KR101865008B1 - Foam-agent master batch composition and foam-agent master batch - Google Patents
Foam-agent master batch composition and foam-agent master batch Download PDFInfo
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- KR101865008B1 KR101865008B1 KR1020170168506A KR20170168506A KR101865008B1 KR 101865008 B1 KR101865008 B1 KR 101865008B1 KR 1020170168506 A KR1020170168506 A KR 1020170168506A KR 20170168506 A KR20170168506 A KR 20170168506A KR 101865008 B1 KR101865008 B1 KR 101865008B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/484—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with two shafts provided with screws, e.g. one screw being shorter than the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/823—Temperature control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The blowing agent master batch composition according to the present invention comprises 5 to 15 parts by weight of a base resin; 75 parts by weight of a hydrolaid type foaming agent; And 10 to 15 parts by weight of an additive. The composition is based on an environmentally-friendly hydrogel base foaming agent and has high thermal stability, so that it has an excellent effect of low possibility of fire, uniformity of foamed cells and high concentration of environmentally friendly.
Description
The present invention relates to a blowing agent masterbatch composition and a foaming agent masterbatch which can be used in the extrusion / foaming of a resin, and more particularly to a foam masterbatch composition and a foaming agent masterbatch which have high thermal stability and are environmentally friendly and highly concentrated.
The master bach (MB) is a pellet-shaped product in which a powdery foaming agent is dispersed at a high concentration using a resin as a main raw material. The master batch (MB) is excellent in workability and dispersibility with resins and can improve work productivity .
Examples of the blowing agent used in the blowing agent master batch include azodicarbonamide (ADCA), 4,4'oxy bisbenzenesulfonyl hydrazide (hereinafter referred to as OBSH), N, N 'dinitrothane Chemical blowing agents such as silane tetramine (DPT) have been widely used (Japanese Patent Laid-Open Publication No. 2004-051871, Japanese Patent Laid-Open Publication No. 2004-323726, Korean Patent Laid-Open Publication No. 2010-0085451, 2002-0086346, etc.).
Of the above chemical foaming agents, ADCA is the most commonly used, and its characteristic is relatively high decomposition temperature, high amount of generated gas, low temperature of decomposition temperature due to the combined use of a foaming auxiliary, Coloring stain due to the color of the trichromatic color, ammonia odor in the gas composition, and contamination with sublimable substances.
On the other hand, OBSH is one of the hydrazide type foaming agents, and has a merit of being very environmentally friendly because it is a white crystalline powder and has very little colored contamination and little decomposition residue toxicity.
However, the hydrorazide blowing agent is disadvantageous in that the amount of generated gas is small, the dispersibility thereof is poor, the thermal stability is low, and the possibility of fire is great.
An object of the present invention is to provide a foam masterbatch composition and a foam masterbatch based on an environmentally-friendly hydrolyzable foaming agent, which have high thermal stability and are environmentally friendly and highly concentrated.
The blowing agent master batch composition according to the present invention comprises 5 to 15 parts by weight of a base resin; 65 to 80 parts by weight of a hydrorazide blowing agent; And 10 to 15 parts by weight of an additive.
The base resin may be selected from styrene-butadiene styrene terpolymer (SBS) and ethylene propylene diene rubber (EPDM).
In addition, the hydrolaid type blowing agent may be a mixture of 4,4'oxybisbenzenesulfohydrolazide (OBSH), p-toluenesulfonylhydrolid (TSH), benzenesulfonylhydrolid (BSH) And the like.
Further, the base resin is ethylene propylene diene rubber (EPDM).
Further, the hydrolage based blowing agent is characterized by being 4,4'oxybisbenzenesulfohydrazide (OBSH).
In addition, the hydrolage based blowing agent is characterized by containing 75 parts by weight of 4,4'oxybisbenzenesulfohydrolazide (OBSH).
Further, the additive is characterized by containing a lubricant and an oil.
Further, the lubricant is characterized by being a wax and pentaerythritol stearate (PETS).
According to another aspect of the present invention, the blowing agent master batch comprises 5 to 15 parts by weight of ethylene propylene diene rubber (EPDM), 75 parts by weight of 4,4'oxybisbenzene sulfohydrolazide (OBSH) Pentaerythritol stearate (PETS) and 10-15 parts by weight of an oil.
According to another aspect of the present invention, the blowing agent master batch comprises 5 to 15 parts by weight of ethylene propylene diene rubber (EPDM); 75 parts by weight of 4,4'oxybisbenzenesulfohydrolazide (OBSH); And 10 to 15 parts by weight of wax, pentaerythritol stearate (PETS) and oil are kneaded in a pressure kneader (S100); A step (S200) of extruding the kneaded material supplied from the pressurized kneader in a twin screw extruder into a sheet or banana-sized kneaded form; (S300) of forming a sheet or a banana-sized extrudate from a twin screw extruder in the form of pellets in a single screw extruder.
