KR101678616B1 - Composition for manufacturing radiation cross-linking thermoplastic high heat resistance olefin elastomer foam and manufacturing method for radiation cross-linking thermoplastic high heat resistance olefin elastomer foam using the same - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a composition for producing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material and an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material using the composition. More particularly, A composition for producing a thermoplastic high-temperature olefinic composite elastomer foamed material which is crosslinked by an electron beam irradiation method using propylene and a propylene-ethylene copolymer as a base resin, and an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material ≪ / RTI >

Electron beam crosslinking, high heat resistance, composite elastomer, homopolypropylene, foam

Description

TECHNICAL FIELD The present invention relates to a composition for producing an electron beam cross-linked thermoplastic high-temperature olefinic composite elastomer foamed material, and an electron beam cross-linked thermoplastic high-temperature olefinic composite elastomer foamed material using the same. for radiation cross-linking thermoplastic high heat resistance olefin elastomer foam using the same}

TECHNICAL FIELD The present invention relates to a composition for producing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material and an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material using the composition. More particularly, A composition for producing a thermoplastic high-temperature olefinic composite elastomer foamed material which is crosslinked by an electron beam irradiation method using propylene and a propylene-ethylene copolymer as a base resin, and an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material ≪ / RTI >

Generally, polyolefin-based resins such as polypropylene (PP) and polyethylene (PE) are representative general-purpose resins, and are environmentally friendly materials having extremely excellent physical properties such as low density, high strength and high heat resistance as well as being recyclable. In addition, it is widely used as a material suitable for various fields ranging from household goods to industrial parts, and it is a plastic material with the greatest growth prediction in the future. However, there are disadvantages such as low temperature impact resistance and paintability due to relatively high glass transition temperature, high crystallinity, inherent non-polarity, etc., and overcoming the above problems, Introduction of rubber phase, FRP, and the like.

A thermoplastic olefin elastomer (hereinafter also abbreviated as TPO) has various properties including the flexibility of a thermosetting rubber at room temperature, such as phase separation, and has a processability similar to that of thermoplastics, It is a polymer blend resin that has been attracting attention as a substitute for existing rubber products or impact resistant reinforcing materials. The hard segment of the commercialized thermoplastic olefinic composite elastomer is composed of a polyolefin resin having a high hardness such as PP and PE. The soft segment includes olefinic elastomers such as EPDM, EPR, EVA, ethylene octene copolymer and ethylene butene copolymer In recent years, attempts have been made to develop thermoplastic olefinic composite elastomer resins having various compositions depending on required physical properties such as blending with NBR, butyl rubber, natural rubber and the like.

As described above, in order to prepare a foaming foam material by selecting an appropriate material with an electron beam crosslinking thermoplastic olefinic composite elastomer resin and then blending it, and then performing an extrusion and foaming process, a blend of a compatibilizer and a compound A composition containing an additional component such as a foaming agent for foaming an elastic body and a crosslinking agent for efficiently proceeding the crosslinking process according to an appropriately selected method.

In particular, an olefinic composite elastomer foamed material is manufactured using random polypropylene among the polyolefin resins as the hard segment. The random polypropylene is used by lowering the stereoregularity of the polymer by adding a small amount of ethylene in the polymerization of polypropylene.

When the foaming material is produced by increasing the content of the random polypropylene of the polyolefin-based resin as the base resin in the production of the foamed foam material using the thermoplastic olefin-based composite elastomer composition, the heating dimensional change rate (heating at 140 DEG C for 1 hour) And the shrinkage rate decreases. However, as the content of the elastomer decreases, the emulsion quality such as flexibility tends to deteriorate, resulting in a problem that the properties are difficult to satisfy the requirements of customers.

Accordingly, it is possible to improve the physical properties of the thermoplastic olefin-based composite elastomer foamed product that is finally produced through various improvements in the composition and content of the composition to be initially prepared, The present invention has been made based on this technical background.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a composition for producing an electron beam crosslinked thermoplastic olefinic composite elastomer foamed material, Heat resistance, recyclability, environment friendliness, formability, flexibility and sensitivity quality as well as reduction of the shrinkage ratio by suggesting the optimum conditions required in the process of manufacturing the electron beam crosslinked thermoplastic high heat resistant olefin The present invention provides a composition for producing a composite elastomer foamed foam material and an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed foam material using the same.

