KR101592894B1 - Copolymer of starch and thermoplastec polymer, manufacturing method of the same and use of the same - Google Patents
Copolymer of starch and thermoplastec polymer, manufacturing method of the same and use of the same Download PDFInfo
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- KR101592894B1 KR101592894B1 KR1020140081181A KR20140081181A KR101592894B1 KR 101592894 B1 KR101592894 B1 KR 101592894B1 KR 1020140081181 A KR1020140081181 A KR 1020140081181A KR 20140081181 A KR20140081181 A KR 20140081181A KR 101592894 B1 KR101592894 B1 KR 101592894B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
Abstract
The present invention provides a graft copolymer of a starch and a thermoplastic polymer, wherein the graft copolymerization of the starch and the thermoplastic polymer is formed via an unsaturated carboxylic acid. When the starch and the thermoplastic polymer of the present invention are replaced with a copolymer of the starch and the thermoplastic polymer of the present invention, it is possible to prevent the phase separation of the starch-based hot-melt adhesive and to minimize the viscosity change, The storage stability of the hot-melt adhesive can be improved. The starch-based hot-melt adhesives of the present invention exhibit the same level of physical properties as commercial products that do not include conventional starch.
Description
One aspect of the present invention relates to a copolymer of a starch and a thermoplastic polymer, and more particularly, to a starch-based hot-melt adhesive used as a component of a starch-based hot-melt adhesive, To a copolymer of starch and a thermoplastic polymer capable of improving the storage stability of the starch.
Another aspect of the present invention relates to a method for producing a copolymer of a starch and a thermoplastic polymer capable of improving the storage stability of a starch-based hot-melt adhesive.
Another aspect of the present invention relates to a starch-based hot-melt adhesive comprising a copolymer of starch and a thermoplastic polymer and a method for producing the same.
Adhesion refers to a state in which two surfaces are attached by the attraction force between molecules, atoms and ions. Adhesion phenomenon is widely applied in daily life to everyday life products such as tapes and bonds as well as automobiles and cutting-edge semiconductor devices Recently, the demand for adhesives for various fields has been diversified according to remarkable industrial development.
Polymer adhesives can be classified into chemical reaction type, solvent type, and hot melt type depending on the solidification process. Among them, hot-melt adhesives are easy to use and are a good example of meeting the requirements of the emerging environment.
Hot-melt adhesives (hot-melt adhesive) are solid-state materials at room temperature. They are used to make only 100% solids in heat without melting or dispersing them in a solvent. Due to DuPont's first development of ethylene-vinyl acetate resin (EVA) in the 1960s, hot-melt adhesives have advantages such as high productivity through process automation, environment-friendly characteristics, wide applicability, Showing a high growth rate. The hot-melt adhesive is applied to the adherend surface in a molten state and then is cooled and solidified by radiating heat to the adherend surface and its surroundings. The hot-melt adhesive is characterized in that it requires less drying space and has a faster bonding speed than other solvent-type adhesives and water-dispersible adhesives. High-speed adhesion enables the automation and productivity increase of the production line, and it has considerable economical efficiency such as improvement of productivity, reduction of labor cost, and reduction of raw material amount due to control of coating amount. Hot melt adhesives have been applied in many fields such as packaging, bookbinding, construction, woodworking, automobiles, textiles, and electrical / electronics.
Conventional commercial hot-melt adhesives generally include ethylene-vinyl acetate nyl, polyolefin, styrene block copolymer, polyamide, polyester, and urethane (reactive hot melt) And the cohesive force is the most important among the physical properties of the resin. In the conventional commercial hot-melt adhesive, since the base resin is mainly composed of petroleum-based materials, there is a lack of environment-friendly characteristics such as a large amount of volatile organic compound (VOC) generated during the manufacturing process or use, There is a problem that the manufacturing cost may be increased due to external factors such as anxiety of supply and demand of the material and exhaustion of the petroleum-based material. In addition, conventional commercial hot melt adhesives have been problematic in workability such as occurrence of threading during use. Therefore, it is necessary to replace all or a part of the base resin, which is a main component of the hot-melt adhesive, with biomass, especially starch, capable of endless regeneration considering environment friendliness, stable supply of water and cost point.
Regarding starch-based hot melt adhesives, Korean Patent Registration No. 10-1145374 discloses a composition comprising starch, a thermoplastic polymer, a tackifier, and a plasticizer, wherein the starch is contained in an amount of 30 to 65% by weight based on the total weight of the composition And the thermoplastic polymer is contained in an amount of 20 to 150 parts by weight based on 100 parts by weight of the starch. The thermoplastic polymer may be an ethylene-vinyl acetate copolymer (EVA), a polyvinyl acetate, a polyvinyl alcohol, -Acrylic acid copolymer, and ethylene-methacrylic acid copolymer, wherein the tackifier is contained in an amount of 25 to 125 parts by weight based on 100 parts by weight of the starch, and the dicyclopentadiene , DCPD), wherein the plasticizer is present in an amount of from 10 to 40 parts by weight per 100 parts by weight of the starch This amount may for starch-based hot-melt adhesive composition characterized in that an amount is disclosed. Also, Korean Patent Registration No. 10-1315784 discloses a composition comprising starch, a thermoplastic polymer, a tackifier, a plasticizer and an adhesion promoter, wherein the starch is contained in an amount of 25 to 55% by weight based on the total weight of the composition, The thermoplastic polymer may be contained in an amount of 20 to 150 parts by weight based on 100 parts by weight of the starch and may be an ethylene-vinyl acetate copolymer (EVA), a polyvinyl acetate, a polyvinyl alcohol, an ethylene- And ethylene-methacrylic acid copolymer, wherein the tackifier is contained in an amount of 25 to 125 parts by weight based on 100 parts by weight of the starch, and the plasticizer comprises 10 to 100 parts by weight of the starch, To 40 parts by weight, and the adhesion promoter is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the starch, and the polyacrylamide, There is disclosed a starch-based hot-melt adhesive characterized in that it is composed of at least one selected from the group consisting of polyvinylamide, polyethyleneimine, epoxidized polyamide, and glyoxylated polyacrylamide. Korean Patent Registration No. 10-1276294 discloses a composition comprising starch, a thermoplastic polymer and a tackifier, wherein the starch is contained in an amount of 20 to 60% by weight based on the total weight of the composition, and the thermoplastic polymer is starch And 20 to 200 parts by weight based on 100 parts by weight of an ethylene-vinyl acetate copolymer (EVA), a polyvinyl acetate, a polyvinyl alcohol, an ethylene-acrylic acid copolymer, -Methacrylic acid copolymer, and the tackifier is contained in an amount of 25 to 150 parts by weight based on 100 parts by weight of the starch, and is composed of a combination of an aliphatic hydrocarbon resin and a hydrogenated hydrocarbon resin Based hot-melt adhesive. However, since the starch constituting the conventional hot-melt-type hot-melt adhesive and the thermoplastic polymer are not compatible with each other, there is a problem that the starch-based hot-melt adhesive is produced during the process of producing or storing the starch-based hot-melt adhesive or the phase is separated, The viscosity change is severe and adversely affect the quality.