Further, in the kneading step (S100), the kneading temperature is maintained at 60 to 70 占 폚.
Further, the sheet or banana-sized extrudate having an elongated shape is continuously fed from a twin screw extruder to a single screw extruder.
The blowing agent master batch composition according to the present invention exhibits an excellent effect of high amount of generated gas, excellent dispersibility, particularly high thermal stability and environmentally friendly high concentration.
Further, the foaming agent master batch according to the present invention has excellent thermal stability, and has a low possibility of fire and uniform foaming cell because it is manufactured using a foam masterbatch composition having high heat stability and high environmental and high concentration.
Further, since the blowing agent master batch according to the present invention extrudes the extrudate in a sheet or banana-sized ladder shape and then continuously feeds the extrudate, the conventional method of introducing the lumpy mixture directly into the extruder, And can be very effective in removing the latent heat which may remain in the extrudate during mixing and kneading due to an increase in unit surface area exposed to the air.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart illustrating a method of making a blowing agent master batch using the foam master composition according to one embodiment of the present invention.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.
It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
In the present invention, the terms "comprising" or "having ", and the like, specify that the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
In the present invention, the term "weight portion" means the weight ratio between the components
In addition, in the present invention, the term "cell" means a microstructure expanded by foaming in a polymer.
The blowing agent master batch composition according to the present invention comprises 5 to 15 parts by weight of a base resin; 65 to 80 parts by weight of a hydrorazide blowing agent; And 10 to 15 parts by weight of an additive. Here, when the above-mentioned hydro-radical blowing agent is not used or its amount is too small, there is a fear that the expansion ratio of the foaming agent composition is lowered.
Preferably, the hydrolaid blowing agent may be used in an amount of 75 parts by weight. If the content of the foaming agent is less than 75 parts by weight, the foaming magnification ratio may be low. If the foaming agent content is more than 75 parts by weight, improvement of the foaming magnification ratio may be limited.
Examples of the resin component used in the present invention include styrene-butadiene styrene terpolymer (SBS), ethylene propylene diene rubber (EPDM), and the like.
In addition, the foaming agent added in the present invention causes an exothermic reaction in the foaming process, and if it is too much, decomposition of the foaming agent is stopped before the decomposition is over to stop the decomposition of the foaming agent. Should not affect the color of
The blowing agent is hydro large deugye -CONHNH 2, or -SO 2 NHNH 2 as a blowing agent having a functional group, examples of the type of blowing agent used in the present invention OBSH, p- toluenesulfonyl dihydro LH de (p-Toluenesulfonylhydrazide: hereinafter, TSH), Benzene sulfonylhydrazide (hereinafter referred to as BSH), and mixtures thereof, and most preferably OBSH can be used.
Particularly, it is preferable to use a hydrolairzer blowing agent used in the present invention having a decomposition temperature of 160 3 캜 and a gas volume of 95 5 ml / g.
It goes without saying that the additive may be added or added in accordance with the characteristics of the master batch of the foaming agent to be produced.
As the kind of the additive used in the present invention, a lubricant, oil, etc. may be used.
According to the present invention, the lubricant may be wax and pentaerythritol stearate (PETS).
The foam masterbatch composition of the present invention thus produced exhibits an excellent effect of high thermal stability and environmentally friendly high concentration.
Hereinafter, a method of producing a foam masterbatch using the above-described foam master composition according to an embodiment of the present invention will be described.
The master batch according to an embodiment of the present invention is manufactured by kneading a raw material (S100), a step of extruding into a sheet or banana-sized elongated shape (S20), and a step of forming into a pellet shape (S40).
The step (S100) of kneading the raw material is a step of mixing / kneading a base resin, a hydrazide type foaming agent, and an additive, preferably 5 to 15 parts by weight of ethylene propylene diene rubber (EPDM) 75 parts by weight of bisbenzene sulfohydrolazide (OBSH), 10 parts by weight of wax, pentaerythritol stearate (PETS) as a lubricant and 10-15 parts by weight of oil were put into a kneader to be softened or kneaded at a temperature In consideration of the decomposition temperature of the foaming agent, the mixture is kneaded and kneaded at a pressing force of 0.12 to 0.5 MPa within about 10 to 25 minutes at 160 ± 3 ° C., and the kneaded product is kneaded at a temperature within 20 ° C. It is preferable to aged for 12 hours or more. The number of revolutions of the main shaft of the kneader is about 120 rpm. At this time, the kneading temperature is preferably maintained at 60 to 70 占 폚.
The step (S200) of extruding the sheet or the banana-sized kneaded product into a kneaded shape is a step of extruding the kneaded material supplied from the pressing type kneader into a kneaded sheet or banana size shape using a conventional twin screw extruder, And is extruded into a sheet having a predetermined thickness and size.
The step (S300) of forming the pellet is a step of extruding a sheet fed from a twin screw extruder or an extrudate having a banana size and having an elongated shape into a pellet in a single screw extruder, wherein a pellet- . Here, the extrusion temperature is preferably kept within 80 DEG C in consideration of the crosslinking temperature.