In order to attain the above object, the composition for producing the electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed foam of the present invention comprises a base resin, a compatibilizing agent, a foaming agent and a crosslinking agent, Wherein the compatibilizer is a polyolefin composite elastomer made of homopolypropylene which is 80% by weight of a polyolefin resin (hard segment) and a propylene-ethylene copolymer which is 20 to 90% by weight of an elastomer (soft segment) Styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer, graphitized ethylene propylene rubber, and functional (meth) acrylate rubber, which are contained in an amount of 5 to 20 parts by weight, Polymer, and the foaming agent is at least one selected from the group consisting of the basic water Or an inorganic foaming agent group composed of ammonium hydrogencarbonate, sodium hydrogencarbonate and sodium borohydride, or a material selected from the group consisting of azodicarbonamide, dinitrosopentamethylene Wherein the cross-linking agent is selected from the group consisting of tetramine, benzene sulfonyl hydrazide, toluene sulfonyl hydrazide, and toluene sulfonyl semicarbazide, Is contained in an amount of 5.0 parts by weight, and is characterized by being any one of organic peroxide, unsaturated resin crosslinking agent and polyurethane crosslinking agent.

Preferably, the propylene-ethylene copolymer comprised as the base resin is made to have the properties of a plastomer and an elastomer by the catalyst of Ziegler Natta or Metalloecene.

The homopolypropylene as the base resin preferably has a melt index of 0.5 to 40 g / 10 min and a melting point of 150 to 170 캜.

The propylene-ethylene copolymer used as the base resin preferably has a melt index (230 占 폚, 2.16 kg) of 2.0 to 25.0 g / 10 min, a density of 0.850 to 0.888 g / cm3, a softening point of 29 to 101 占 폚 .

Preferably, the functional polymer selected as the compatibilizing agent is selected from the group consisting of polypropylene having maleic anhydride incorporated therein, ethylene ethyl acrylate having maleic anhydride incorporated therein, ethylene vinyl acetate having maleic anhydride incorporated therein, Butadiene styrene, polystyrene copolymerized with maleic anhydride, polyethylene containing maleic anhydride, and ethylene ethyl acetate with maleic anhydride incorporated therein.

Preferably, the organic peroxide selected as the crosslinking agent is selected from the group consisting of hydroperoxides, dialkyl-aryl peroxides (dicumyl peroxide), diacyl peroxides, peroxyketals, peroxyesters, peroxycarbonates, It is one of the selected materials.

Preferably, the unsaturated resin crosslinking agent selected as the crosslinking agent is any one selected from a vinyl monomer, an acrylic compound, a methacrylic compound and an epoxy compound.

Preferably, at least one of an antioxidant and a heat stabilizer may be further added to the composition for preparing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed foam, The thermosetting agent is contained in an amount of 0.2 to 5.0 parts by weight based on 100 parts by weight of the base resin. The thermosetting agent is contained in an amount of 2.0 to 5.0 parts by weight and is selected from the group consisting of phenol, amino, phosphorus and sulfur And a heat stabilizer group selected from the group consisting of Cd / Ba / Zn based, Cd / Ba based, Ba / Zn based, Ca / Zn based, Na / Zn based, Sn based, Pb based, to be.

According to another aspect of the present invention, there is provided a method for manufacturing a thermoplastic high-temperature olefinic composite elastomer foam material, which comprises the steps of: (S10) mixing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foam material Preparing a composition for manufacturing; (S20) extruding a master batch and a base resin prepared by mixing a foaming agent and an additive in the prepared composition with an extruder; (S30) irradiating an accelerated electron beam to the extruded product to crosslink the result; And (S40) foaming the cross-linked resultant.

Preferably, the twin extruder is used for the extrusion of step (S20), the temperature of the twin extruder cylinder is maintained at 140 to 210 DEG C, and the temperature of the screw at the end of the twin extruder is maintained at 50 to 120 DEG C do.

Preferably, the crosslinking step of (S30) proceeds so that the accelerated electron beam is irradiated with a voltage of 300 to 900 kV and an electron dose of 1.0 to 5.0 Mrad.

Preferably, the foaming step of (S40) is a horizontal foaming method in which a foaming furnace is horizontally installed, a vertical foaming method in which a foaming furnace is vertically installed, and a foaming method in which a liquid foaming agent is used as a heat transfer medium Go ahead.