An object of the present invention is to provide a copolymer of a starch and a thermoplastic polymer which can improve the storage stability of a starch-based hot-melt adhesive when used as a component of a starch-based hot-melt adhesive. .
Another object of the present invention is to provide a method for producing a copolymer of a starch and a thermoplastic polymer capable of improving storage stability of a starch-based hot-melt adhesive.
Another object of the present invention is to provide a starch-based hot-melt adhesive having improved storage stability such as prevention of phase separation or minimization of viscosity change, and a method for producing the same.
The inventors of the present invention have found that when starch and a thermoplastic polymer which are constituents of a conventional starch-based hot-melt adhesive are replaced with a copolymer of a starch and a thermoplastic polymer, it is possible to prevent phase separation of the starch-based hot- And the storage stability of the starch-based hot-melt adhesive can be improved, thereby completing the present invention.
In order to solve one object of the present invention, the present invention provides a graft copolymer of starch and a thermoplastic polymer, wherein the graft copolymerization of the starch and the thermoplastic polymer is formed via an unsaturated carboxylic acid. A copolymer of a thermoplastic polymer is provided.
(A) reacting starch and an unsaturated carboxylic acid in the presence of a plasticizer to form a first composition comprising an unsaturated carboxylic acid-bound starch; And (b) reacting the wax and the thermoplastic polymer in the first composition and reacting the thermoplastic polymer with an unsaturated carboxylic acid bonded to the starch in the presence of a radical reaction initiator to form a graft of the thermoplastic polymer and the starch formed through the unsaturated carboxylic acid The method comprising the steps of: forming a second composition comprising a copolymer of a starch and a thermoplastic polymer.
In order to solve still another object of the present invention, the present invention provides a starch-based hot-melt adhesive in the form of a composition comprising a copolymer of the starch and a thermoplastic polymer, a plasticizer, a wax and a tackifier. According to another embodiment of the present invention, there is provided a method for manufacturing a starch-based hot-melt adhesive, comprising: (a) reacting starch and an unsaturated carboxylic acid in the presence of a plasticizer to form a first composition comprising an unsaturated carboxylic acid-bound starch; (b) adding a wax and a thermoplastic polymer to the first composition and reacting the thermoplastic polymer with an unsaturated carboxylic acid bonded to the starch in the presence of a radical reaction initiator to form grafts of the starch formed through the unsaturated carboxylic acid and the thermoplastic polymer Forming a second composition comprising a copolymer; And (c) adding a tackifier to the second composition and mixing to form a third composition.
When the starch and the thermoplastic polymer of the present invention are replaced with a copolymer of the starch and the thermoplastic polymer of the present invention, it is possible to prevent the phase separation of the starch-based hot-melt adhesive and to minimize the viscosity change, The storage stability of the hot-melt adhesive can be improved. The starch-based hot-melt adhesives of the present invention exhibit the same level of physical properties as commercial products that do not include conventional starch.
FIG. 1 schematically shows the structure of a copolymer of a starch and a thermoplastic polymer according to a preferred embodiment of the present invention.
Fig. 2 is a photograph of the starch-based hot-melt adhesive prepared in Production Example 1. Fig.
3 is a photograph of the starch-based hot-melt adhesive prepared in Comparative Production Example 4. Fig.
As used herein, the term "unsaturated carboxylic acid" is a generic term for organic compounds having at least one ethylenically unsaturated bond and at least one carboxyl group in the molecule.
As used herein, the term "unsaturated dicarboxylic acid" is a generic term of organic compounds having at least one ethylenic unsaturated bond and at least two carboxyl groups in the molecule, and includes an anhydride of an unsaturated dicarboxylic acid.
Hereinafter, the present invention will be described in detail.
Starch and thermoplastic Of polymer Copolymer
One aspect of the present invention relates to a starch-based hot-melt adhesive composition which can be used as a component of a starch-based hot-melt adhesive to prevent phase separation of a hot-melt adhesive and minimize viscosity change, To copolymers of thermoplastic polymers.
