[go: up one dir, main page]

WO2020059916A1 - Composition de résine contenant un agent gonflant composite à blancheur améliorée - Google Patents

Composition de résine contenant un agent gonflant composite à blancheur améliorée Download PDF

Info

Publication number
WO2020059916A1
WO2020059916A1 PCT/KR2018/011194 KR2018011194W WO2020059916A1 WO 2020059916 A1 WO2020059916 A1 WO 2020059916A1 KR 2018011194 W KR2018011194 W KR 2018011194W WO 2020059916 A1 WO2020059916 A1 WO 2020059916A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
resin composition
foaming agent
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/011194
Other languages
English (en)
Korean (ko)
Inventor
조강진
전영배
유해나
김재춘
이상진
박진욱
김지후
김명우
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KEUM YANG CO Ltd
Original Assignee
KEUM YANG CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by KEUM YANG CO Ltd filed Critical KEUM YANG CO Ltd
Priority to PCT/KR2018/011194 priority Critical patent/WO2020059916A1/fr
Publication of WO2020059916A1 publication Critical patent/WO2020059916A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/003—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material
    • 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
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®

Definitions

  • the present invention relates to a composite foaming agent comprising a chemical blowing agent and a physical blowing agent and a resin composition having improved whiteness.
  • Foam or sponge is prepared by mixing a blowing agent into a resin or polymer, placing it in a mold, heating and pressing.
  • the foaming process as described above is largely divided into chemical foaming using a chemical foaming agent and physical foaming using a physical foaming agent such as a capsule-type foaming agent.
  • a chemical or physical blowing agent is used alone, problems such as generation of harmful gas and a decrease in foaming magnification due to a relatively low foaming pressure occur.
  • Chemical blowing agents have a problem in that harmful gases such as ammonia and formamide are generated during processing.
  • thermally expandable microspheres use expansion mechanism due to phase change due to heat.
  • the thermally expandable microspheres are a form of sealing hydrocarbons in the outer resin, and when heat is applied, a large volume expansion occurs due to a phase change of the hydrocarbons, thereby expanding the volume of the thermally expandable microspheres by about 50 times or more.
  • the thermally expandable microspheres compensate for disadvantages such as the problem of generating harmful gases of the chemical foaming agent, but the foaming rate of the final product is lower than that of the chemical foaming agent, and although there are differences depending on the resin, it is difficult to obtain a uniform foam.
  • Korean Registered Patent No. 10-1425039 relates to a method of molding a foamed plastic using a foaming agent, and discloses a method of using a chemical foaming agent sodium bicarbonate (NaHCO 3 ) as a foaming agent.
  • a chemical foaming agent sodium bicarbonate (NaHCO 3 ) sodium bicarbonate
  • harmful gases may be generated during processing, and the surface of the molded foam is rough and irregular.
  • Korean Patent Publication No. 2017-0012203 discloses a method for manufacturing a thermally expandable microsphere and its use, and discloses a microsphere that exhibits excellent expandability and shows good thermal expansion when mixed with a resin. However, it is not specific enough to be applied as an actual blowing agent because it does not reveal the exact content according to the use.
  • the present invention is to solve the above problems, the specific purpose is as follows.
  • the present invention aims to propose a suitable foaming form through a combination of a chemical blowing agent and a physical blowing agent.
  • Thermally expandable microspheres have a lower internal pressure than chemical foaming agents, so it is difficult to expect a high foaming rate.
  • the present invention has a technical feature that a physical foaming agent and a chemical foaming agent are appropriately mixed to cope with this. Specifically, it is chemically applied to base resins of EVA (Ethylene Vinyl Acetate copolymer), PVC (Poly Vinyl Chloride), and SBR (Styrene-butadiene Rubber) to be applied to products that require white coloring such as shoes, sandals, mats, and wallpaper.
  • a hybrid blowing agent is used which is a mixture of blowing agent and physical blowing agent.
  • a whiteness (WI) value of about 80 or more, and an inhibitory effect of yellowing depending on the content of the appropriate foaming agent. The purpose.
  • the present invention is a base resin; And a chemical foaming agent and a composite foaming agent including a physical foaming agent, wherein the chemical foaming agent is an azo-based foaming agent, and the physical foaming agent provides a resin composition comprising a composite foaming agent having improved whiteness as a thermally expandable microsphere.