When the product is prepared by using the composition for preparing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed foam material according to the present invention, it is possible to manufacture an environmentally friendly product with improved physical properties, and the appearance characteristics and various mechanical properties Crosslinked thermoplastic high-heat-resistant olefinic composite elastomer foamed foam material capable of improving the heat resistance and the heat resistance.

Currently, TPO foam materials can be divided into two fields: automotive materials, general goods, and electronic materials. The field of automobile interior materials is the field that is most interested in TPO foam materials in Korea and abroad. The interior parts of a car are largely divided into a pat-type (soft type) and a non pad type (hard type). Non-pad type is hard surface parts, such as instrument panel, door trim, console box, and garnish. However, modern people who desire emotion tend to prefer parts which are better in terms of visual and touch than hard feeling. Therefore, a pad type is used for a door trim, an instrument panel, a head liner, and a side pillar. At this time, the material used for the pad type has a structure of three layers (skin / foam / core) unlike the material used for the non-pad type. The currently applied structure is not easily recycled in the form of PVC skin / PU foam / ABS core, and PVC is a material expected to be regulated as environmentally harmful substance. Therefore, research is actively underway to replace the existing structure with TPO skin / TPO foam / PP core, and it is applied to some models.

In addition, studies are underway to apply general merchandise and electronic materials, and the areas that are expected to be applied soonest are tapes and non-slip mats. In the case of tapes, a typical target product is Norton Tape, which is currently being imported and applied to the construction market. The expansion ratio is low, has excellent flexibility as compared with hardness, and is used as a spacer for maintaining the shape of a silicone sealant. These tapes must have good adhesion and good shape retention. Currently, other companies are trying to replace them with polyurethane and PVC foam, but they are still in an insufficient stage. In addition, by applying non-slip properties to TPO foam, it can be applied to various fields such as general household mat, mouse pad, and packing material of electronic products. Particularly, Poron foam, which is used as a sealing material for electronic products, is currently being imported and used all over the world. However, researches to replace such imported products have been actively conducted in Korea, but the present situation is insufficient. The market for this type of foil foam also has the advantage of providing the sealing characteristic of the TPO foam and also the possibility of market exploration.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

The base resin is preferably a polyolefin composite elastomer composed of a polyolefin-based resin containing 10 to 80% by weight and an elastomer of 20 to 90% by weight.

The polyolefin-based resin blended with the base resin is composed of a hard segment, and the elastomer blended with the base resin is composed of a soft segment. The mechanical properties of the product change depending on the content of the hard segment and the content of the soft segment constituting the base resin. Particularly, as the content of the polyolefin resin constituting the hard segment is increased, heat resistance and mechanical properties are improved, and extrusion and foaming workability are improved. On the other hand, flexibility in producing a thermoplastic olefin-based composite elastomer foam by electron beam crosslinking So that the performance as an elastic body may be deteriorated. Therefore, attention should be paid to its content control. In other words, with respect to the content of the polyolefin resin constituting the hard segment, the heat resistance, mechanical properties and workability are lowered when the lower limit is exceeded, and when exceeding the upper limit, flexibility for use as an elastic material is lowered. In addition, with respect to the numerical range of the content of the elastomer constituting the soft segment, if it is below the lower limit, flexibility for use as an elastic material can not be ensured. If the upper limit is exceeded, heat resistance, mechanical properties and workability are deteriorated Which is undesirable.

In the composition for producing an electron beam cross-linked thermoplastic high-temperature olefinic composite elastomer foamed material, the polyolefin-based resin (hard segment) included as the base resin is preferably homo polypropylene, and the electron-crosslinked thermoplastic high- In the composition for preparing an elastic foam foamed material, the elastomer contained as the base resin is preferably a propylene-ethylene copolymer. Here, the propylene-ethylene copolymer is made to have properties of a plastic polymer and an elastomer by means of a Ziegler Natta or metallocene catalyst.

On the other hand, it is preferable that the homopolypropylene as the base resin has a melt index of 0.5 to 40 g / 10 min and a melting point of 150 to 170 ° C. At this time, with respect to the numerical value range of the homopolypropylene, if the melt index falls short of the lower limit of the melt index, the extrusion flowability is not smooth, so that the extrusion process is degraded in the extruder and the extrusion processability is lowered. The extrusion flowability is excellent but the constant thickness of the extrusion sheet can not be maintained smoothly and the workability is deteriorated, which is not preferable. If it is lower than the lower limit of the melting point, the heat resistance and the mechanical properties are lowered. If the upper limit of the melting point is exceeded, the extrusion and foaming workability are lowered, which is not preferable.