The copolymer of the starch and the thermoplastic polymer according to the present invention is obtained by grafting a thermoplastic polymer onto starch. Specifically, graft copolymerization of the starch and the thermoplastic polymer is performed by mixing a carboxylic acid having an ethylenically unsaturated bond (hereinafter referred to as an unsaturated carboxylic acid Quot;) or an anhydride thereof. Thermoplastic polymers commonly used in hot melt adhesives are composed of monomers with ethylenically unsaturated bonds, and such thermoplastic polymers are difficult to chemically bond directly with the hydroxyl groups of the starch. The inventors of the present invention have introduced an unsaturated carboxylic acid or an anhydride thereof as a linker in order to graft the thermoplastic polymer to starch. FIG. 1 schematically shows the structure of a copolymer of a starch and a thermoplastic polymer according to a preferred embodiment of the present invention. As shown in FIG. 1, the copolymer of starch and thermoplastic polymer according to the present invention is a copolymer of an unsaturated carboxylic acid and an unsaturated carboxylic acid (hereinafter, referred to as " thermoplastic polymer "Lt; RTI ID = 0.0 > ethylenically unsaturated bond < / RTI >
At this time, the type of the starch is not particularly limited, and examples thereof include corn starch, waxy corn starch, tapioca starch, potato starch, sweet potato starch, rice starch, wheat starch and the like. The starch also includes non-modified starches or certain modified starches. The unmodified starch is a starch obtained from a conventional starch manufacturing process, and includes modified starches (for example, acid-treated starches, enzyme-treated starches, starch-modified starches, and starch-modified starches) whose physical properties (viscosity, thermal stability, Oxidized starch, acetyl adipic acid pre-starch, acetyl phosphate pre-starch, octenyl succinate starch, phosphate pre-phosphate, pre-phosphate phosphate, phosphoric phosphate pre-phosphate, acetic acid starch, hydroxypropyl phosphate pre-min, hydroxypropyl starch and the like. ). The starch constituting the copolymer of the starch and the thermoplastic polymer according to the present invention is preferably a modified starch whose degree of polymerization of the starch is reduced by an acid treatment or an enzyme treatment in consideration of the ease of reaction and the storage stability of the starch-based hot- Do. Modified starches with reduced degree of polymerization of starch usually have reduced viscosity of the liquor. Such modified starches include acid-treated starch (also called thin starch or thin boiling starch), enzyme-treated starch ; Dextrin is also included in the enzyme-treated starch). The modified starch having a reduced degree of polymerization of the starch preferably has a viscosity of 20 wt% of the gelatinized solution at 50 ° C in a range of 10 to 100 centipoise (cPs), preferably 20 to 80 centipoise (cPs) Range.
The thermoplastic polymer is not particularly limited as long as it is generally used in a hot melt adhesive. Examples of the thermoplastic polymer include an ethylene-vinyl acetate copolymer (EVA), a polyvinyl acetate, a polyvinyl acetate A polyvinyl alcohol, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-butyl acrylate copolymer, an ethylene-ethylhexyl acrylate copolymer and an ethylene-methyl acrylate copolymer Or an ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA). The thermoplastic polymer may also be selected from thermoplastic polyolefins. The thermoplastic polyolefin may be a homopolymer formed of one type of monomer such as polyethylene or polypropylene, or may be a copolymer formed of two or more different monomers selected from ethylene, propylene, butene, hexene, octene, Chain is preferable. Particularly, the thermoplastic polyolefin is a copolymer of ethylene and an alpha-olefin having 4 to 20 carbon atoms (for example, a copolymer of 1-butene, 1-hexene, 1-octene or a copolymer of propylene and an alpha olefin having 4 to 20 carbon atoms (Ethylene-alpha olefin copolymer) obtained by metallocene-catalyzed polymerization or an ethylene-alpha olefin copolymer obtained by metallocene-catalyzed polymerization. - The propylene-alpha olefin copolymer is also called a polyolefin plastomer, which is a material in which the properties of plastics and elastomers are harmonized. Polyolefin plastics polymerized by metallocene catalysts Commercially available products of Merck include Affinity GA 1900 from Dow Chemical, Affinity GA 1950, etc. The starches and thermal The weight ratio of the starch to the thermoplastic polymer in the copolymer of the sintered polymer is not particularly limited and is preferably 0.5: 1 to 1: 5, more preferably 1: 1 to 1: 5 in view of the storage stability of the starch- More preferably 1: 2 to 1: 4.
The unsaturated carboxylic acid or its anhydride is not particularly limited as long as it has at least one ethylenic unsaturated bond and at least one carboxyl group in the molecule, and examples thereof include acrylic acid, methacrylic acid, maleic acid ), Fumaric acid, glutaconic acid, anhydride, traumatic acid, muconic acid, citraconic acid, and anhydrides thereof. (Maleic acid, fumaric acid, glutaconic acid, anhydride), traumatic acid (such as Traumatic acid), maleic acid (maleic acid, at least one unsaturated dicarboxylic acid or at least one unsaturated dicarboxylic acid selected from the group consisting of acetic acid, muconic acid, citraconic acid and anhydrides thereof, The die is preferably an anhydride of a carboxylic acid. The weight ratio of the unsaturated carboxylic acid (or an anhydride thereof), particularly unsaturated dicarboxylic acid (or an anhydride thereof) used as a starch to a linker in a copolymer of the starch and the thermoplastic polymer of the present invention is not particularly limited, It is preferably 1: 0.01 to 1: 0.2, more preferably 1: 0.04 to 1: 0.1 in view of the storage stability of the hot melt adhesive.
Starch-thermoplastic Polymer Process for producing a copolymer
Another aspect of the present invention relates to a method for producing a copolymer of the above-mentioned starch and a thermoplastic polymer (hereinafter referred to as a " starch-thermoplastic polymer copolymer "). The method for producing a starch-thermoplastic polymer copolymer according to the present invention comprises the steps of: (a) reacting starch and an unsaturated carboxylic acid or an anhydride thereof in the presence of a plasticizer to form a first composition comprising an unsaturated carboxylic acid- ; And (b) reacting the wax and the thermoplastic polymer in the first composition and reacting the thermoplastic polymer with an unsaturated carboxylic acid bonded to the starch in the presence of a radical reaction initiator to form a graft of the thermoplastic polymer and the starch formed through the unsaturated carboxylic acid And forming a second composition comprising the copolymer. The contents of starch, unsaturated carboxylic acid and thermoplastic polymer in the preparation of the starch-thermoplastic polymer copolymer according to the present invention are the same as those described in the above-mentioned starch-thermoplastic polymer copolymer.
In the step (a) of the process for producing a starch-thermoplastic polymer copolymer according to the present invention, an ester bond is formed between a hydroxyl group present in the starch and a carboxyl group present in the unsaturated carboxylic acid and the hydroxyl group of the starch is converted into an unsaturated carboxylic acid Substituted modified starches are produced. The reaction of step (a) is carried out in the presence of a plasticizer from the viewpoint of improving the reaction between the starch and the unsaturated carboxylic acid and from the viewpoint of simplifying the process for preparing the starch-based hot-melt adhesive described later. The plasticizer is used for imparting flexibility and adhesion to the polar polymer, and its type is not limited to a great extent. For example, the plasticizer may be selected from conventional surfactants, urea, and the like. Considering the ease of reaction and the storage stability of the starch-based hot-melt adhesive described below, the plasticizer may be selected from sorbitol, ethylene glycol, glycerin, glycerin diacetate, Ritolitol, and more preferably at least one selected from the group consisting of sorbitol and ethylene glycol. In the step (a), the weight ratio of the starch to the plasticizer is not particularly limited, and is preferably 1: 0.5 to 1: 3, and more preferably 1: 1 to 1: 2. The reaction temperature in step (a) is preferably 80 to 120 ° C, more preferably 90 to 110 ° C, but is not limited thereto.
