developed countries, restrict the use of expanded polystyrenes, which prohibits the development of the expanded polystyrenes as construction materials.

    [0008] In order to solve these problems, great efforts have been devoted to developing flame-retardant or fire-resistant expanded polystyrenes. For example, U.S. Patent No. 6,384,094 discloses a process for preparing a fire-resistant expandable polystyrene by adding 112 wt% of an expandable graphite or an expanded graphite to a suspension containing a styrene monomer. In addition, the patent publication proves the usefulness of the expandable polystyrene thus prepared.

    [0009] However, the expandable graphite begins to expand at about 900°C, whereas the polystyrene leaves 3 wt% of ash behind at 500°C or above because of its extremely low heat resistance. The expandable graphite is expanded upon high-temperature heating to perform its thermal insulation, but the graphite loses its structure due to the absence of a material capable of binding the graphite, resulting in poor fire resistance.

    [0010] On the other hand, Korean Utility Model No. 323680 describes a flame-retardant expanded polystyrene panel manufactured by coating an aqueous sodium silicate solution on the surface of an expanded polystyrene particle, and irradiating microwaves to the coating to heat-bond the sodium silicate to the polystyrene. This technology has disadvantages in that the coating of the sodium silicate is poor in water resistance and expensive equipment is required for the microwave irradiation.

    [0011] Furthermore, US patent No. 3 428 579 describes compositions comprising expanded polystyrene particles coated with an aqueous dispersion comprising a vinyl or vinylidene polymer such as a polyvinyl acetate polymer. The coated expanded particles are prepared by first preparing polystyrene particles comprising an expanding agent followed by coating the particles with an aqueous dispersion comprising the coating agent such as polyvinyl acetate. The coated particles are then expanded. The resulting expanded and coated polystryrene beads are used for the manufacture of molded articles.

    [0012] GB patent No. 1 602 381 is directed to insulating material having flame retardant properties comprising particles of expanded polystyrene dispersed into a binder consisting of a synthetic polymer latex and an organic bromine-containing compound wherein the synthetic polymer latex is a vinylacetate copolymer and the bromine-containing compound as functional additive is used as flame retardant additive.

    [0013] Finally, US patent No. 5 286 756 describes a process for the preparation of expandable styrene polymer beads being coated with a mixture comprising a bisamide compound from alkylene diamine and an aliphatic carboxylic acid with an antistatic agent as functional additive. The expanded polystyrene particles are prepared by coating polystyrene particles comprising an expanding agent. The coated particles are then expanded.

    Disclosure of the Invention



    [0014] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide an expanded polystyrene that can be produced using conventional molding equipment without the need for additional expensive equipment and developed into various functional products superior in flame retardation, fire resistance, antibacterial properties, waterproofness, aromatic properties, coloration properties, etc.

    [0015] The object of the present invention can be achieved by coating the surface of expanded polystyrene particles with a functional coating composition to form a functional skin layer inside the particles, followed by molding. The functional coating composition used herein contains at least one functional additive, and a polyvinyl acetate resin with high affinity to the expanded polystyrene particles and low-temperature melt bonding property so as to be suitable for steam molding.

    [0016] In accordance with one aspect of the present invention, there are provided expanded polystyrene particles with a functional skin layer consisting of:
    an inner pre-expanded polystyrene layer; and the functional skin layer containing 10∼99 wt% of a vinyl acetate based polymer and 0.1∼90 wt% of at least one functional additive, wherein the functional skin layer is formed by coating the surface of the inner pre-expanded polystyrene layer with a coating composition comprising a vinyl acetate based polymer solution and at least one functional additive, and drying the coated surface to separate the expanded polystyrene particle into individual particle. The expanded polystyrene particles having a functional skin layer are spherical particles having a skin-core structure wherein the overall diameter of the expanded polystyrene particles is between about 1 mm and about 30 mm, the diameter of the expanded polystyrene particles constituting the inner core layer is between about 0.999 mm and about 29.999 mm, and the thickness of the outer skin layer is between about 1 µm and about 100 µm.

    [0017] In accordance with another aspect of the present invention, there is provided a process for producing the expanded polystyrene particles with a functional skin layer, comprising the steps of:

    heating and pre-expanding expandable polystyrene beads or pellets to produce pre-expanded polystyrene particles;

    applying a functional coating composition to the surface of the above pre-expanded polystyrene particles, the functional coating composition being prepared by mixing or dissolving at least one functional additive with a vinyl acetate based polymer solution to form a functional skin layer; and

    adding a release agent to the pre-expanded polystyrene particles whose surface is coated with the functional coating composition, to separate the expanded polystyrene particles having the functional skin layer into individual particles, and drying the separated particles.