The propylene-ethylene copolymer used as the base resin preferably has a melt index (230 占 폚, 2.16 kg) of 2.0 to 25.0 g / 10 min, a density of 0.850 to 0.888 g / cm3, a softening point of 29 to 101 占 폚 . At this time, with respect to the numerical value range of the physical properties of the propylene-ethylene copolymer, when it is less than the lower limit of the melt index, the mechanical properties are excellent, while the extrusion and foaming processability is deteriorated. When the upper limit of the melt index is exceeded, Which is not preferable due to deterioration of extrusion processability. If the density is below the lower limit, the mechanical properties and flexibility are excellent, while the extrusion and foaming workability is deteriorated. If the density is above the upper limit, mechanical properties and flexibility are deteriorated. If the lower limit of the softening point is below the lower limit, the heat resistance is lowered. If the upper limit of the softening point is exceeded, the flexibility is not ensured.

The compatibilizing agent is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the base resin, and includes a styrene-ethylene-butylene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-acrylonitrile copolymer , Graphitized ethylene propylene rubber (EPDM), and a functionalized polymer. At this time, with respect to the numerical range of the content of the compatibilizer, if it is below the lower limit, there is no influence on the binding force generated at the interface between the hard segment and the soft segment constituting the base resin, It is difficult to ensure the physical properties of the product. If the upper limit is exceeded, the bonding force generated at the interface between the hard segment and the soft segment constituting the base resin is excessively influenced, There is no increase and the cost is increased only because the cost is increased, which is not preferable.

On the other hand, the functional polymer selected and used as the compatibilizing agent is polypropylene-grafted-maleic anhydride (also referred to as PP-g-MAH) into which maleic anhydride is introduced, ethylene ethyl acrylate (Ethylene-acrylate-grafted-maleic anhydride, also referred to as 'EEA-MAH'), maleic anhydride-introduced ethylene vinyl acetate Maleic anhydride (also referred to as SEBS-g-MAH), maleic anhydride-grafted polystyrene (PS (polystyrene)) copolymerized with maleic anhydride, maleic anhydride-modified styrene ethylene butadiene styrene- (maleic anhydride), PE (polyethylene) -GMA (grafted maleic anhydride), and maleic anhydride-introduced ethylene ethyl acetate EEA (GMA) (grafted malei c anhydride)].

The foaming agent is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin and is a group of an inorganic foaming agent composed of ammonium bicarbonate, sodium bicarbonate and sodium borohydrate Any one of the selected substances or one or more of azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), benzenesulfonylhydrazide, toluenesulfonylhydrazide (TSH) and toluenesulfonylsemicarbazide (PTSS ) Is preferable as the organic foaming agent. At this time, with respect to the numerical range with respect to the content of the foaming agent, if the foaming agent is below the lower limit value, foaming required is not sufficiently performed. If the foaming agent is above the upper limit value, foaming becomes excessive, Which is undesirable.

The crosslinking agent contained in the composition for preparing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material is contained in an amount of 0.2 to 5.0 parts by weight based on 100 parts by weight of the base resin, and is selected from among organic peroxides, unsaturated resin crosslinking agents and polyurethane crosslinking agents Any one of them is preferable. The crosslinking agent is a component added to maintain an optimum resin viscosity at the time of foaming. At this time, with respect to the numerical range with respect to the content of the crosslinking agent, if it is below the lower limit value or exceeds the upper limit value, it is not preferable because the optimum resin viscosity can not be secured at the time of foaming. On the other hand, the organic peroxide selected and used as the crosslinking agent is selected from the group consisting of hydroperoxides, dialkyl-aryl peroxides (dicumyl peroxide), diacyl peroxides, peroxyketals, peroxyesters, peroxycarbonates and ketone peroxides And the unsaturated resin crosslinking agent selected and used as the crosslinking agent is preferably any one selected from a vinyl monomer, an acrylic compound, a methacrylic compound and an epoxy compound.

Meanwhile, at least one or more of an antioxidant and a heat stabilizer may be further added to the electron beam crosslinked thermoplastic high-temperature-resistant olefinic composite elastomer foam composition.