In the step (b) of the process for producing a starch-thermoplastic polymer copolymer according to the present invention, at the ethylenic unsaturated bond position of the unsaturated carboxylic acid bonded with the starch, the thermoplastic polymer (in particular, the end of the thermoplastic polymer) Chemically bonded to form a starch-thermoplastic polymer copolymer. At this time, in step (b), the wax is used together with the thermoplastic polymer from the viewpoint of simplifying the manufacturing process of the starch-based hot-melt adhesive described later. The wax has a function of improving the fluidity of the starch-based hot-melt adhesive or increasing the thermal stability, and the type thereof is not limited to a great extent. For example, the wax may be at least one selected from the group consisting of paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, amide wax, and Fischer-Tropsch wax. The Fischer-Tropsch wax may also be classified as paraffin wax. Commercially available products of paraffin waxes that can be used in the present invention include Okerin 236 TP, available from Astor Wax Corporation (Doraville, GA); Penreco 4913, available from Pennzoil Products Co. (Houston, Tex.); R-7152 paraffin wax sold by Moore & Munger (Shelton, Conn.); Paraffin wax 1297 available from International Waxes, Ltd. (Ontario, Canada); Pacemaker marketed by Citgo; And R-2540 available from Moore and Munger; And other paraffin waxes such as 1230, 1236, 1240, 1245, 1246, 1255, 1260, and 1262, paraffin waxes available from CP Hall. The microcrystalline wax comprises at least 50% by weight of a cyclic alkane or a branched alkane containing a chain having from 30 to 100 carbon atoms. In general, microcrystalline wax has a lower crystallinity than paraffin wax and polyethylene wax, and has a melting point higher than about 70 캜. Commercial products of microcrystalline waxes that can be used in the present invention include Victory Amber Wax, available from Petrolite Corp. of Tulsa, Okla., USA, having a melting point of 70 占 폚; Bareco ES-796, available from Bareco (Chicago, Ill., USA), having a melting point of 70 캜; Okerin 177 sold by Astor Wax Corp. with a melting point of 80 ° C; Besquare 175 and 195 Amber Waxes available from Petrolite Corp. (Tulsa, Oklahoma) having melting points of 80 ° C and 90 ° C, respectively; Indramic 91 having a melting point of 90 ° C and commercially available from Industrial Raw Materials (Smesport, Pa.); But are not limited to, Petrowax 9508 Light sold by Petrowax PA, Inc. of New York, NY, with a melting point of 90 ° C. Commercial products of polyethylene waxes that may be used in the present invention include, but are not limited to, Polywax 500, Polywax 1500, and Polywax 2000 available from Petrolite, Inc. of Tulsa, Okla. In addition, the amide wax which can be used in the present invention may be selected from the compounds represented by the following general formula (1).
[Chemical Formula 1]
Wherein R 1 is an alkanediyl group having 2 to 4 carbon atoms, R 2 is a hydrocarbon group having 15 to 20 carbon atoms or a hydroxy hydrocarbon group having 15 to 20 carbon atoms, R 3 and / R < 4 > are independent of each other and represent a hydrocarbon group having 1 to 3 carbon atoms or hydrogen)
In the present invention, the hydrocarbon group is a functional group composed of carbon and hydrogen, and includes an alkyl group, an alkenyl group, and an aryl group. The compound represented by Formula 1 may be obtained by reacting a fatty acid or a hydroxy fatty acid such as oleic acid, linoleic acid, arachidonic acid, palmitic acid, stearic acid, Two amide bonds are formed by the reaction of diamines such as ethylenediamine, 1,4-diaminobutane and 1,3-diaminopropane. And generally has a high melting point of about 135 캜 to 165 캜. In the general formula (1), R 2 is a hydrocarbon group such as an alkyl group, an alkenyl group or an aryl group, or a hydroxy hydrocarbon group thereof, preferably an alkyl group or a hydroxyalkyl group. In the formula (1), R 3 and R 4 are preferably hydrogen or a methyl group. Specific examples of the compound represented by the formula (1) include 1,2-ethylenebis (stearamide); CAS Registry No. 110-30-5], 1,2-Ethylenebis (hydroxystearamide); 1,2-Ethylenebis (hydroxystearamide); CAS Registry No. 38162-95-7 or 123-26-2] and 1,3-propylenebis (palmitamide) [1,3-Propylenebis (palmitamide); CAS Registration No. 54535-68-1], N-N'-ethane-1,2-diylbis (N-ethylstearamide) ; CAS registration number 262-923-7].
Further, the Fischer-Tropsch wax is a synthetic wax produced by the Fischer-Tropsch method, which is commercially available as Sasolwax (R) product (for example, Sasolwax (R) H1) , Paraflint® products, or Polywax® products from Baker Petolite (eg Polywax® C80).
The weight ratio of the thermoplastic polymer to the wax in the step (b) is not particularly limited, and is preferably 1: 0.5 to 1: 2, more preferably 1: 0.5 to 1: 1.