Preferably, in step S300 of forming the pellet, the sheet or banana sized extrudate in the form of stripes is fed continuously from a twin screw extruder to a single screw extruder.
Since the extrudate is extruded into a sheet or banana-sized ladder shape and then continuously supplied, cooling can be performed in combination with the conventional method in which the lumpy mixture is directly introduced into the extruder , It is very effective in removing the latent heat which may remain in the extrudate in the processes of mixing and kneading by increasing the unit surface area exposed to the air.
Hereinafter, the physical properties of the foam masterbatch prepared according to one embodiment of the present invention will be described by way of examples.
≪ Example 1 >
5 to 15 parts by weight of EPDM as a base resin and 75 parts by weight of OBSH as a blowing agent of hydrolaid are added to a pressurized kneader to raise the temperature to the softening point or the melting point and 10 to 15 parts by weight of a foaming regulator, In consideration of the decomposition temperature of the foaming agent, the mixture is kneaded at a pressing force of 0.12 to 0.5 MPa within about 10 to 25 minutes at 160 占 폚 and aged for 12 hours or more at a temperature within 20 占 폚 to stabilize the heat history of the raw material, The kneaded material fed from the pressurized kneader is extruded in a twin screw extruder in the form of sheet or banana and extruded in a sheet or banana size extrudate fed from a twin screw extruder in a single screw extruder in the form of pellets To prepare a master batch of a foaming agent in the form of a pellet.
≪ Example 2 >
The procedure of Example 1 was followed except that the raw materials were kneaded without any aging process in the kneader and then the subsequent steps were carried out to prepare a blowing agent master batch.
≪ Comparative Example 1 &
An OBSH-based master batch manufactured by EIWA was obtained.
<Test Example>
The decomposition temperature, gas amount, foamability, moldability and foam density of the master batches according to Examples and Comparative Examples were measured, and the results are shown in Table 1 below.
(1) Decomposition temperature and gas amount
The decomposition temperature (DT) and the decomposition gas amount (GV) of the blowing agent master batch were measured using a decomposition temperature measuring instrument (CELL TECHNO (JAPAN)).
(2) foaming property
After the master batch was aged, the shape of the master batch and the uniformity of the size of the bubbles were observed with naked eyes to obtain "○" (the surface was uniform and no roughness), "Δ" (the surface was not uniform but not rough) And "X" (surface unevenness and roughness due to papermaking).
(3) Moldability
The master batch and the general polymer resin were mixed and molded using an extrusion molding apparatus, extrusion molding was carried out in a cup shape, and the molded body was observed with naked eyes to obtain "?" (Surface is uniform), "?" ) And "X" (surface uneven).
(4) Foam density
The density of the master batch was determined by dividing the mass of the master batch by the volume, with the apparently increased volume of water when the master batch was immersed in water, as the volume of the master batch.
Referring to Table 1, it can be confirmed that the masterbatch of the blowing agent produced according to the present invention has almost the same quality as the master batch of the blowing agent of IWA, such as decomposition temperature, gas amount, foamability and moldability. However, as in Example 2, it can be seen that the amount of gas generated is slightly reduced in the case where the aging process is not performed.
The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.
Claims (13)
A step (S200) of extruding the kneaded material supplied from the pressurized kneader in a twin screw extruder into a sheet or banana-sized kneaded form;
(S300) of forming a sheet or a banana-sized elongated extrudate fed from a twin screw extruder in the form of pellets in a single screw extruder,
In the kneading step (S100), the kneading temperature is maintained at 60 to 70 占 폚, and since the OBSH has a decomposition temperature of 160 占 占 폚 and a gas amount of 95 占 ml / g, The mixture is kneaded at a pressing force of 0.12 to 0.5 MPa within 25 minutes and aged for 12 hours or more at a temperature of 20 ° C or less for stabilizing the heat history of the raw material,
Characterized in that the sheet or banana sized extrudate in the form of stripes is fed continuously from a twin screw extruder to a single screw extruder.
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| KR1020170168506A KR101865008B1 (en) | 2017-12-08 | 2017-12-08 | Foam-agent master batch composition and foam-agent master batch |
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| KR1020170168506A KR101865008B1 (en) | 2017-12-08 | 2017-12-08 | Foam-agent master batch composition and foam-agent master batch |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016518A (en) * | 2004-07-02 | 2006-01-19 | Jsr Corp | Composition for foam |
| CN103819709A (en) * | 2014-02-21 | 2014-05-28 | 宁波硫华聚合物有限公司 | Granular foaming agent pre-dispersed colloidal master batch and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016518A (en) * | 2004-07-02 | 2006-01-19 | Jsr Corp | Composition for foam |
| CN103819709A (en) * | 2014-02-21 | 2014-05-28 | 宁波硫华聚合物有限公司 | Granular foaming agent pre-dispersed colloidal master batch and preparation method thereof |
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