The antioxidant is preferably contained in an amount of 0.2 to 2.0 parts by weight based on 100 parts by weight of the base resin. At this time, with respect to the numerical range with respect to the content of the antioxidant, if it is below the lower limit, the processability upon extrusion and foaming is lowered. If the upper limit is exceeded, economical efficiency is lowered due to addition of more than necessary, Which is undesirable.

The heat stabilizer is preferably contained in an amount of 0.2 to 5.0 parts by weight based on 100 parts by weight of the base resin. At this time, with respect to the numerical range with respect to the content of the heat stabilizer, if it is below the lower limit value, the processability at the time of extrusion and foaming is lowered and the resin is decomposed to deteriorate the physical properties. If the upper limit is exceeded, And the mechanical properties of the product may be deteriorated as well as being undesirable.

Hereinafter, a method for manufacturing the electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foam will be described with reference to the accompanying drawings. 1 is a flowchart illustrating a process for producing a thermoplastic high-temperature olefinic composite elastomer foam according to the present invention.

1, it can be seen that the process proceeds through the following four steps (S10 to S40). First, a composition for preparing the electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foam is prepared (Step S10). Thereafter, the master batch prepared by mixing the foaming agent and the additive in the composition prepared in the step S10 and the base resin are fed into an extruder to be extruded (step S20). Then, an accelerated electron beam is irradiated to the extrudate of the step (S20) and cross-linked (S30). Finally, the crosslinked product of step S30 is foamed (step S40).

With respect to the composition prepared in the step (S10), the composition of the composition for preparing the thermoplastic high-temperature olefinic composite elastomer foam is prepared (step S10). In this case, the master composition is prepared by mixing the foaming agent and the additives before the entire composition is mixed and before the extruder is introduced in the subsequent step (Step S20), and the other resin components, i.e., the homopolypropylene and the propylene- The coalescence is put into the extruder together with the master batch. This is to maximize the kneadability of the manufactured composition by separately injecting the master batch of the foaming agent and the additive and the base resin in the extrusion step (S20).

With respect to the extruder used in the extrusion step (S20), a conventional single extruder is used to produce a thermoplastic high-temperature olefinic composite elastomer foam composition containing the blowing agent according to the present invention, Since the extrusion is not sufficiently performed, it is preferable to use a twin extruder in the present invention. On the other hand, the twin extruder can use both a counter-rotation type and a co-rotation type. However, when the twin extruder of the latter type is used, more preferable extrusion performance can be secured . That is, in the extrusion step (S20), as described above, the master batch prepared by mixing the foaming agent and the additive and the base resin are fed through the inlet of the extruder while the extrusion process is carried out to maximize the kneadability of the composition, It is possible to solve the problem that the foaming performance is lowered.

The temperature of the twin extruder cylinder is preferably maintained at 140 to 210 ° C. Regarding the numerical range with respect to the temperature of the twin extruder cylinder, when the lower limit value is exceeded, the supplied composition is not properly kneaded, If the upper limit is exceeded, the foaming agent may be decomposed and the foam performance may be deteriorated.

The number of kneading blocks in the screw inside the twin extruder cylinder should be controlled to about 10 to 40%. If the kneading block is below the lower limit of the numerical value range, the kneading property of the resin composition is lowered, If the amount exceeds the above range, foaming performance of the foaming agent deteriorates, which is undesirable.

The temperature of the twin extruder screw is preferably maintained at 50 to 120 ° C. Regarding the numerical value range, if the lower limit value is exceeded, the resin composition is rapidly solidified and molding of the mother sheet is difficult, If the upper limit value is exceeded, the composition containing the foaming agent can be decomposed at a high temperature, and the subsequent foaming step (step S40) can not be effectively performed. As a result, Resulting in defective product performance. Thus, a cooling system capable of lowering the temperature of the screw of the twin extruder to an appropriate range can be introduced, thereby solving the problems of productivity and yield reduction.

The cross-linking method adopted in the cross-linking step (S30) adopted in the method for producing the electron beam cross-linking thermoplastic high-temperature olefinic composite elastomer foam is a cross-linking method through electron beam irradiation, which is eco-friendly as compared with the conventional chemical cross- And the process stability can be ensured. The crosslinking step of (S30) is preferably carried out such that the accelerated electron beam is irradiated at a voltage of 300 to 900 kV and an electron dose of 1.0 to 5.0 Mrad, and the control of the crosslinking voltage is preferably performed through the extrusion step (S20) The crosslinking electron dose is preferably adjusted according to the density and physical properties of the blowing agent previously injected.