    [0018] In accordance with another aspect of the present invention, there is provided a process for manufacturing the functional expanded polystyrene molded product comprising the steps of introducing the expanded polystyrene particles having a functional skin layer into a molder, and applying high-pressure steam to the molder to bond the expanded polystyrene particles with each other.

    [0019] In accordance with yet another aspect of the present invention, there is provided a functional expanded polystyrene molded product made of the expanded polystyrene particles with functional skin layer according to the present invention.

    [0020] A more detailed explanation concerning the structure of the expanded polystyrene particles having a functional skin layer according to the present invention will be given below. The expanded polystyrene particles constituting the core layer account for 5-99 wt%, the functional skin layer accounts for 1-95 wt%, and other residues account for 5 wt% or less, based on the total weight of the expanded polystyrene particles.

    [0021] The expanded polystyrene particles constituting the core layer include those previously known in the art. The components and production processes are as explained in the above prior art.

    [0022] On the other hand, the functional skin layer is formed by coating the surface of expanded polystyrene particles with a functional coating composition containing a vinyl acetate based polymer solution and at least one functional additive, followed by separating (to individual particles) and drying. The vinyl acetate based polymer solution is prepared by dissolving 3∼80 wt% of a vinyl acetate based polymer in a solvent. The vinyl acetate based polymer can be a vinyl acetate homopolymer, or a copolymer of vinyl acetate and at least one monomer selected from: vinyl esters, such as vinyl caproate and vinyl stearate; acrylic esters, such as ethyl acrylate, butyl acrylate and octyl acrylate; fumaric acid esters, such as dibutyl maleate; carboxylic acids, such as maleic acid, acrylic acids and itaconic acid; vinyl alcohols; butadienes; and caprolactones; or a mixture or a blend thereof. The vinyl acetate based polymer has a degree of polymerization (DP) of 10-100,000. It is preferred that the content of the vinyl acetate monomer in the vinyl acetate based polymer is 55% or more.

    [0023] Examples of suitable solvents to prepare the vinyl acetate based polymer solution include water, and organic solvents such as alcohols, esters, ketones, carboxylic acids, aromatics, and halogenated hydrocarbons. It is preferred to select a solvent having relatively high volatility and reduced human toxicity, particularly, minimally dissolving or eroding the surface of expanded polystyrene particles. In this respect, alcohols are preferred. The concentration of the resin component is determined within the range defined above, taking into account the adhesion to the surface of the expanded polystyrene particles and workability upon handling.

    [0024] The functional additive can be added for intended functions without particular limitations so long as it is readily dissolved or dispersed in the vinyl acetate based polymer solution and does not erode or dissolve the surface of the expanded polystyrene particles. Examples of such additives include expanding agents, nucleating agents, lubricants, antioxidants, heat stabilizers, ultraviolet stabilizers, biostabilizers, fillers, reinforcing agents, plasticizers, colorants, impact-resistant agents, flame retardants, antistatic agents, cross-linking agents, fluorescent whitening agents, thermal conductivity-imparting agents, electrical conductivity-imparting agents, permeability modifiers, magnetism-imparting agents, surfactants, stabilizers, excipients, drugs, solvents, hardeners, desiccants, fortifying agents, flavoring agents, antibacterial agents, etc. These additives may be added alone or in combination as a mixture of two or more agents compatible with each other.

    [0025] In particular, when a flame retardant, such as antimony trioxide, a phosphoric compound, boron, boric acid or aluminum oxide, is added, a kind of fire wall surrounding the surface of the expanded polystyrene particles is built, which prevents the spread of a fire to sites not directly reached by the flame and maintains the overall shape of the skin layer acting as a skeleton unchanged, leading to a very effective flame-retardant expanded polystyrene product.

    [0026] The vinyl acetate based polymer solution containing the functional additive is uniformly applied to the surface of the expanded polystyrene particles. At this step, if the viscosity of the polymer solution is low, it is advantageous to stir the expanded polystyrene particles while the polymer solution is sprayed on the surface of the particles. Meanwhile, if the polymer solution is highly viscous, the expanded polystyrene particles can be mixed with the polymer solution in a mixer with stirring to apply the polymer solution to the surface of the particles.