  • the base resin may be selected from the group consisting of ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), styrene-butadiene rubber (SBR), and combinations thereof. have.
  • EVA ethylene-vinyl acetate
  • PVC polyvinyl chloride
  • SBR styrene-butadiene rubber
  • the azo-based foaming agent may be azodicarbonamide.
  • the thermally expandable microspheres include an outer shell comprising a thermoplastic resin; And a foaming compound encapsulated in the shell.
  • thermoplastic resin is acrylonitrile (AN), methaacrylonitrile (MAN), methyl methacrylate (Methylmethacrylate, MMA), methacrylic acid (MAA), acrylic acid (Acrylic acid, AA) and combinations thereof
  • foaming compound is composed of hydrocarbons, iso-Butane, iso-Pentane, Hexane, Octane (Octane) and combinations thereof.
  • the resin composition may include 2 parts by weight to 5 parts by weight of the composite blowing agent based on 100 parts by weight of the base resin.
  • the composite blowing agent may include the chemical blowing agent and the physical blowing agent in a mass ratio of 1: 0.5 to 1: 1.
  • the resin composition may further include an additive selected from the group consisting of a foaming accelerator, filler, lubricant, crosslinking agent, crosslinking accelerator, plasticizer, and combinations thereof.
  • One form of the resin composition is 100 parts by weight of a blend resin of ethylene-vinyl acetate (EVA), or ethylene-vinyl acetate (EVA) and low-density polyethylene (LDPE) as the base resin; 1 to 3 parts by weight of azodicarbonamide as the chemical blowing agent;
  • the outer shell is selected from the group consisting of acrylonitrile (AN), methacryrylonitrile (MAN), and combinations thereof, and the thermal expansion property of the foaming compound is iso-Pentane 1 to 3 parts by weight of microspheres;
  • Another form of the resin composition is 100 parts by weight of polyvinyl chloride (PVC) as the base resin;
  • PVC polyvinyl chloride
  • the outer shell is selected from the group consisting of acrylonitrile (AN), methacryrylonitrile (MAN), and combinations thereof, and the thermal expansion property of the foaming compound is iso-Pentane 1 to 3 parts by weight of microspheres; Stabilizer 1 to 5 parts by weight; 10 to 50 parts by weight of a filler; 1 to 5 parts by weight of lubricant; And 50 to 200 parts by weight of a plasticizer.
  • the resin composition is 100 parts by weight of styrene-butadiene rubber (Styrene-Butadiene Rubber) as the base resin; 1 to 3 parts by weight of azodicarbonamide as the chemical blowing agent;
  • the outer shell is selected from the group consisting of acrylonitrile (AN), methacryrylonitrile (MAN), and combinations thereof, and the thermal expansion property of the foaming compound is iso-Pentane 1 to 3 parts by weight of microspheres;
  • the resin composition may be foamed.
  • the foam may be a midsole / insole / outsole of shoes, wallpaper or mat.
  • thermoly expandable microspheres which are physical foaming agents, as foaming agents.
  • Figure 1 shows a photograph of the foam prepared according to the method of Example 1 and Comparative Example 1 when the base resin is made of EVA.
  • Figure 2 shows a photograph of the foam prepared according to the method of Example 2 and Comparative Example 2 when the base resin is made of PVC.
  • Figure 3 shows a photograph of the foam prepared according to the method of Example 3 and Comparative Example 3 when the base resin is SBR.
  • first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from other components.
  • the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.
  • Singular expressions include plural expressions unless the context clearly indicates otherwise.
  • the terms “include” or “have” are intended to indicate the presence of features, numbers, steps, actions, components, parts or combinations thereof described herein, one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, actions, components, parts or combinations thereof are not excluded in advance.
  • a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case “directly above” the other part but also another part in the middle.
  • a portion of a layer, film, region, plate, or the like is said to be “under” another portion, this includes not only the case “underneath” the other portion but also another portion in the middle.
  • variable includes all values within the described range including the described endpoints of the range.
  • a range of “5 to 10” includes values of 5, 6, 7, 8, 9, and 10, as well as any subrange of 6 to 10, 7 to 10, 6 to 9, 7 to 9, and the like. It will be understood to include, and include any value between integers pertinent to the stated range of ranges such as 5.5, 6.5, 7.5, 5.5 to 8.5 and 6.5 to 9, and the like.