With respect to the numerical range with respect to the crosslinking voltage, when the lower limit is not reached, crosslinking is not performed to a sufficient depth with respect to the extrudate obtained in the step (S20). If the upper limit is exceeded, Cross-linking reaction occurs at the overlapping part, which causes a serious problem in foaming, and of course, it is also undesirable because it is economically disadvantageous. With respect to the numerical range with respect to the crosslinked electron dose, when the lower limit is not reached, sufficient crosslinking is not performed with respect to the extrudate obtained in the step (S20), and a problem arises in the subsequent foaming step (S40) , The crosslinking reaction reaches a supersaturated state due to excessive crosslinking electron dose, which causes a serious problem in foaming and, at the same time, the economical efficiency is also undesirable.

In the crosslinking method using electron beam irradiation conducted under the conditions as described above, accelerated electron beams are irradiated to the extruded sheet, which is the result of the step S20, which is an object of crosslinking, so that hydrogen contained in the olefin resin contained in the extruded sheet Whereby radicals are produced in the olefin-based resin. The radicals thus produced have high reactivity and are characterized in that crosslinking reaction is induced in the olefin resin.

In the method for producing the electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foam foam, the foaming step of (S40) comprises a horizontal foaming method in which a foaming furnace is horizontally installed, a vertical foaming method in which a foaming furnace is vertically installed, It is preferable to proceed by any one method selected from the method of spraying the sulphate using a liquid-phase sulphate.

At this time, all of the three foaming methods are performed at normal pressure, and are classified according to the method of installing the foaming furnace and the heat transfer medium. In the first horizontal foaming method, the foaming furnace is installed horizontally so that the foams are produced horizontally at the time of foaming, and all processes proceed horizontally. Such a horizontal foaming method is advantageous in that the physical properties in the longitudinal direction and the width direction are small because the expansion ratio in the longitudinal direction is small at the time of foaming since there is little influence by the gravity in the arrangement and the process progress of the foaming furnace. The second vertical foaming method is a method in which foaming furnaces are vertically installed and foamed while lowering the mother sheet. Such a vertical foaming method is advantageous in appearance because it is foamed in air at the time of foaming, and the deviation in the width direction is small. In the third method, the liquid phase sulphate is used as a heat transfer medium. In the third method, the liquid phase sulphate is used. However, unlike the vertical firing method, the air is not used as a heat transfer material, The heat transfer effect is excellent and the foaming can be performed uniformly on the sheet. Especially, since the physical property deviation in the longitudinal direction and the width direction is very small as compared with the foam product produced by the above-described horizontal or vertical foaming method, And the characteristic is evaluated excellent.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

For example, in Examples (1-2) and Comparative Examples (1) and (2), taking into consideration the composition of each composition, the type of extruder used, the adoption of the screw cooling system of the extruder, the crosslinking method, (1-2).

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polyolefin series (% by weight) 30 60 30 60 Elastomer (% by weight) 70 40 70 40 Compatibilizer 10 5 10 5 blowing agent 5 5 5 5 stabilizator 0.3 0.3 0.3 0.3 Extruder type Twin Twin Twin Twin Cooling system apply apply apply apply Crosslinking method Electron beam Electron beam Electron beam Electron beam Foaming method Perpendicular Perpendicular Perpendicular Perpendicular

Example

In Table 1, the polyolefin resin used homopolypropylene as the hard segment constituting the base resin, and the elastomer used the propylene-ethylene copolymer as the soft segment constituting the base resin, and the compatibilizer was a polyethylene resin , ADCA was used as the foaming agent, acrylic compound was used as the crosslinking agent, and tetrakis (methylene) methane was used as the stabilizer. Regarding the type of the extruder, a twin type extruder of the reverse rotation type was used as the twin. In the context of the cooling system, the application is indicated as having a cooling system capable of lowering the temperature of the extruder screw. As the crosslinking method, an electron beam method was used, and the electron dose was 3 Mrad. With respect to the foaming method, a vertical foaming method was adopted.

