KR102035503B1 - Composition of the hot-melt adhesive - Google Patents
Composition of the hot-melt adhesive Download PDFInfo
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- KR102035503B1 KR102035503B1 KR1020130020578A KR20130020578A KR102035503B1 KR 102035503 B1 KR102035503 B1 KR 102035503B1 KR 1020130020578 A KR1020130020578 A KR 1020130020578A KR 20130020578 A KR20130020578 A KR 20130020578A KR 102035503 B1 KR102035503 B1 KR 102035503B1
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- resin
- melt adhesive
- hot melt
- adhesive composition
- polyalkylene carbonate
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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
- C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
Abstract
The present invention blends an amorphous polyalphaolefin resin having excellent compatibility with a polypropylene carbonate resin, thereby providing excellent adhesion to both polar and nonpolar surfaces, easy handling at low temperatures, good cold resistance, and bleeding and stickiness of the surface. In particular, the present invention provides a hot melt adhesive composition capable of maximizing productivity by increasing the processing speed by reducing the open time in processing.
Description
The present invention relates to hotmelt adhesive compositions having excellent adhesion to both polar and nonpolar surfaces.
The hot melt adhesive including the thermoplastic polymer material is liquefied by heat and applied to the adherend to express adhesion. Solvent-type adhesives use organic solvents as a base material for liquefaction, and thus there is always a risk of environmental pollution and fire due to volatilization of organic solvents during use. On the other hand, the hot melt adhesive does not contain an organic solvent, which is environmentally friendly and harmful to the human body, and its use is increasing.
Typical hot melt adhesives include ethylene vinyl acetate, styrene-based, and olefin-based resins as main components, and include tackifying resins, waxes, and other additives as constituents.
As the tackifying resin, rosin and its derivatives, C5, C9 petroleum resin, terpene resin, and the like are used, and as wax, paraffin wax, microcrystalline wax, polyethylene wax, and the like are used.
The resins are not necessarily excellent in adhesion to all surfaces, and may or may not be excellent in adhesion to a specific surface depending on the physical and chemical properties of each resin.
US Patent Publication No. 2011-0229721 (Patent Document 1) discloses a hot melt adhesive comprising an ethylene-vinylacetate copolymer, a styrene block copolymer, a tackifier resin and a plasticizer. Although the hot melt adhesives exhibit adhesive strength to various materials, they do not show adhesive strength as epoxy or urethane adhesives, and have low flexibility and low adhesive strength at low temperatures, and thus are limited to various applications.
Amorphous polyalphaolefin (APAO) is mainly used for the assembly of parts such as automobiles, refrigerators, CRTs, batteries, etc., and has a wide distribution range of softening points, so it can be applied to places requiring both cold resistance and heat resistance. It is applicable to fields such as filters. In particular, adhesion to non-polar surfaces such as PE and PP is superior to other resins. However, the APAO has a weak adhesive strength to the polar surface, it is difficult to apply to the field of fast line speed due to the low solidification rate, and for this reason it is difficult to apply to the field that requires a lot of initial adhesive force.
PPC-based hot melt has a relatively high adhesive strength to the polar surface compared to the conventional ethylene vinyl acetate-based hot melt, but relatively low adhesion to the non-polar surface it is necessary to supplement the physical properties through the combination of tackifying resin or other thermoplastic resin. In this case, when the compatibility is not good, the tensile strength, elongation, etc. are weak, which lowers the mechanical strength of the adhesive, which weakens the final physical properties of the adhesive and causes the performance of the adhesive itself to deteriorate.
The technical problem to be achieved is to blend an amorphous polyalphaolefin resin having excellent compatibility with a polypropylene carbonate resin, thereby providing excellent adhesion to both polar and non-polar surfaces, easy handling at low temperatures, and good cold resistance. It is an object of the present invention to provide a hot melt adhesive composition that is free from bleeding phenomenon and non-stickiness, and in particular, can increase productivity by reducing open time in processing.
In order to achieve the above technical problem, the present invention provides a hot melt adhesive composition comprising a polyalkylene carbonate resin and an amorphous poly alpha-olefin resin (APAO).
In the hot melt adhesive composition according to an embodiment of the present invention, the weight mixing ratio of the polyalkylene carbonate resin and the amorphous polyalphaolefin resin may be 5:95 to 95: 5.
In the hot melt adhesive composition according to an embodiment of the present invention, the weight mixing ratio of the polyalkylene carbonate resin and the amorphous polyalphaolefin resin may be 10:90 to 40:60 or 90:10 to 60:40.
In the hot melt adhesive composition according to an embodiment of the present invention, the amorphous polyalphaolefin resin may have a crystallinity of 0.1 to 40% and a softening point of 90 to 150 ° C.
In the hot melt adhesive composition according to an embodiment of the present invention, the amorphous polyalphaolefin resin may have a glass transition temperature of -40 to -18 ℃.
In the hot melt adhesive composition according to an embodiment of the present invention, the amorphous polyalphaolefin resin may be a copolymer or terpolymer containing any one or more selected from ethylene, butene and hexene in propylene.