  • the range of “10% to 30%” is 10% to 15%, 12% to 10%, 11%, 12%, 13%, etc., and all integers including up to 30%. It will be understood that it includes any subranges such as 18%, 20% to 30%, etc., and also includes any value between valid integers within the scope of the stated range, such as 10.5%, 15.5%, 25.5%, and the like.
  • the resin composition according to the present invention is a base resin; And composite blowing agents including chemical blowing agents and physical blowing agents.
  • the chemical blowing agent is an azo-based blowing agent, and the physical blowing agent is a thermally expandable microsphere.
  • the base resin is selected from the group consisting of ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), styrene-butadiene rubber (SBR), and combinations thereof.
  • EVA ethylene-vinyl acetate
  • PVC polyvinyl chloride
  • SBR styrene-butadiene rubber
  • the base resin may be provided in the form of a masterbatch (Materbatch, M / B). However, it is not limited thereto, and may be provided in the form of powder, granule, and flake.
  • the EVA, PVC and SBR are excellent in heat resistance and cold resistance, and have little deformation according to temperature. In addition, it has strong fusion, excellent stiffness, and excellent shock absorption and resilience. In addition, it has excellent oil and chemical resistance, flame retardant treatment, and in particular, it does not generate toxic gases (such as dioxin) during incineration, and is chemically stable, thereby securing stability to the human body and the environment.
  • the present invention is one technical feature of using the azo-based foaming agent as the chemical foaming agent.
  • the azo-based foaming agent is preferably azodicarbonamide (ADCA).
  • ADCA azodicarbonamide
  • the azodicarbonamide is an organic foaming agent, and has a higher decomposition temperature than other chemical blowing agents and has a large amount of gas generation.
  • the physical foaming agent is characterized in that it is a thermally expandable microsphere.
  • the thermally expandable microspheres include an outer shell and a foaming compound enclosed in the outer shell.
  • the thermally expandable microspheres have a core-shell structure.
  • the average particle diameter of the thermally expandable microspheres is not particularly limited, but is preferably 10 to 100 ⁇ m. More preferably, it is 10 to 50 ⁇ m. If the average particle diameter of the thermally expandable microspheres is less than 10 ⁇ m, the expansion performance of the microspheres may be lowered, and if the average particle diameter exceeds 100 ⁇ m, the filling efficiency of the foaming compound decreases, and when mixed with the base resin, workability may decrease. have.
  • the average particle diameter can be measured using a commercially available laser diffraction scattering type particle size distribution measuring device, for example, a micro track particle size distribution measuring device. In addition, 200 particles may be arbitrarily extracted from the electron micrograph and an average particle diameter may be calculated.
  • the thermally expandable microspheres contain 10 to 50% by weight, preferably 10 to 40% by weight, of the foamed compound (hydrocarbon) based on the total weight of the thermally expandable microspheres.
  • the temperature for initiating expansion of the thermally expandable microspheres is not particularly limited, but is preferably 80 ° C to 200 ° C. It is more preferably 100 ° C to 190 ° C. At this time, when the expansion start temperature is less than 80 ° C, the heat resistance is low and the expansion performance of the thermally expandable microspheres may be lowered. In addition, when the temperature exceeds 200 ° C, the maximum foaming temperature increases and the expansion performance of the thermally expandable microspheres may deteriorate.
  • the maximum expansion temperature of the thermally expandable microspheres is less than 300 ° C. If it is outside the above range, sufficient foaming magnification cannot be obtained.
  • the thermally expandable microspheres are excellent in heat resistance, and thus are preferable for use in injection molding and the like.
  • the maximum expansion ratio of the thermally expandable microspheres is 20 to 200 times. It is preferably 50 to 180 times. When the maximum expansion magnification exceeds 200 times, the surface of the foam containing the thermally expandable microspheres may be irregular and rough.
  • the method of manufacturing the thermally expandable microspheres includes preparing an oil phase comprising a thermoplastic monomer and a foaming compound; Preparing an aqueous phase comprising distilled water and a dispersion stabilizer; Mixing the oil phase and the water phase to form a suspension; And suspension polymerization of the suspension to produce thermally expandable microspheres.
  • thermoplastic monomer is acrylonitrile (AN), methacrylonitrile (MAN), methyl methacrylate (Methylmethacrylate, MMA), methacrylic acid (MAA), acrylic acid (Acrylic acid, AA) and combinations thereof.