Comparative Example

As the polyolefin resin, random polypropylene copolymerized with ethylene and propylene, which is a polypropylene resin having a higher ethylene content than the polyolefin resin of the embodiment, was used as a hard segment constituting the base resin, A plastomer, which is a propylene-ethylene copolymer, was used as a soft segment constituting the resin. At this time, the compatibilizing agent, the foaming agent, the crosslinking agent and the stabilizer were carried out under the same conditions and the same conditions as those of the examples.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Extrudability Good Good Good Good Foaming Great Great Good Good productivity Great Great Great Great flexibility
(Compression hardness: kgf / cm2) 0.9 1.2 0.7 1.05 Density (kg / m3) 67 67 67 67 Heat resistance
(% Change in heating dimension) Longitudinal direction: -12.0
Width direction: -2.5 Longitudinal direction: -7.1
Width direction: -0.8 Longitudinal direction: -42.1
Width direction: -28.4 Longitudinal direction: -35.1
Width direction: -12.6

※ Evaluation level: Excellent> Good> Average> Poor

As can be seen from the above Table 2, the extrudability, foamability and productivity of the examples and comparative examples according to the present invention are not less than good, and thus no problems are caused by using them in existing processes. However, in order to measure flexibility and heat resistance in Table 2, the compression hardness was measured and compared at the time of 25% extrusion. In order to measure the thermal resistance, the amount of change of the foam after being left at 140 ° C for 1 hour was measured. The KS M 3014 measurement method was applied to these measurements. In the case of Comparative Examples 1 and 2, the heating dimension change was -42.1 to -35.1% in the longitudinal direction of the foam foam, -28.4 to -12.6% in the width direction of the foam foam, and the compression hardness was 0.7 to 1.05 kgf / Respectively. On the other hand, in the case of Examples 1 and 2, the heating dimension change was -12.0 to -7.1% in the longitudinal direction of the foam foam, -2.5 to -0.8% in the width direction of the foam foam, 1.2kgf / cm < 2 > In other words, it can be seen that the examples show better heat resistance and flexibility than the comparative examples.

As a result, homopolypropylene and soft polyolefin composite elastomers having a high molecular structure with excellent stereoregularity and high melting temperature can satisfy the heat resistance, flexibility and sensitivity quality. That is, it can be used as a material for an automobile interior material in accordance with molding conditions of a high temperature and a molding condition of an automobile interior material requiring a complicated design.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood that various modifications and changes may be made without departing from the scope of the appended claims.

1 is a flow chart for explaining a process for producing an electron beam crosslinked thermoplastic high-temperature-resistant olefinic composite elastomer foam material according to the present invention.

Claims (12)