    [0027] The application of the vinyl acetate based polymer solution containing the functional additive to the expanded polystyrene particles may cause the polystyrene particles to be agglomerated due to the viscosity of the polymer solution, which makes it difficult to manufacture a molded product from the expanded polystyrene particles. Therefore preferably, the polymer solution is uniformly applied to the surface of the expanded polystyrene particles, followed by the steps of separating and drying, to produce the final expanded polystyrene particles having the functional skin layer.

    [0028] As the release agent used for separating, there may be used a liquid material or a solid powder different from the solvent used to prepare the vinyl acetate based polymer solution. When the solid powder is used, the moldability of the expanded polystyrene particles is degraded and dust is created during drying. When the liquid material is too lipophilic, it is more compatible with the polystyrene than with the vinyl acetate based polymer, causing the separation of the polystyrene from vinyl acetate based polymer. Accordingly, the use of excessively lipophilic liquid materials should be avoided. Thus, preferred release agent should be more or less hydrophilic liquid type material such that it can be uniformly applied to the exterior surface of the vinyl acetate based polymer, and should remain until the solvent of the polymer solution is appropriately removed such that it can. Examples of suitable release agents include, but are not limited to, hydrophilic liquid materials, such as water, ethylene glycol and glycerin, containing two or more hydroxyl groups (-OH) in their molecular structure, and silicone oils. These release agents can be used alone or as a mixture of two or more thereof. The release agent is used in an amount of 1-40 wt% of the vinyl acetate based polymer. The amount of the release agent used is properly selected depending on the surface area of the expanded polystyrene particles and the kind of the functional coating composition constituting the skin layer.

    [0029] After the release agent is uniformly added, the mixture is dried with stirring to separate the expanded polystyrene particles into individual particles. Drying is carried out in hot air at 100°C or lower with stirring. Alternatively, the drying may be carried out in a drier at 100°C or lower with stirring, or may be carried out under reduced pressure. For better workability, a combination of vacuum drying and heating is most effective.

    [0030] The functional skin layer thus formed contains 10∼99 wt% of the vinyl acetate based polymer, 0.1-90 wt% of the functional additive, and 20 wt% or less of residues of the solvent and the release agent. The content of the functional additives is greatly dependent on functions to be imparted. For example, flame-retardants, reinforcing agents and fillers are added in large amounts, but colorants can attain desired effects using only small amounts. Within the range defined above, the vinyl acetate based polymer can serve as a matrix capable of forming the skin layer.

    [0031] The expanded polystyrene particles having the functional skin layer are stored in a silo before use. For use, the expanded polystyrene particles are taken out of the silo, placed in a mold having a desired shape, and molded using high-pressure steam to manufacture a functional expanded polystyrene molded product. This molding may be performed in accordance with the same procedure as conventional molding processes of expanded polystyrenes.

    Brief Description the Drawings



    [0032] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

    Fig. 1 is an electron micrograph (30x) showing a cutaway portion of the surface of an expanded polystyrene particle (C1) having a flame-retardant skin layer produced in Example 1 of the present invention;

    Fig. 2 is an electron micrograph (400 x) showing an interface between a skin layer and a core layer of the cutaway portion shown in Fig. 1;

    Fig. 3 is a photograph showing the initial state of a sample for a flame-retardation test, produced in Example 1 of the present invention;

    Figs. 4 and 5 are front and side photographs taken after the flame-retardation test for the sample shown in Fig. 3, respectively;

    Fig. 6 is a photograph showing the results of an antibacterial performance test for an expanded polystyrene molded product manufactured in Example 2 of the present invention; and

    Fig. 7 is an enlarged photograph showing the cross section of an aesthetic expanded polystyrene molded product manufactured in Example 3 of the present invention.


    Best Mode for Carrying Out the Invention



    [0033] The present invention will now be described in more detail with reference to the following several examples of the manufacture of functional expanded polystyrene molded products.

    Example 1: Manufacture of flame-retardant expanded polystyrene molded product


    A. Preparation of flame-retardant polyvinyl acetate solution (A1)



    [0034] 450g of a polyvinyl acetate resin having a degree of polymerization of 500 was uniformly dissolved in 550g of methanol to prepare 1 kg of polyvinyl acetate solution. To the polymer solution was added 1 kg of aluminum hydroxide particles having an average particle size of 7.5 µm. The resulting mixture was uniformly dispersed to prepare 2 kg of a methanolic polyvinyl acetate solution (A1) containing the flame-retardant additive.

    B. Coating on expanded polystyrene particles



    [0035] Expandable polystyrene particles were expanded to an average of 80 fold, and dried. 2 kg of the expanded polystyrene particles were charged into a 200-liter ribbon mixer. 2 kg of the flame-retardant polyvinyl acetate polymer solution (A1) prepared in step A was added to the expanded polystyrene particles with stirring at 50 rpm for one minute to uniformly coat the expanded particles, yielding 4 kg of expanded polystyrene particles whose surface was coated with the flame-retardant polyvinyl acetate polymer solution.