  • the foaming compound is selected from the group consisting of iso-Butane, iso-Pentane, Normal pentane, N-pentane, Hexane, Octane, and combinations thereof. It may be a hydrocarbon (Hydrocarbon).
  • the oil phase of the present invention may further include an organic solvent as necessary in addition to the thermoplastic monomer and the foaming compound.
  • the oil phase of the present invention may be prepared by mixing the thermoplastic monomer, a foaming compound, an organic solvent, and the like.
  • the dispersion stabilizer may be selected from the group consisting of Colloidal Silica (C.S), aluminasol, magnesium hydroxide, and combinations thereof. It may be preferably colloidal silica.
  • the method of mixing the oil phase and the water phase in the step of forming the suspension is not particularly limited, for example, the oil phase may be mixed with the water phase, the water phase may be mixed with the water phase, and the water phase and the oil phase are respectively in separate containers. It can also be added and mixed. However, it can be mixed through a shear stress using an additional homogenizer.
  • the weight ratio of the oil phase and the water phase is 20:80 to 40:60.
  • the average particle diameter of the thermally expandable microspheres there is a high probability that small particles less than 10 ⁇ m will be distributed, and the amount of hydrocarbons present in the oil phase is low, so the foaming rate is low, so it functions properly as a blowing agent. It may not be possible.
  • the synthesis reaction is started after mixing with a homogenizer, the viscosity rises rapidly during initiation and crosslinking, so that rotational shear force cannot be applied to the reactant, so that synthesis of thermally expandable microspheres may be impossible.
  • the suspension can be obtained by mixing the aqueous phase and the oil phase at 1000 to 1500 rpm for 10 to 30 minutes using a homogenizer. If it is less than 1000 rpm, the mixing of the water phase and the oil phase may not be properly performed, and thus the particle size deviation of the thermally expandable microspheres may increase, and if it exceeds 1500 rpm, it may be difficult to form particles in a desired shape by being separated again by a homogenizer after droplets are formed. In addition, if less than 10 minutes, the water phase and the oil phase may not be properly mixed, so that droplets may not be formed, and if it exceeds 30 minutes, the amount of the blowing agent may be reduced by evaporation of hydrocarbons, which are boiling points at or below room temperature.
  • a polymerization initiator such as t-butyl peroxy acetate, diisopropylbenzene hydroperoxide, surfactant, and the like can be further added.
  • the "suspension polymerization” means polymerization in a state in which a water phase and an oil phase are mixed. Accordingly, a crosslinkable portion in the suspension is crosslinked to form a shell, and a thermally expandable microsphere containing hydrocarbons can be formed inside the shell.
  • suspension polymerization suspension polymerization is carried out in a reactor having a structure capable of applying pressure, a temperature increase reaction and a rotational force.
  • the pressure is 1 to 5 kgf / cm 2 .
  • the viscosity does not rise sufficiently, so that even shear force due to rotation of the impeller may not occur, and when it exceeds 5kgf / cm 2 , it may be difficult to control the particle size of the thermally expandable fine particles.
  • the rotational force may be 50 to 800 rpm. If it is out of the above range, it may be difficult to control the particle size of the thermally expandable microspheres.
  • the rotational shear force is applied by the impeller structure of the reactor, and the temperature during polymerization is performed at 50 ° C to 70 ° C.
  • the resin composition may include 2 parts by weight to 5 parts by weight of the composite blowing agent based on 100 parts by weight of the base resin.
  • the composite blowing agent may include the chemical blowing agent and the physical blowing agent in a mass ratio of 1: 0.5 to 1: 1.
  • the mass ratio of the physical foaming agent exceeds the above range, the whiteness of the foam produced by foaming the resin composition may be lowered and the foaming ratio may be lowered.
  • the mass ratio of the physical foaming agent is less than the above range, the surface of the foam may not be smooth. The cross-linking process is necessary and the process convenience may decrease.
  • the resin composition may further include an additive.
  • the additive may be selected from the group consisting of a foaming accelerator, filler, lubricant, crosslinking agent, crosslinking accelerator, plasticizer, rubber and combinations thereof.
  • the additive is not limited, as long as it can be used for the purpose.
  • the base resin can be ethylene-vinyl acetate (EVA), or a blend of ethylene-vinyl acetate (EVA) and low density polyethylene (LDPE).
  • EVA ethylene-vinyl acetate
  • LDPE low density polyethylene