A composition for producing an electron beam crosslinked thermoplastic high-temperature-resistant olefinic composite elastomer foamed foam material comprising a base resin, a compatibilizing agent, a foaming agent and a crosslinking agent, The base resin is a polyolefin composite elastomer composed of a homopolypropylene having 30 to 60 wt% of a polyolefin resin (hard segment) and a propylene-ethylene copolymer of 40 to 70 wt% of an elastomer (soft segment) The compatibilizing agent is contained in an amount of 5 to 10 parts by weight based on 100 parts by weight of the base resin. The compatibilizing agent is selected from the group consisting of styrene-ethylene-butylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-acrylonitrile copolymer , Graphitized ethylene-propylene rubber, and functional polymer, The foaming agent is contained in an amount of 5 parts by weight based on 100 parts by weight of the base resin and is any one selected from the group consisting of ammonium hydrogen carbonate, sodium hydrogencarbonate and sodium borohydride, or azodicarbonamide, di An organic blowing agent group composed of nitroso pentamethylene tetramine, benzene sulfonyl hydrazide, toluene sulfonyl hydrazide and toluene sulfonyl semicarbazide, The crosslinking agent is contained in an amount of 0.2 to 5.0 parts by weight based on 100 parts by weight of the base resin, and is any one selected from organic peroxides, unsaturated resin crosslinking agents and polyurethane crosslinking agents, The homopolypropylene has a melt index (230 占 폚, 2.16 kg) of 0.5 to 40 g / 10 min, a melting point of 150 to 170 占 폚, Wherein the propylene-ethylene copolymer has a melt index (230 占 폚, 2.16 kg) of 2.0 to 25.0 g / 10 min, a density of 0.850 to 0.888 g / cm3, and a softening point of 29 to 101 占 폚. (EN) COMPOSITION FOR THE PREPARATION OF FOAMED FOAM MATERIALS. The method according to claim 1, The propylene-ethylene copolymer, which is contained in the base resin, A composition for manufacturing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed foam material, characterized by being made to have properties of a plastomer and an elastomer by a Ziegler Natta or metallocene catalyst. delete delete The method according to claim 1, The functional polymer selected as the compatibilizing agent may be, Polypropylene with maleic anhydride incorporated therein, ethylene ethyl acrylate with maleic anhydride incorporated, ethylene vinyl acetate with maleic anhydride incorporated, styrene ethylene butadiene styrene with maleic anhydride incorporated, polystyrene copolymerized with maleic anhydride, A polyethylene having an acid anhydride introduced thereinto, and ethylene ethyl acetate having maleic anhydride introduced therein. 11. The composition for the production of an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foamed material according to claim 1, The method according to claim 1, The organic peroxide selected as the cross- Wherein the electron beam cross-linking agent is any one selected from the group consisting of peroxides, hydroperoxides, dialkyl-aryl peroxides (dicumyl peroxide), diacyl peroxides, peroxyketals, peroxyesters, peroxycarbonates and ketone peroxides Composition for producing thermoplastic high - temperature olefinic composite elastomer foamed foam material. The method according to claim 1, Wherein the unsaturated resin crosslinking agent selected as the crosslinking agent is any one selected from the group consisting of a vinyl monomer, an acrylic compound, a methacrylic compound and an epoxy compound, and a composition for manufacturing the foamed foam material of an electron beam crosslinked thermoplastic high heat resistant olefinic composite elastomer. The method according to claim 1, At least one or more of an antioxidant and a heat stabilizer may further be added to the electron beam crosslinked thermoplastic high-temperature-resistant olefinic composite elastomer foam composition. The antioxidant is contained in an amount of 0.2 to 2.0 parts by weight based on 100 parts by weight of the base resin and is selected from the group consisting of phenol, amino, phosphorus, and sulfur, The heat stabilizer is contained in an amount of 0.2-5.0 parts by weight based on 100 parts by weight of the base resin. The heat stabilizer is contained in an amount of 0.2-5.0 parts by weight based on 100 parts by weight of the base resin, and is composed of Cd / Ba / Zn, Cd / Ba, Ba / Zn, Ca / Zn, Based thermoplastic high-heat-resistant olefinic composite elastomer foamed material, wherein the thermoplastic elastomer is one selected from the group consisting of a thermosetting resin, a thermoplastic resin, a Pb-based resin, a Cd-based resin and a Zn-based thermosetting resin. A method for producing an electron beam crosslinked thermoplastic high-temperature-resistant olefinic composite elastomer foam foam material, (S10) preparing a composition according to any one of claims 1, 2 and 5 to 8; (S20) extruding a master batch and a base resin prepared by mixing a foaming agent and an additive in the prepared composition with an extruder; (S30) irradiating an accelerated electron beam to the extruded product to crosslink the result; And (S40); and foaming the resultant crosslinked product. The method of manufacturing an electron beam crosslinked thermoplastic high-temperature olefinic composite elastomer foam material according to claim 1, 10. The method of claim 9, The twin extruder is used for the extrusion of the twin extruder (S20). The temperature of the twin extruder cylinder is maintained at 140 to 210 DEG C, and the temperature of the screw at the end of the twin extruder is maintained at 50 to 120 DEG C Based crosslinked thermoplastic high-heat-resistant olefinic composite elastomer foaming foam material. 10. The method of claim 9, Wherein the step (S30) is carried out such that accelerated electron beams are irradiated at a voltage of 300 to 900 kV and an electron dose of 1.0 to 5.0 Mrad, so that the electron beam cross-linking thermoplastic high-temperature-resistant olefinic composite elastomer foam material is produced. 10. The method of claim 9, The foaming step of (S40) may be carried out by any one of a horizontal foaming method in which a foaming furnace is installed horizontally, a vertical foaming method in which a foaming furnace is vertically installed, and a foaming method in which a liquid foaming agent is used as a heat transfer medium Wherein said crosslinked thermoplastic high-heat-resistant olefinic composite elastomer foaming foam material is a crosslinked thermoplastic elastomer.

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