    C. Drying, separating, and production of expanded polystyrene particles having flame-retardant skin layer



    [0036] Stirring was continued for about 10 seconds while applying hot air at 60°C to the ribbon mixer. Then, 50g of ethylene glycol were sprayed with stirring to allow the expanded polystyrene particles coated with the flame-retardant polyvinyl acetate polymer solution to separate into individual particles. The separated particles were dried with stirring for 3 minutes to produce expanded polystyrene particles (C1) having a flame-retardant skin layer.

    D. Production of flame-retardant expanded polystyrene molded product



    [0037] The expanded polystyrene particles (C1) having a flame-retardant skin layer produced in step C were put in a steam molder for EPS, heated at a steam pressure of 0.6 kg/cm3 for 50 seconds, sustained for 10 seconds, and cooled to manufacture a flame-retardant expanded polystyrene molded product (D1) having a density of 35 kg/m3.

    E. Observation of skin-core structure



    [0038] For observation of the skin-core structure of the expanded polystyrene particles having a flame-retardant skin layer produced in step C, one particle (C1) of the expanded polystyrene particles was selected. A portion of the surface of the particle (C1) was cut, and then the cutaway portion was observed under an electron microscope with a magnification of 30x (see Fig. 1). This observation reveals that the expanded polystyrene particle (C1) produced in this example is a spherical particle having an expanded structure completely coated with the flame-retardant skin layer.

    [0039] A higher magnification (400 x) of the interface between the skin layer and the core layer of the expanded polystyrene particle (C1) is shown in Fig. 2. As shown in Fig. 2, the skin layer was completely adhered to the inner expanded polystyrene layer.

    F. Flame-retardation test



    [0040] The flame-retardant expanded polystyrene molded product D1 manufactured in step D was cut into a plate-shaped sample having dimensions of 2 cm (1) x 2 cm (w) x 1 cm (h) (see Fig. 3), which was used for the flame-retardation test.

    [0041] The sample was exposed to a 4 cm high flame from a Bunsen burner for 30 seconds to conduct a flame-retardation test, and the obtained results are shown in Figs. 4 and 5.

    [0042] As shown in Figs. 4 and 5, only a portion of the expanded polystyrene particles exposed to the surface were collapsed by heating, but heat and flame were blocked by means of the skin layer and the skeleton of the molded product (D1) was maintained, confirming that the original structure of the molded product (D1) was unchanged.

    Example 2: Manufacture of antibacterial expanded polystyrene molded product


    A. Preparation of antibacterial polyvinyl acetate solution



    [0043] 450g of a polyvinyl acetate resin having a degree of polymerization of 500 was uniformly dissolved in 550g of methanol to prepare 1 kg of a polyvinyl acetate solution, and then 0.2 kg of ethyl paraben was added thereto. The resulting mixture was completely dissolved with stirring for one hour to prepare 1.2 kg of a methanolic polyvinyl acetate solution (A2) containing the antibacterial additive.

    B. Coating on expanded polystyrene particles



    [0044] 2.5 kg of expanded polystyrene particles coated with the antibacterial polyvinyl acetate solution were produced in the same manner as in Example 1 (B), except that 0.5 kg of the antibacterial polyvinyl acetate solution (A2) prepared in step A was added instead of the flame-retardant polyvinyl acetate solution (A1).

    C. Drying, separating, and preparation of expanded polystyrene particles having antibacterial skin layer



    [0045] Drying and separating were carried out in the same manner as in Example 1 to produce expanded polystyrene particles (C2) having an antibacterial skin layer.

    D. Manufacture of antibacterial expanded polystyrene molded product



    [0046] The expanded polystyrene particles (C2) having an antibacterial skin layer produced in step C were charged into a steam molder for EPS, heated at a steam pressure of 0.6 kg/cm3 for 40 seconds, sustained for 10 seconds, and cooled to manufacture an antibacterial expanded polystyrene molded product (D2) having a density of 15 kg/m3.

    E. Antibacterial performance Test



    [0047] A portion of the antibacterial expanded polystyrene molded product D2 manufactured in step D was ground. After 0.4g of the ground molded product and a test bacterial solution in which Staphylococcus aureus was incubated were subjected to shaking culture at a shaking frequency of 150 cycles per minute at 35°C for 24 hours, the number of the bacteria was counted and the bacterial decrease rate (bacteriostatic rate) was determined.