In the step (b) of the method for producing a starch-thermoplastic polymer copolymer according to the present invention, a radical reaction initiator is used to induce the reaction between the unsaturated carboxylic acid and the thermoplastic polymer. The radical reaction initiator may be an organic peroxide, an azo compound (for example, 2,2-azobisbutyronitrile, 2,2'-azobis-2-methylbutyronitrile, etc.), sodium persulfate, But is not limited to a kind usually used for radical reactions such as potassium persulfate and the like, and organic peroxide is preferable in view of the reactivity between the unsaturated carboxylic acid and the thermoplastic polymer. The organic peroxide may be selected from the group consisting of benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cumyl But are not limited to, cumyl hydroperoxide, di-t-butyl hydroperoxide, dibenzoyl peroxide, succinic peroxide, dilauryl peroxide, Dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane [2,5-dimethyl-2,5- di- (t-butylperoxy) hexane], [alpha] -cumyl peroxy-neodecanoate, 1,1-dimethyl-3-hydroxybutylperoxy-2-ethylhexanoate 1-dimethyl-3-hydroxybutyl peroxy-2-ethyl hexanoate, t-amyl peroxy-benzoate, Selected from t-butyl peroxy-pivalate, 2,5-dihydroperoxy-2,5-dimethylhexane, cumene hydroperoxide and the like. But may not be limited thereto. Considering that the degree of reaction between the unsaturated carboxylic acid and the thermoplastic polymer is related to the storage stability of a starch-based hot-melt adhesive described later, the amount of the radical reaction initiator used in step (b) Is preferably 0.1 to 1 part by weight, more preferably 0.2 to 0.8 part by weight, and most preferably 0.3 to 0.6 part by weight.
The reaction temperature in step (b) is preferably 110 to 150 ° C, and more preferably 115 to 145 ° C in terms of the hue of the starch-based hot-melt adhesive described below. However, the reaction temperature is not limited thereto. For example, when the ethylene-vinyl acetate copolymer is used as the thermoplastic polymer, if the reaction temperature of step (b) is higher than 130 ° C, the color of the starch-based hot-melt adhesive may become stronger and the application range may be limited. When the ethylene-alpha-octene copolymer is used as the thermoplastic polymer, the color of the starch-based hot-melt adhesive becomes stronger and the application range may be limited if the reaction temperature of step (b) exceeds 140 ° C.
Starch-based Hot melt Adhesive and its manufacturing method
Another aspect of the present invention relates to a starch-based hot-melt adhesive having improved storage stability and a method for producing the same.
The starch-based hot-melt adhesive according to the present invention is in the form of a composition comprising a copolymer of the aforementioned starch and a thermoplastic polymer, a plasticizer, a wax and a tackifier. In the starch-based hot-melt adhesive according to the present invention, the same components as those described above are omitted for the starch, the unsaturated carboxylic acid, the thermoplastic polymer, the plasticizer and the wax.
In the starch-based hot-melt adhesive according to the present invention, the content of the copolymer of the starch and the thermoplastic polymer is not particularly limited, but it is preferably 15 to 50% by weight based on the total weight of the composition, considering compatibility with other components , More preferably 20 to 45 wt%, and most preferably 25 to 40 wt%. The content of the plasticizer is not limited, but is preferably 30 to 50 parts by weight, more preferably 35 to 45 parts by weight, based on 100 parts by weight of the copolymer of the starch and the thermoplastic polymer, considering compatibility with other components . The content of the wax is not particularly limited, but is preferably 45 to 70 parts by weight, more preferably 50 to 65 parts by weight, based on 100 parts by weight of the copolymer of the starch and the thermoplastic polymer, considering compatibility with other components .
Also, in the starch-based hot-melt adhesive according to the present invention, the tackifier is a low-molecular-weight resin and when used in combination with a copolymer of a starch and a thermoplastic polymer as basic components, the melt viscosity is lowered to improve workability, In some cases, a functional group may be imparted to improve the initial wetting property of the adhesive and the adhesion of the starch-based hot-melt adhesive to the surface of the adherend, and to control the solidification time. In the starch-based hot-melt adhesive according to the present invention, the tackiness-imparting agent is not limited to a rosin-based resin, a terpene resin, a coumarone-indene resin, a petroleum resin and the like. Examples of rosin-based resins include gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, , Resinates, and polymerized rosins, and the like; Natural rosins and modified rosins, including pale rosin, glycerol ester of wood rosin, glycerol ester of hydrogenated rosin, glycerol ester of polymerized rosin, pentaerythritol ester of hydrogenated rosin, phenol-modified pentaerythritol ester of rosin Of glycerol esters and pentaerythritol esters. Commercial products of rosin-based resins include Komotac KF382S, Komotac KF392S, Komotac KF452S, Komotac KF462S, Komotac KS-2090, Komotac KS-2100, Komotac KS-2110, Komotac KZ223S and Komotac KZ224S of Komo Chemical. . In the present invention, the rosin ester is obtained by reacting rosin acid with an alcohol such as methanol, triethylene glycol or pentaerythritol to convert the rosin acid into an ester, and includes esters of natural rosin and esters of modified rosin Concept. Commercially available rosin esters include Pinerez 2130, Pinerez 2220, Pinerez 2240, Pinerez 2330, Pinerez 2385 from Akzo Nobel-Eka chemicals; Ester Gum 105 from Arakawa Chemical, Ester Gum 106, Ester Gum A, Ester Gum AAL, Ester Gum AAV; Aquatac E 5375, Aquatac E 6180, Sylvalite RE 10L, Sylvalite RE 80 HP, Sylvalite RE 85L from Arizona Chemical; Pentalyn 710-M, Permalyn 2085, TACOLYN 3100, and TACOLYN 3179 H from Eastman Chemical Company. In the present invention, when the rosin ester is used as the tackifier, the melt viscosity of the hot melt adhesive and the adhesion time indicated by the set time can be maintained at an optimum level, so that the workability can be improved. Among the tackifier resins used in the present invention, terpene resins include natural terpene copolymers and terpolymers including styrene / terpene and alpha methylstyrene / terpene; A polyterpene resin having a softening point measured according to ASTM method E28-58T of about 70 deg. C to about 150 deg. A phenol-modified terpene resin containing a resin product produced by condensation reaction of bicyclic terpene and phenol in an acidic medium, and hydrogenated derivatives thereof. As the petroleum resin among the tackifiers used in the present invention, an aliphatic hydrocarbon resin, a cycloaliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an aromatic-modified aliphatic hydrocarbon Resins, aromatic modified aliphatic hydrocarbon resins, and hydrogenated hydrocarbon resins. Commercial products of aliphatic hydrocarbon resins include Hikorez A-1100, Hikorez A-1100S, Hikorez C-1100, Hikorez R-1100, and Hikorez R-1100S from Kolon Oil Company (Korea). The alicyclic hydrocarbon resin includes a hydrocarbon resin containing dicyclopentadiene (DCPD) as a monomer, and disclosed in Korean Patent Publication No. 1998-013719 