  • the resin composition is based on 100 parts by weight of the base resin, 1 to 3 parts by weight of a chemical blowing agent and a physical blowing agent, 1 to 5 parts by weight of a foaming accelerator, 10 to 30 parts by weight of a filler, and 1 to 5 parts by weight of a lubricant And 0.1 to 2 parts by weight of a crosslinking agent.
  • the base resin may be polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the resin composition is based on 100 parts by weight of the base resin, 1 to 3 parts by weight of a chemical blowing agent, 1 to 3 parts by weight of a physical blowing agent, 1 to 5 parts by weight of a stabilizer, 10 to 50 parts by weight of a filler, 1 to 1 lubricant 5 parts by weight and 50 to 200 parts by weight of a plasticizer.
  • the base resin may be styrene-butadiene rubber (SBR).
  • SBR styrene-butadiene rubber
  • the resin composition is based on 100 parts by weight of the base resin, 1 to 3 parts by weight of a chemical blowing agent, 1 to 3 parts by weight of a physical blowing agent, 1 to 5 parts by weight of a foaming accelerator, 1 to 5 parts by weight of a lubricant, 1 to 1 part of a crosslinking agent 5 parts by weight and 0.1 to 2 parts by weight of a crosslinking accelerator.
  • the present invention foams the resin composition to form a foam.
  • the base resin is compounded into a kneader, an open roll, etc. together with the composite foaming agent, and then molded into a hollow shape by extrusion, injection or compression molding, or the like.
  • foaming is performed at high pressure to form a foam.
  • the foam is foamed by pressing at a high temperature.
  • the foam is characterized in that it can be applied to a window (midsole / insole / outsole), wallpaper or mat of shoes or sandals.
  • a base resin blended with EVA and PE (LDPE or LLDPE) is used.
  • EVA EVA
  • LLDPE low density polyethylene
  • LDPE or LLDPE LDPE
  • LDPE or LLDPE non-polar compared to EVA, which may cause difficulties when bonding the sole to the upper.
  • LDPE or LLDPE is non-polar compared to EVA, which may cause difficulties when bonding the sole to the upper.
  • LDPE or LLDPE is non-polar compared to EVA, which may cause difficulties when bonding the sole to the upper.
  • a rubber material is adhered to the front and rear parts of the floor where a lot of wear occurs.
  • adhesion is not easy.
  • PVC is used as a base resin to improve price competitiveness and productivity.
  • DOP Dioctyl Phthalate
  • PVC is mixed with DOP to undergo curing through interaction at high temperatures. Accordingly, it is preferable that PVC and DOP are applied 1: 1.
  • SBR can be used as the base resin.
  • SBR is used as a base resin, it is a feature that a traditional vulcanization process can be used. Accordingly, when the SBR is used as the base resin, it is preferable to add sulfur to the additive and heat it to change the elasticity.
  • a mixture of PVC and DOP is applied, but a method of heating for 30 seconds to 1 minute at a high temperature after casting thinly (less than 1T) is applied, so that a composite foaming agent and stabilizer requiring heat resistance thereto are applied. It should be applied appropriately.
  • a resin composition according to an embodiment of the present invention described above was prepared. Specifically, according to the ratio shown in Table 1, the resin compositions of Example 1 and Comparative Example 1 and Comparative Example 4 were prepared.
  • a resin composition according to another embodiment of the present invention described above was prepared. Specifically, according to the ratio shown in Table 2, the resin compositions of Example 2 and Comparative Example 2 were prepared.
  • Resin composition composition Example 2 (parts by weight) Comparative Example 2 (parts by weight) Base resin PVC (LP-090, LG) 100 100
  • Chemical blowing agent AC (Geumyang Co., Ltd.) 2 4 Physical blowing agent Thermally expandable microspheres (CAP / 563J, Geumyang Co., Ltd.) 2 - additive Stabilizer Ca-St (Dansuk) 2.5 2.5 Filler CaCO 3 (Yujin Industrial Co., Ltd.) 50 50 slush St / A (Stearic acid, LG) One One Plasticizer DOP (Dioctyl phthalate, Siyaku) 100 100
  • a resin composition according to another embodiment of the present invention described above was prepared. Specifically, according to the ratio shown in Table 3, the resin compositions of Example 3 and Comparative Example 3 were prepared.
  • Resin composition composition Example 3 (parts by weight) Comparative Example 3 (parts by weight) Base resin SBR 100 100 Chemical blowing agent AC (Geumyang Co., Ltd.) 2 4 Physical blowing agent Thermally expandable microspheres (CAP / 563J, Geumyang Co., Ltd.) 2 - additive Foaming accelerator ZnO (KS-1, Hanil Chemical Industry) 3 3 Crosslinker Sulfur 3 3 slush St / A (Stearic acid, LG) One One Crosslinking accelerator TT (Accelerator) 0.5 0.5 0.5 0.5 0.5 0.5 0.5
  • Foams were prepared using the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3, and the observed results were analyzed as follows.