    [0048] After the shaking culture, the initial bacterial concentration (1.3 x 105 count/ml) of the test bacterial solution was decreased to 10 count/ml (Fig. 6).

    [0049] As apparent from the results shown in Fig 6, the antibacterial test performed by the shake-flask method confirms a bacterial decrease of 99.9% in the antibacterial expanded polystyrene molded product D2 produced in this example.

    Example 3: Manufacture of aesthetic expanded polystyrene molded product


    A. Preparation of colored polyvinyl acetate solution



    [0050] 25g of a polyvinyl acetate resin having a degree of polymerization of 500 was uniformly dissolved in 475g of methanol to prepare 0.5 kg of a polyvinyl acetate solution. 10g of a black pigment was added to the polymer solution, and was completely dissolved with stirring for one hour to prepare 0.51 kg of a methanolic black-colored polyvinyl acetate solution (A3).

    B. Coating on expanded polystyrene particles



    [0051] 2.51 kg of expanded polystyrene particles coated with the colored polyvinyl acetate polymer solution were prepared in the same manner as in Example 1 (B), except that 0.51 kg of the colored polyvinyl acetate polymer solution (A3) prepared in step A was added instead of the flame-retardant polyvinyl acetate solution (A1).

    C. Drying, separating, and production of expanded polystyrene particles having colored skin layer



    [0052] Expanded polystyrene particles (C3) having a black skin layer were produced in the same manner as in Example 1 (C), except that 250g of water was used instead of ethylene glycol.

    D. Manufacture of aesthetic expanded polystyrene molded product



    [0053] The expanded polystyrene particles (C3) having a black skin layer produced in step C were charged into a steam molder for EPS, heated at a steam pressure of 0.6 kg/cm3 for 40 seconds, sustained for 10 seconds, and cooled to manufacture an aesthetic expanded polystyrene molded product (D3) having a density of 15 kg/m3.

    E. Observation of cross section of aesthetic expanded polystyrene molded product



    [0054] The surface of the expanded polystyrene molded product D3 manufactured in step D was wholly black-colored. A 5 cm deep piece was cut from the expanded polystyrene molded product D3, and then the cross section of the piece was observed under a microscope. The photograph is shown in Fig. 7.

    [0055] As apparent from the photograph, the cross section of the expanded polystyrene molded product (D3) had a slightly irregular shape similar to a honeycomb wherein the black-colored skin layer was formed between the white expanded polystyrene particles.

    [0056] In the case of a commercial block molding product manufactured by cutting the block-shaped molded product to a desired thickness, the size and color of the expanded polystyrene particles, and the color of the skin layer are varied, making it possible to manufacture aesthetic expandable polystyrene panels exhibiting various color effects.

    Industrial Applicability



    [0057] As apparent from the above description, according to the expanded polystyrene particles of the present invention, inherent properties of expanded polystyrene, e.g., light weight, thermal insulation properties, shape stability, buffering properties and sound absorption, are ensured by the expanded polystyrene particles constituting the core layer, and at the same time, superior low-temperature bonding properties, air-tightness, waterproofness and durability are provided by the low-softening point vinyl acetate based polymer constituting the skin layer.

    [0058] In addition, superior adhesion of the vinyl acetate based resin to polystyrene, and relatively good low-temperature adhesion properties of the vinyl acetate based polymer enable improvement of the physical properties, e.g., compressive strength, tensile strength and flexural strength, of the molded products of the present invention. Optionally, various functional additives, including flame retardants, water repellents, antibacterial agents, colorants, flavoring agents, etc., can be added to the vinyl acetate based polymer to impart a variety of functions to the expanded polystyrene particles of the present invention in a simple manner. Therefore, the expanded polystyrene particles of the present invention can be applied to manufacture of lightweight industrial materials, particularly construction materials, with various functions.

    [0059] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope of the invention as disclosed in the accompanying claims.


    Claims

    1. An expanded polystyrene particle with a functional skin layer comprising: an inner expanded polystyrene layer; and a functional skin layer, wherein the inner expanded polystyrene layer is formed by heating and expanding an expandable polystyrene bead or pellet, and the functional skin layer is formed by coating the surface of the inner expanded polystyrene layer with a functional coating composition having 10 to 99 wt % of a vinyl acetate based polymer and 0.1 to 90 wt % of at least one functional additive, wherein the overall diameter of the expanded polystyrene particles is between 1 mm and 30 mm, the diameter of the expanded polystyrene particles constituting the inner core layer is between 0.999 mm and 29.999 mm, and the thickness of the outer skin layer is between 1 micrometer and about 100 micrometer.
     