and Korean Patent Publication No. 2008-0093733. Commercial products of aromatic hydrocarbon resins include Hikotack P-110S, Hikotack P-120, Hikotack P-120HS, Hikotack P-120S, Hikotack P-140, Hikotack P- 140M, Hikotack P-150, Hikotack P-160, Hikotack P-90, Hikotack P-90S, Hirenol PL-1000 and Hirenol PL-400. Commercial products of aromatic modified aliphatic hydrocarbon resins include Hikorez T-1080 and Hikorez T-1100 from Kolon Chemical Industries, Ltd. (Korea). Hydrogenated hydrocarbon resins may be further classified into hydrogensified aliphatic hydrocarbon resins, hydrogeneated aromatic hydrocarbon resins, etc. Commercially available products include Sukorez D-300, Sukorez D-390 , Sukorez SU-100, Sukorez SU-110, Sukorez SU-120, Sukorez SU-130, Sukorez SU-90, Hikorez H-2100, Hikorez H-2130, Hikorez H-2200 and Hikorez H-2300. In addition, the tackifier used in the present invention may include a hydrocarbon resin having 4 to 10 carbon atoms in the monomer, and more specifically, a C5 aliphatic resin, a C9 aromatic resin, and a C5 / C9 aliphatic / aromatic copolymer resin. In addition, the tackifier used in the present invention may include a hydrocarbonated hydrocarbon resin containing dicyclopentadiene (DCPD) as a monomer, and commercially available products include Sukorez D-300, Sukorez D-390, Sukorez SU-100, Sukorez SU-110, Sukorez SU-120, Sukorez SU-130 and Sukorez SU-90. The content of the tackifier is not particularly limited, but is preferably 100 to 200 parts by weight, more preferably 125 to 175 parts by weight, based on 100 parts by weight of the copolymer of the starch and the thermoplastic polymer, considering compatibility with other components .
The starch-based hot-melt adhesive according to the present invention may further comprise an auxiliary additive in addition to a copolymer of starch and a thermoplastic polymer, a plasticizer, a wax and a tackifier, and the auxiliary additive may be added to the hot- Specific functions. The auxiliary additives included in the starch-based hot-melt adhesive according to the present invention may be at least one selected from the group consisting of polybutene, oil, filler, and antioxidant. Polybutene is added for improvement of water resistance or imparting flexibility. The oil is added for imparting flexibility, improving the process such as melt kneading, and the like. Filler is a substance that is added to the purpose of anti-aging, reinforcement, and increase in the practical use of rubber or plastic, and is used to control the flowability of the hot-melt adhesive. The type of filler is not critical and may be selected from, for example, one or more of calcium carbonate, clay, bentonite, or calcium stearate. The antioxidant may be added when a material containing a structure that can be easily oxidized due to its low thermal stability is used to improve the viscosity change due to oxidation and decomposition, yellowing, lowering of adhesion and lowering of durability. The kind of the antioxidant is not particularly limited, and examples thereof include phenols, aromatic amines, citric acid, and ascorbic acid. The content of the auxiliary additive in the starch-based hot-melt adhesive according to the present invention is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the copolymer of the starch and the thermoplastic polymer.
The method for producing a starch-based hot melt adhesive according to the present invention comprises the steps of: (a) reacting starch and an unsaturated carboxylic acid or an anhydride thereof in the presence of a plasticizer to form a first composition comprising an unsaturated carboxylic acid-bound starch; (b) adding a wax and a thermoplastic polymer to the first composition and reacting the thermoplastic polymer with an unsaturated carboxylic acid bonded to the starch in the presence of a radical reaction initiator to form grafts of the starch formed through the unsaturated carboxylic acid and the thermoplastic polymer Forming a second composition comprising a copolymer; And (c) adding a tackifier to the second composition and mixing to form a third composition. The method for producing a starch-based hot-melt adhesive according to the present invention refers to the above-mentioned contents in a copolymer of starch and a thermoplastic polymer, a method for producing the same, or a starch-based hot-melt adhesive.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are intended to clearly illustrate the technical features of the present invention and do not limit the scope of protection of the present invention.
1. Explanation of analysis method
(1) Melt viscosity
The melt viscosity of the hot melt adhesive was measured using a viscometer (model name: HBDV-11 + P) equipped with a Thermosel system (a constant temperature device) manufactured by Brookfield. Specifically, 13 ml of the hot-melt adhesive was placed in a sample chamber, melted completely at about 140 ° C, and the melt viscosity was measured using a SC4-28 spindle.
(2) Softening point
The softening point was measured by the ring and ball method specified in KS M 2250.
(3) Set time
A predetermined amount of hot melt adhesive was applied to a paper material cut to a size of 40 mm x 40 mm and then a certain pressure was applied to measure the time until the adhesion was completed, Respectively.
2. Starch and thermoplastic
Of polymer
Copolymers and copolymers thereof
Starch-based
Hot melt
Manufacture of adhesives
Production Example 1
11.52 parts by weight of D-sorbitol, which is a plasticizer, was added to the reactor, and the temperature of the reactor was raised to 100 DEG C to melt the plasticizer. Thereafter, while maintaining the temperature of the reactor at 100 占 폚, 0.5 part by weight of maleic anhydride, which is a reactive monomer, was added to the reactor and mixed with the plasticizer. Thereafter, 7.94 parts by weight of acid-treated corn starch (viscosity at 50 ° C: 30 to 50 cPs of a 4 wt% enrichment liquid; viscosity: 30-50 cPs; manufactured by Toho Kagaku Co., Ltd.) was added to the reactor while the temperature of the reactor was maintained at 100 ° C, And reacted for 50 minutes to obtain a first composition containing a modified starch wherein the hydroxyl value of the starch was replaced with maleic acid. Then, an ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA; Product name: VA910 (VA content 28%); , 8.65 parts by weight of a polyethylene wax as a wax and 7.14 parts by weight of Fischer-Tropsch wax (trade name: Sasolwax H1; manufactured by Sasol wax, South Africa) 1 composition. Thereafter, the temperature of the reactor was raised to 120 ° C, and a radical reaction initiator, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane [2,5- tert-butylperoxy) hexane] as a polymerization initiator, and the mixture was reacted for about 90 minutes to obtain a starch-thermoplastic polymer graft having an ethylene-vinyl acetate copolymer graft-copolymerized with maleic acid (or maleic anhydride) A second composition comprising a copolymer was obtained. Thereafter, 20.85 parts by weight of rosin ester (product name: Pinerez 2130; supplier: Akzo Nobel-Eka chemicals), 17.86 parts by weight of a hydrocarbon resin of C5 monomer (product name: Piccotac P1095, manufactured by Eastman Chemical Co.) And 4.29 parts by weight of a hydrocarbon resin of a C5 monomer modified with C9 aromatic hydrocarbon (trade name: Wingtack® ET; manufactured by Cray Valley) were added and mixed, and 0.23 part by weight of an antioxidant was added thereto and mixed to prepare a starch-type hot- .