  • the foaming rate (%), whiteness (White Index, WI) and yellowness index (Yellowness Index, b) are shown in Table 4 below. At this time, the whiteness was measured according to ASTM-E313.
  • Example 1 Comparative Example 1 Example 2 Comparative Example 2
  • Example 3 Comparative Example 3 Foaming rate (%) 150 160 145 150 145 150 WI 83.2 78.3 85.2 76.5 82.8 77.7 b 8.5 12.5 7.4 13.1 7.2 12.8
  • Example 1 has a whiteness of 83.2 and Comparative Example 1 has a whiteness of 78.3.
  • Example 1 has improved whiteness by 6.3% compared to Comparative Example 1.
  • the yellowing index of Example 1 is 8.5
  • the yellowing index of Comparative Example 1 is 12.5.
  • the yellowing index of Example 1 is improved by 32% compared to Comparative Example 1.
  • Figure 1 shows a photograph of the foam prepared using the resin composition of Example 1 and Comparative Example 1. It can be seen that the foam according to Example 1 of the drawing exhibits a color that is significantly closer to white compared to the foam according to Comparative Example 1.
  • Example 2 has a whiteness of 85.2 and Comparative Example 2 has a whiteness of 76.5. As a result, it can be seen that Example 2 improved the whiteness by 11.4% compared to Comparative Example 2. In addition, the yellowing index of Example 2 is 7.4, and the yellowing index of Comparative Example 2 is 13.1. Similarly, it can be seen that the yellowing index of Example 2 is improved by 43.5% compared to Comparative Example 2.
  • Figure 2 shows a photograph of the foam prepared using the resin composition of Example 2 and Comparative Example 2. It can be seen that the foam according to Example 2 of the drawing exhibits a color that is almost white compared to the foam according to Comparative Example 2.
  • Example 3 has a whiteness of 82.8 and Comparative Example 3 has a whiteness of 77.7. As a result of this, it can be seen that Example 3 has improved whiteness by 6.6% compared to Comparative Example 3. In addition, the yellowing index of Example 3 is 7.2, the yellowing index of Comparative Example 3 is 12.8, and it can be seen that the Yellowing Index of Example 3 was improved by 43.8% compared to Comparative Example 3.
  • Figure 3 shows a photograph of the foam produced using the resin composition of Example 3 and Comparative Example 3. It can be seen that the foam according to Example 3 of the drawing exhibits a color that is significantly closer to white compared to the foam according to Comparative Example 3.
  • the present invention is based on EVA as the base resin, and when a chemical foaming agent and a physical foaming agent are applied, the whiteness can be improved by 6.3% and the yellowing index is improved by 32% compared to using only the chemical foaming agent. It can be confirmed that it can provide the resin composition type and the resin composition content. This difference can also be confirmed by looking at the comparative picture of FIG. 1.
  • the present invention is a base resin made of PVC, and when a chemical foaming agent and a physical foaming agent are applied, the optimal resin composition type and resin composition capable of improving the whiteness by 11.4% and the yellowing index by 43.5% when using only the chemical foaming agent It can be confirmed that the content can be provided. This difference can also be confirmed by looking at the comparative picture of FIG. 2.
  • the base resin is SBR, and when a chemical blowing agent and a physical blowing agent are applied, the optimal resin composition type and resin that can improve the whiteness by 6.6% and the yellowing index by 43.8% when using only the chemical blowing agent It can be seen that the composition content can be provided. This difference can also be confirmed by looking at the comparative picture of FIG. 3.
  • Example 4 is a photograph observing the cross-section of the foam prepared using the resin composition according to Example 1 (Capsule + AC) and Comparative Example 4 (Capsule alone).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention concerne un agent gonflant composite comprenant un agent gonflant chimique et un agent gonflant physique. De façon spécifique, l'invention concerne un agent gonflant composite comprenant un agent gonflant chimique et un agent gonflant physique, et une composition de résine le comprenant. En particulier, la présente invention est caractérisée en ce qu'elle permet de résoudre un problème classique par l'application, à la composition de résine, d'un agent gonflant composite dans lequel un agent gonflant chimique à base d'azo et un agent gonflant physique qui est une microsphère thermiquement expansible sont mélangés.
PCT/KR2018/011194 2018-09-20 2018-09-20 Composition de résine contenant un agent gonflant composite à blancheur améliorée Ceased WO2020059916A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2018/011194 WO2020059916A1 (fr) 2018-09-20 2018-09-20 Composition de résine contenant un agent gonflant composite à blancheur améliorée