    2. The expanded polystyrene particle with functional skin layer according to claim 1, wherein the vinyl acetate based polymer is a vinyl acetate homopolymer, or a copolymer of vinyl acetate and at least one monomer selected from: vinyl esters, such as vinyl caproate and vinyl stearate; acrylic esters, such as ethyl acrylate, butyl acrylate and octyl acrylate; fumaric acid esters, such as dibutyl maleate; carboxylic acids, such as maleic acid, acrylic acids and itaconic acid; vinyl alcohols; butadienes; and caprolactones; or a mixture or a blend thereof, and has a degree of polymerization (DP) of 10-100,000.
     
    3. The expanded polystyrene particle with functional skin layer according to claim 1, wherein the functional skin layer has a thickness corresponding to 0.003-10% of the overall diameter of the particle, and makes up 1-95 wt% based on the total weight of the particle.
     
    4. The expanded polystyrene particle according to claim 1, wherein the functional additive is selected from expanding agents, nucleating agents, lubricants, antioxidants, heat stabilizers, ultraviolet stabilizers, biostabilizers, fillers, reinforcing agents, plasticizers, colorants, impact-resistant agents, flame retardants, antistatic agents, crosslinking agents, fluorescent whitening agents, thermal conductivity-imparting agents, electrical conductivity-imparting agents, permeability modifiers, magnetism-imparting agents, surfactants, stabilizers, excipients, drugs, solvents, hardeners, desiccants, fortifying agents, flavoring agents, antibacterial agents, and mixtures thereof.
     
    5. A functional expanded polystyrene molded product manufactured by steam-heated expanding molding of the expanded polystyrene particle with functional skin layer according to any one of claims 1 to 4.
     
    6. A process for producing expanded polystyrene particles with functional skin layer, comprising the steps of:

    heating and pre-expanding expandable polystyrene beads or pellets to produce pre-expanded polystyrene particles;

    applying a functional coating composition to the surface of the above pre-expanded polystyrene particles, the functional coating composition being prepared by mixing or dissolving at least one functional additive with a vinyl acetate based polymer solution to form a functional skin layer; and

    adding a release agent to the pre-expanded polystyrene particles whose surface is coated with the functional coating composition, to separate the expanded polystyrene particles having the functional skin layer into individual particles, and drying the separated particles.


     
    7. The process according to claim 6, wherein the solvent used to prepare the vinyl acetate based polymer solution is water, or an organic solvent selected from alcohols, esters, ketones, carboxylic acids, aromatics, and halogenated hydrocarbons, or mixtures thereof.
     
    8. The process according to claim 6, wherein the vinyl acetate based polymer solution contains 3-80 wt% of a vinyl acetate based polymer.
     
    9. The process according to claim 6, wherein the release agent is selected from hydrophilic liquid materials containing two or more hydroxyl groups (-OH) in their molecular structure, such as water, ethylene glycol and glycerin, and silicone oils, and mixtures thereof.
     


    Ansprüche

    1. Expandiertes Polystyrolpartikel mit einer funktionellen Hautschicht, umfassend eine innere expandierte Polystyrolschicht und eine funktionelle Hautschicht, wobei die innere expandierte Polystyrolschicht durch Erhitzen und Expandieren eines expandierbaren Polystyrolkügelchens oder -pellets gebildet wird und die funktionelle Hautschicht durch Beschichten der Oberfläche der inneren expandierten Polystyrolschicht mit einer funktionellen Beschichtungszusammensetzung gebildet wird, die 10 bis 99 Gew.-% eines Polymers auf Vinylacetatbasis und 0,1 bis 90 Gew.-% von mindestens einem funktionellen Additiv aufweist, wobei der Gesamtdurchmesser der expandierten Polystyrolpartikel zwischen 1 mm und 30 mm liegt, der Durchmesser der expandierten Polystyrolpartikel, die die innere Kernschicht bilden, zwischen 0,999 mm und 29,999 mm liegt und die Dicke der äußeren Hautschicht zwischen 1 Mikrometer und etwa 100 Mikrometer liegt.
     