Fig. 2 is a photograph of the starch-based hot-melt adhesive prepared in Production Example 1. Fig. As shown in FIG. 1, the starch-based hot-melt adhesive prepared in Preparation Example 1 shows good compatibility among the components.
Production Example 2
Except that the reaction temperature was changed to 130 占 폚 instead of 120 占 폚 in the grafting of the ethylene-vinyl acetate copolymer to the modified starch substituted with maleic acid in the same manner as in Production Example 1, A hot-melt adhesive was prepared.
Production Example 3
A hot-melt starch-based adhesive was prepared in the same manner and under the same conditions as in Preparation Example 1, except that the amount of maleic anhydride as a reactive monomer was changed to 0.45 parts by weight instead of 0.5 parts by weight.
Production Example 4
As a radical reaction initiator, 0.07 part by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane [2,5-Dimethyl- A hot-melt starch-based adhesive was prepared in the same manner and under the same conditions as in Preparation Example 1, except that 0.11 part by weight of dicumyl peroxide was used.
Production Example 5
11.46 parts by weight of D-sorbitol, which is a plasticizer, was added to the reactor, and the temperature of the reactor was raised to 100 DEG C to melt the plasticizer. Thereafter, while maintaining the temperature of the reactor at 100 占 폚, 0.5 part by weight of maleic anhydride, which is a reactive monomer, was added to the reactor and mixed with the plasticizer. Thereafter, 8.44 parts by weight of acid-treated corn starch (viscosity at 50 DEG C of 30 to 50 cPs of a 4 wt% enrichment liquid at 30 DEG C; manufactured by TOKYO CO., LTD., Korea) was added to the reactor while the temperature of the reactor was maintained at 100 DEG C, And reacted for 50 minutes to obtain a first composition containing a modified starch wherein the hydroxyl value of the starch was replaced with maleic acid. Thereafter, 19.02 parts by weight of an ethylene-1-octene coplymer (product name: Affinity GA 1900; manufactured by Dow Chemical) polymerized by a methocarbon catalyst as a thermoplastic polymer and 17.8 parts by weight of polyethylene wax as a wax And the mixture was mixed with the first composition. Thereafter, the temperature of the reactor was raised to 135 ° C, and a radical reaction initiator, 2,5-dimethyl-2,5-di (tert-butylperoxy) tert-butylperoxy) hexane was added thereto, and the mixture was allowed to react for about 90 minutes to prepare a starch-thermoplastic polymer graft (hereinafter referred to as " starch-thermoplastic polymer graft copolymer " A second composition comprising a copolymer was obtained. Then, 43 parts by weight of a hydrogenated hydrocarbon resin (trade name: Hikorez H-2100; supplied by Kolon Chemical Industries, Ltd., Korea) as a tackifier, and 0.23 part by weight of an antioxidant were added to the reactor, Based hot melt adhesive.
Production Example 6
Alpha-octene copolymer was grafted on a modified starch substituted with maleic acid, the reaction temperature was changed to 140 DEG C instead of 135 DEG C to obtain a starch-based copolymer A hot-melt adhesive was prepared.
Production Example 7
Except that the reaction temperature was changed to 150 ° C instead of 135 ° C in the grafting of the ethylene-alpha-octene copolymer to the modified starch substituted with maleic acid, A hot-melt adhesive was prepared.
Comparative Production Example 1
11.52 parts by weight of D-sorbitol, which is a plasticizer, was added to the reactor, and the temperature of the reactor was raised to 100 DEG C to melt the plasticizer. Thereafter, 7.94 parts by weight of acid-treated corn starch (viscosity at 50 캜 of 30 to 50 cPs of 4 wt% enrichment liquid: 30 to 50 cPs; manufactured by Toho Kagaku Co., Ltd.) was added to the reactor while the temperature of the reactor was maintained at 100 캜, To obtain a first composition. Then, an ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA; Product name: VA910 (VA content 28%); , 8.65 parts by weight of a polyethylene wax as a wax and 7.14 parts by weight of Fischer-Tropsch wax (trade name: Sasolwax H1; manufactured by Sasol wax, South Africa) 1 composition. Thereafter, the temperature of the reactor was raised to 120 ° C, and a radical reaction initiator, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane [2,5- tert-butylperoxy) hexane] was added and reacted for about 90 minutes to obtain a second composition. Thereafter, 20.85 parts by weight of rosin ester (product name: Pinerez 2130; supplier: Akzo Nobel-Eka chemicals), 17.86 parts by weight of a hydrocarbon resin of C5 monomer (product name: Piccotac P1095, manufactured by Eastman Chemical Co.) And 4.29 parts by weight of a hydrocarbon resin of a C5 monomer modified with C9 aromatic hydrocarbon (trade name: Wingtack® ET; manufactured by Cray Valley) were added and mixed, and 0.23 part by weight of an antioxidant was added thereto and mixed to prepare a starch-type hot- .