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2018/011194 WO2020059916A1 (fr) 2018-09-20 2018-09-20 Composition de résine contenant un agent gonflant composite à blancheur améliorée

Publications (1)

Publication Number Publication Date
WO2020059916A1 true WO2020059916A1 (fr) 2020-03-26

Family

ID=69887282

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/011194 Ceased WO2020059916A1 (fr) 2018-09-20 2018-09-20 Composition de résine contenant un agent gonflant composite à blancheur améliorée

Country Status (1)

Country Link
WO (1) WO2020059916A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679839A (zh) * 2020-12-24 2021-04-20 快思瑞科技(上海)有限公司 一种复合发泡功能母粒及其制备方法和应用
CN112831082A (zh) * 2021-01-29 2021-05-25 高密浩翰木塑材料科技有限公司 一种用于pvc发泡鞋底的物理发泡剂的生产工艺
CN113801364A (zh) * 2021-11-08 2021-12-17 安踏（中国）有限公司 一种哑光耐磨中底发泡材料的制备方法及应用
WO2022101118A1 (fr) * 2020-11-11 2022-05-19 Sika Technology Ag Matériau expansible ayant des propriétés d'isolation thermique améliorées et son utilisation
CN115403816A (zh) * 2022-09-30 2022-11-29 湖南方锐达科技有限公司 一种可膨胀热塑性发泡微球的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005212377A (ja) * 2004-01-30 2005-08-11 Eidai Kako Kk 複合板
KR100625456B1 (ko) * 2006-03-29 2006-09-20 박상은 피복박리제 조성물
JP2012140608A (ja) * 2010-12-15 2012-07-26 Matsumoto Yushi Seiyaku Co Ltd 発泡性樹脂組成物およびその用途
JP2012213615A (ja) * 2011-03-22 2012-11-08 Ube Industries Ltd 靴底用発泡体ゴム組成物及びアウトソール
KR20130103511A (ko) * 2010-09-06 2013-09-23 세키스이가가쿠 고교가부시키가이샤 발포성 수지 조성물 및 발포 성형체
KR20170017611A (ko) * 2015-08-07 2017-02-15 현대자동차주식회사 발포성 마스터배치 및 이를 포함하는 발포성과 무도장 특성이 우수한 폴리올레핀 수지 조성물
JP6277617B2 (ja) * 2012-07-23 2018-02-14 セントラル硝子株式会社 接着性組成物およびその接着方法、および接着後の剥離方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005212377A (ja) * 2004-01-30 2005-08-11 Eidai Kako Kk 複合板
KR100625456B1 (ko) * 2006-03-29 2006-09-20 박상은 피복박리제 조성물
KR20130103511A (ko) * 2010-09-06 2013-09-23 세키스이가가쿠 고교가부시키가이샤 발포성 수지 조성물 및 발포 성형체
JP2012140608A (ja) * 2010-12-15 2012-07-26 Matsumoto Yushi Seiyaku Co Ltd 発泡性樹脂組成物およびその用途
JP2012213615A (ja) * 2011-03-22 2012-11-08 Ube Industries Ltd 靴底用発泡体ゴム組成物及びアウトソール
JP6277617B2 (ja) * 2012-07-23 2018-02-14 セントラル硝子株式会社 接着性組成物およびその接着方法、および接着後の剥離方法
KR20170017611A (ko) * 2015-08-07 2017-02-15 현대자동차주식회사 발포성 마스터배치 및 이를 포함하는 발포성과 무도장 특성이 우수한 폴리올레핀 수지 조성물