    2. Expandiertes Polystyrolpartikel mit funktioneller Hautschicht nach Anspruch 1, wobei das Polymer eines Polymerisationsgrads (PG) von 10 bis 100.000 auf Vinylacetatbasis ein Vinylacetathomopolymer oder ein Copolymer aus Vinylacetat und mindestens einem Monomer ist, ausgewählt aus Vinylestern, wie Vinylcaproat und Vinylstearat, Acrylestern, wie Ethylacrylat, Butylacrylat und Octylacrylat, Fumarsäureestern, wie Dibutylmaleat, Carbonsäuren, wie Maleinsäure, Acrylsäuren und Itaconsäure, Vinylalkoholen, Butadienen und Caprolactonen oder einem Gemisch oder einer Mischung davon.
     
    3. Expandiertes Polystyrolpartikel mit funktioneller Hautschicht nach Anspruch 1, wobei die funktionelle Hautschicht eine Dicke hat, die 0,003 ∼ 10 % des Gesamtdurchmessers des Partikels entspricht und 1 ∼95 Gew.-%, bezogen auf das Gesamtgewicht des Partikels, ausmacht.
     
    4. Expandiertes Polystyrolpartikel nach Anspruch 1, wobei das funktionelle Additiv ausgewählt ist aus Treibmitteln, Keimbildnern, Schmiermitteln, Antioxidationsmitteln, Wärmestabilisatoren, UV-Stabilisatoren, Biostabilisatoren, Füllstoffen, Verstärkungsmitteln, Weichmachern, Farbstoffen, schlagfesten Mitteln, Flammschutzmitteln, antistatischen Mitteln, Vernetzungsmitteln, optischen Aufhellungsmitteln, Wärmeleitfähigkeit verleihenden Mitteln, elektrische Leitfähigkeit verleihenden Mitteln, Permeabilitätsmodifikatoren, Magnetismus verleihenden Mitteln, Tensiden, Stabilisatoren, Hilfsstoffen, Arzneimitteln, Lösungsmitteln, Härtern, Trockenmitteln, Stärkungsmitteln, Aromastoffen, antibakteriellen Mitteln und deren Gemischen.
     
    5. Funktionelles Formprodukt aus expandiertem Polystyrol, das durch dampferhitztes Expansionsformen des expandierten Polystyrolpartikels mit funktioneller Hautschicht nach einem der Ansprüche 1 bis 4 hergestellt ist.
     
    6. Verfahren zum Produzieren von expandierten Polystyrolpartikeln mit funktioneller Hautschicht, umfassend die folgenden Schritte:

    Erhitzen und Vorexpandieren von expandierbaren Polystyrolkügelchen oder - pellets, um vorexpandierte Polystyrolpartikel zu produzieren,

    Aufbringen einer funktionellen Beschichtungszusammensetzung auf die Oberfläche der obigen vorexpandierten Polystyrolpartikel, wobei die funktionelle Beschichtungszusammensetzung durch Mischen oder Lösen von mindestens einem funktionellen Additiv mit einer Polymerlösung auf Vinylacetatbasis zur Bildung einer funktionellen Hautschicht hergestellt wird, und

    Zugeben eines Trennmittels zu den vorexpandierten Polystyrolpartikeln, deren Oberfläche mit der funktionellen Beschichtungszusammensetzung beschichtet ist, um die expandierten Polystyrolpartikel mit der funktionellen Hautschicht in einzelne Partikel zu trennen, und

    Trocknen der getrennten Partikel.


     
    7. Verfahren nach Anspruch 6, wobei das zur Herstellung der Polymerlösung auf Vinylacetatbasis verwendete Lösungsmittel Wasser oder ein organisches Lösungsmittel ist, das aus Alkoholen, Estern, Ketonen, Carbonsäuren, Aromaten und halogenierten Kohlenwasserstoffen oder deren Gemischen ausgewählt wird.
     
    8. Verfahren nach Anspruch 6, wobei die Polymerlösung auf Vinylacetatbasis 3 ∼ 80 Gew.-% eines Polymers auf Vinylacetatbasis enthält.
     
    9. Verfahren nach Anspruch 6, wobei das Trennmittel aus hydrophilen flüssigen Materialien, die zwei oder mehr Hydroxylgruppen (-OH) in ihrer Molekülstruktur enthalten, wie Wasser, Ethylenglykol und Glycerin, und Silikonölen und deren Gemischen ausgewählt wird.
     