Comparative Preparation Example 2
11.52 parts by weight of D-sorbitol, which is a plasticizer, was added to the reactor, and the temperature of the reactor was raised to 100 DEG C to melt the plasticizer. Thereafter, while maintaining the temperature of the reactor at 100 占 폚, 0.5 part by weight of maleic anhydride, which is a reactive monomer, was added to the reactor and mixed with the plasticizer. Thereafter, 7.94 parts by weight of acid-treated corn starch (viscosity at 50 ° C: 30 to 50 cPs of a 4 wt% enrichment liquid; viscosity: 30-50 cPs; manufactured by Toho Kagaku Co., Ltd.) was added to the reactor while the temperature of the reactor was maintained at 100 ° C, And reacted for 50 minutes to obtain a first composition containing a modified starch wherein the hydroxyl value of the starch was replaced with maleic acid. Then, an ethylene-vinyl acetate copolymer (Ehtylene Vinyl Acetate Copolymer, EVA; Product name: VA910 (VA content 28%); , 8.65 parts by weight of a polyethylene wax as a wax and 7.14 parts by weight of Fischer-Tropsch wax (trade name: Sasolwax H1; manufactured by Sasol wax, South Africa) 1 composition to obtain a second composition. Thereafter, 20.85 parts by weight of rosin ester (product name: Pinerez 2130; supplier: Akzo Nobel-Eka chemicals), 17.86 parts by weight of a hydrocarbon resin of C5 monomer (product name: Piccotac P1095, manufactured by Eastman Chemical Co.) And 4.29 parts by weight of a hydrocarbon resin of a C5 monomer modified with C9 aromatic hydrocarbon (trade name: Wingtack® ET; manufactured by Cray Valley) were added and mixed, and 0.23 part by weight of an antioxidant was added thereto and mixed to prepare a starch-type hot- .
Comparative Production Example 3
11.46 parts by weight of D-sorbitol, which is a plasticizer, was added to the reactor, and the temperature of the reactor was raised to 100 DEG C to melt the plasticizer. Thereafter, 8.44 parts by weight of acid-treated corn starch (viscosity at 50 캜 of 30 to 50 cPs of a 4 wt% enrichment liquid at 30 캜, manufactured by KABUSHIKI CO., LTD., Korea) was added to the reactor while the temperature of the reactor was maintained at 100 캜, To obtain a first composition. Thereafter, 19.02 parts by weight of an ethylene-1-octene coplymer (product name: Affinity GA 1900; manufactured by Dow Chemical) polymerized by a methocarbon catalyst as a thermoplastic polymer and 17.8 parts by weight of polyethylene wax as a wax And the mixture was mixed with the first composition. Thereafter, the temperature of the reactor was raised to 135 ° C, and a radical reaction initiator, 2,5-dimethyl-2,5-di (tert-butylperoxy) tert-butylperoxy) hexane] was added and reacted for about 90 minutes to obtain a second composition. Then, 43 parts by weight of a hydrogenated hydrocarbon resin (trade name: Hikorez H-2100; supplied by Kolon Chemical Industries, Ltd., Korea) as a tackifier, and 0.23 part by weight of an antioxidant were added to the reactor, Based hot melt adhesive.
Comparative Preparation Example 4
29.85 parts by weight of common corn starch, 0.5 parts by weight of a sorbitan fatty acid ester as a plasticizer (product name: Almax 2070; supplied by Ilshin Wells, Korea) and Urea, 0.5 part by weight of an ethylene-vinyl acetate copolymer (Trade name: Pinerez 2130; supplied by Akzo Nobel-Eka chemicals) as a tackifier, a paraffin wax (trade name: Okerin 236 (trade name) manufactured by Wako Pure Chemical Industries, TP: supplier: Astor Wax Corporation) and 1.99 parts by weight of polyethylene wax were sequentially charged into a kneader (kneader) preheated to about 170 to 180 DEG C and melt kneaded to prepare a starch-based hot melt adhesive.
3 is a photograph of the starch-based hot-melt adhesive prepared in Comparative Production Example 4. Fig. As shown in FIG. 4, the starch-based hot-melt adhesive prepared in Comparative Preparation Example 4 has poor compatibility among components and part of the starch exists in the form of particles.
3. Hot melt Evaluation of properties of adhesives
(1) Evaluation of storage stability of hot melt adhesive
The initial viscosity of the starch-based hot-melt adhesive prepared in Preparative Examples 1 to 7 and Comparative Preparative Examples 1 to 3 was measured after melting at 140 ° C and stored at 140 ° C for 24 hours, And the viscosity stability was evaluated by the amount of viscosity change.
When the precipitate was generated, the phase separation was evaluated as "poor" and when the precipitate was not generated, the phase separation was evaluated as "good". In addition, the viscosity stability was evaluated as "good" when the viscosity was reduced to more than 500 cPs, "poor ", and less than 50 cPs, .
In the case of the hot-melt adhesives prepared in Preparation Examples 1 to 7, even after storage at 140 ° C for 24 hours, no precipitates were formed, viscosity changes were not observed or their levels were very small. On the other hand, in the case of the hot-melt adhesive prepared in Comparative Production Examples 1 to 3, when the adhesive was melted at 140 ° C and then stored for 24 hours, a large amount of precipitates were formed and the viscosity was decreased by 500 cPs or more compared with the initial value. 1 was reduced by more than 800 cPs.
(2) Comparison of properties with commercial hot melt adhesives
The melt viscosity, softening point and set time of the hot melt adhesive prepared in Preparation Example 1 and the commercially available non-conductive hot melt adhesive at 140 ° C were measured, and the results are shown in Table 2 below.
The starch-based hot-melt adhesive according to the present invention exhibited the same level of physical properties as commercial non-conductive hot-melt adhesive.
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, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the protection scope of the present invention should not be construed as being limited to the specific embodiments disclosed as the best mode contemplated for carrying out the invention, but includes all embodiments falling within the scope of the appended claims.
Claims (29)
Wherein the copolymer of the starch and the thermoplastic polymer is a graft copolymer formed by graft copolymerization of the starch and the thermoplastic polymer via an unsaturated carboxylic acid.
(b) adding a wax and a thermoplastic polymer to the first composition and reacting the thermoplastic polymer with an unsaturated carboxylic acid bonded to the starch in the presence of a radical reaction initiator to form a copolymer of a starch formed through an unsaturated carboxylic acid and a thermoplastic polymer ≪ / RTI > And
(c) adding a tackifier to the second composition and mixing to form a third composition.
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| PCT/KR2015/005173 WO2016003069A1 (en) | 2014-06-30 | 2015-05-22 | Copolymer of starch and thermoplastic polymer, method for preparing same, and use thereof |
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