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022101118A1 (fr) * 2020-11-11 2022-05-19 Sika Technology Ag Matériau expansible ayant des propriétés d'isolation thermique améliorées et son utilisation
EP4001352A1 (fr) * 2020-11-11 2022-05-25 Sika Technology AG Matériau extensible avec des propriétés d'isolation thermique améliorées et son utilisation
US12460061B2 (en) 2020-11-11 2025-11-04 Sika Technology Ag Expandable material with improved thermal insulation properties and use thereof
CN112679839A (zh) * 2020-12-24 2021-04-20 快思瑞科技(上海)有限公司 一种复合发泡功能母粒及其制备方法和应用
CN112831082A (zh) * 2021-01-29 2021-05-25 高密浩翰木塑材料科技有限公司 一种用于pvc发泡鞋底的物理发泡剂的生产工艺
CN113801364A (zh) * 2021-11-08 2021-12-17 安踏（中国）有限公司 一种哑光耐磨中底发泡材料的制备方法及应用
CN113801364B (zh) * 2021-11-08 2022-10-11 安踏（中国）有限公司 一种哑光耐磨中底发泡材料的制备方法及应用
CN115403816A (zh) * 2022-09-30 2022-11-29 湖南方锐达科技有限公司 一种可膨胀热塑性发泡微球的制备方法
CN115403816B (zh) * 2022-09-30 2023-08-22 湖南方锐达科技有限公司 一种可膨胀热塑性发泡微球的制备方法

Similar Documents

Publication Publication Date Title
WO2020059916A1 (fr) Composition de résine contenant un agent gonflant composite à blancheur améliorée
JP3323284B2 (ja) 微孔質発泡製品の製造に適した、フッ化ビニリデン、ヘキサフルオロプロペン、および所望によりテトラフルオロエチレンからなるエラストマー性重合体を基剤とする組成物
KR102160077B1 (ko) 수축률이 향상된 혼합발포제 포함하는 수지 조성물
WO2016180306A1 (fr) Semelle de chaussure en mousse, son procédé de préparation, et chaussures
WO2019124233A1 (fr) Composition de résine, corps moulé, et microsphère thermiquement expansible
JP2012213615A (ja) 靴底用発泡体ゴム組成物及びアウトソール
TW202000779A (zh) Eva熱塑性複合物、其方法及得自其之物件
JP3405821B2 (ja) シリコーンゴムスポンジ組成物
WO2020059917A1 (fr) Composition de résine à retrait amélioré comprenant un agent gonflant mixte
JP6448416B2 (ja) 発泡樹脂シート用樹脂組成物、および、発泡樹脂シート
JPS59202975A (ja) 自動車用ステアリングホイ−ル
KR20010009382A (ko) 발포용 열가소성 수지조성물
JPH1160868A (ja) 発泡押出し成形用塩化ビニル系樹脂組成物
JPH01215773A (ja) 無機質系軽量発泡体用組成物および無機質系軽量発泡体の製造方法
JP6688194B2 (ja) 発泡樹脂シート用樹脂組成物、および、発泡樹脂シート
WO2019194590A1 (fr) Procédé de fabrication d'une semelle de chaussure possédant de multiples couleurs
WO2018110841A1 (fr) Formulation d'agent moussant inorganique
KR20200034073A (ko) 백색도가 향상된 복합발포제를 포함하는 수지 조성물
JP4829185B2 (ja) 発泡成形体、発泡性熱可塑性エラストマー組成物およびその製造方法
FR2519344A1 (fr) Melange expansible a base de chlorure de polyvinyle donnant un produit alveolaire de faible densite
US20030082364A1 (en) Foam sheet and a method to manufacture a foam sheet
US5770641A (en) Vinyl chloride-based plastisol
CN115916876A (zh) 发泡成形用母料及其用途
JPH059325A (ja) オレフイン系エラストマー組成物の架橋発泡体の製造方法
CN1365374A (zh) 发泡性氯乙烯树脂组合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18933795

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18933795

Country of ref document: EP

Kind code of ref document: A1