    Revendications

    1. Particule de polystyrène expansé ayant une couche superficielle fonctionnelle comprenant : une couche de polystyrène expansé interne ; et une couche superficielle fonctionnelle, où la couche de polystyrène expansé interne est formée par chauffage et expansion d'une bille ou d'une pastille de polystyrène expansible, et la couche superficielle fonctionnelle est formée par revêtement de la surface de la couche de polystyrène expansé interne avec une composition de revêtement fonctionnelle ayant 10 à 99% en poids d'un polymère à base d'acétate de vinyle et 0,1 à 90% en poids d'au moins un additif fonctionnel, où le diamètre total des particules de polystyrène expansé est compris entre 1 mm et 30 mm, le diamètre des particules de polystyrène expansé constituant la couche de noyau interne est compris entre 0,999 mm et 29,999 mm, et l'épaisseur de la couche superficielle externe est comprise entre 1 micromètre et environ 100 micromètres.
     
    2. Particule de polystyrène expansé ayant la couche superficielle fonctionnelle selon la revendication 1, dans laquelle le polymère à base d'acétate de vinyle est un homopolymère d'acétate de vinyle, ou un copolymère d'acétate de vinyle et d'au moins un monomère choisi parmi : des esters de vinyle, tels que le caproate de vinyle et le stéarate de vinyle ; des esters acryliques, tels que l'acrylate d'éthyle, l'acrylate de butyle et l'acrylate d'octyle ; des esters d'acide fumarique, tels que le maléate de dibutyle ; des acides carboxyliques, tels que l'acide maléique, des acides acryliques et l'acide itaconique ; des alcools vinyliques ; des butadiènes ; et des caprolactones ; ou un mélange ou une combinaison de ceux-ci, et a un degré de polymérisation (DP) compris entre 10 et 100000.
     
    3. Particule de polystyrène expansé ayant la couche superficielle fonctionnelle selon la revendication 1, dans laquelle la couche superficielle fonctionnelle a une épaisseur correspondant à une valeur comprise entre 0,003 et 10% du diamètre total de la particule et représente 1-95% en poids par rapport au poids total de la particule.
     
    4. Particule de polystyrène expansé selon la revendication 1, dans laquelle l'additif fonctionnel est choisi parmi des agents d'expansion, des agents de nucléation, des lubrifiants, des antioxydants, des stabilisants thermiques, des stabilisants ultraviolets, des biostabilisants, des charges, des agents renforçants, des plastifiants, des colorants, des agents résistant aux chocs, des retardateurs de flammes, des agents antistatiques, des agents de réticulation, des agents de blanchiment fluorescents, des agents conférant une conductivité thermique, des agents conférant une conductivité électrique, des modificateurs de perméabilité, des agents conférant du magnétisme, des tensioactifs, des stabilisants, des excipients, des médicaments, des solvants, des durcisseurs, des déshydratants, des agents fortifiants, des agents aromatisants, des agents antibactériens et des mélanges de ceux-ci.
     
    5. Produit moulé en polystyrène expansé fonctionnel fabriqué par moulage par expansion chauffé à la vapeur de la particule de polystyrène expansé ayant la couche superficielle fonctionnelle selon l'une quelconque des revendications 1 à 4.
     
    6. Procédé de production de particules de polystyrène expansé ayant une couche superficielle fonctionnelle, comprenant les étapes consistant :

    à chauffer et à pré-expanser des billes ou des pastilles de polystyrène expansible pour produire des particules de polystyrène pré-expansé ;

    à appliquer une composition de revêtement fonctionnelle à la surface des particules de polystyrène pré-expansé précitées, la composition de revêtement fonctionnelle étant préparée par mélange ou dissolution d'au moins un additif fonctionnel avec une solution de polymère à base d'acétate de vinyle pour former une couche superficielle fonctionnelle ; et

    à ajouter un agent de démoulage aux particules de polystyrène pré-expansé dont la surface est revêtue de la composition de revêtement fonctionnelle, pour séparer les particules de polystyrène expansé ayant la couche superficielle fonctionnelle en particules individuelles, et à sécher les particules séparées.


     
    7. Procédé selon la revendication 6, dans lequel le solvant utilisé pour préparer la solution de polymère à base d'acétate de vinyle est de l'eau, ou un solvant organique choisi parmi des alcools, des esters, des cétones, des acides carboxyliques, des hydrocarbures aromatiques et des hydrocarbures halogénés ou des mélanges de ceux-ci.
     
    8. Procédé selon la revendication 6, dans lequel la solution de polymère à base d'acétate de vinyle contient 3 à 80% en poids d'un polymère à base d'acétate de vinyle.
     
    9. Procédé selon la revendication 6, dans lequel l'agent de démoulage est choisi parmi des matières liquides hydrophiles contenant deux groupes hydroxyle (-OH) ou plus dans leur structure moléculaire, telles que l'eau, l'éthylène glycol et la glycérine et des huiles de silicone et des mélanges de ceux-ci.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description