In the hot melt adhesive composition according to an embodiment of the present invention, the polyalkylene carbonate resin has a weight average molecular weight of 10,000 to 100,000 g / mol, it may be selected from polypropylene carbonate or polyethylene carbonate.
In the hot melt adhesive composition according to an embodiment of the present invention, the polyalkylene carbonate resin may be a glass transition temperature (Tg) of 0 ~ 45 ℃.
In the hot melt adhesive composition according to an embodiment of the present invention, the hot melt adhesive composition is a tackifier resin, a plasticizer, a wax, an antioxidant, an elastomer, a pigment, a dye, a filler, a sunscreen, an antistatic agent, an antiblocking agent, a slip agent, It may further include one or two or more additives selected from inorganic fillers, kneading agents, stabilizers, modified resins, leveling agents, optical brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers or lubricants.
The present invention provides a hot melt adhesive comprising the hot melt adhesive composition described above.
Hot melt adhesive composition according to the present invention has the advantage of excellent compatibility and excellent adhesion to both polar and non-polar surface. In addition, the hot melt adhesive composition of the present invention is easy to handle at low temperatures and good cold resistance, there is no bleeding phenomenon and stickiness of the surface, in particular, it is possible to maximize productivity by increasing the processing speed by reducing the open time in the processing.
Figure 1 shows a schematic configuration for measuring the adhesive force of the hot melt adhesive and the adhesive according to the present invention.
Hereinafter, the present invention may be better understood by the following examples, which are intended to illustrate the present invention and are not intended to limit the protection scope of the present invention.
Hereinafter, preferred embodiments and evaluation test items for hot melt adhesive compositions excellent in adhesion to both polar and nonpolar surfaces of the present invention will be described in detail. The invention may be understood more specifically by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
The present invention relates to a hot-melt adhesive composition comprising a polyalkylene carbonate and an amorphous poly alpha-olefin (APAO), wherein the polyalkylene carbonate is a carbon dioxide and one or more epoxide compounds different from each other. It may be a copolymerized reaction.
Epoxide compounds include (C2-C10) alkylene oxides unsubstituted or substituted with halogen or alkoxy; (C4-C20) cycloalkylene oxide unsubstituted or substituted with halogen or alkoxy; And (C8-C20) styrene oxide unsubstituted or substituted with halogen, alkoxy, alkyl or aryl.
Alkoxy specifically includes (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6-C20) ar (C1-C20) aralkyloxy, and the like, and aryloxy is phenoxy, biphenyloxy, Naphthyloxy etc. are mentioned. Alkoxy, alkyl and aryl may be those having a substituent selected from halogen elements or alkoxy groups.
More specifically, the aliphatic polycarbonate may be represented by Formula 1 below.
[Formula 1]
[Formula 1 m is 2 to 10, n is 1 to 3, R is hydrogen, (C1-C4) alkyl or -CH2-O-R '(R' is (C1-C8) alkyl), x : y is 5:95 to 99.99: 0.01]
Specific examples of the epoxide compound in the present invention, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene Monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl Ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxidenorbornene, limonene Oxide, dieldrin, 2,3-epoxidepropylbenzene, styrene oxide, phenylpropylene oxide, Bene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxidepropyl ether, Epoxypropyl methoxyphenyl ether biphenyl glycidyl ether, glycidyl naphthyl ether, and the like.
Solution polymerization or bulk polymerization may be carried out as a method of polymerizing polyalkylene carbonate, and more specifically, carbon dioxide may be introduced by the presence of an epoxide compound and a catalyst using an organic solvent as a reaction medium.
Examples of the solvent include aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, chloromethane, methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2- Halogenated hydrocarbons such as dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene and bromobenzene It can be used alone or in combination of two or more. The pressure of carbon dioxide can be up to 100 atm at normal pressure, preferably from 5 atm to 30 atm. The polymerization temperature at the time of copolymerization reaction can be 20-120 degreeC, Preferably 50-90 degreeC is suitable. More preferably, bulk polymerization using the monomer itself as a solvent can be carried out.
The aliphatic polycarbonate is a polyalkylene carbonate prepared on the basis of those disclosed in Korean Patent Laid-Open Publication Nos. 2008-0015454, 2009-0090154, 2010-067593, and 2010-0013255 filed by the present applicant. As the alkylene, ethylene, propylene, 1-butylene, cyclohexene, alkylglycidyl ether, n-butyl, n-octyl, and the like, are not limited thereto.
In the present invention, the polyalkylene carbonate resin is not limited in weight average molecular weight, but more practical example, a weight average molecular weight of 10,000 to 100,000 g / mol is effective in terms of having a strong cohesive strength and low melt viscosity as a hot melt adhesive. If the weight average molecular weight is more than 100,000g / mol may cause a problem of high viscosity when the hot melt adhesive composition is melted, when less than 10,000g / mol may cause a problem that the cohesive force is weak to reduce the adhesion.
In the present invention, the polyalkylene carbonate resin preferably has a glass transition temperature (Tg) of 0 to 45 ° C.
The hot melt adhesive composition of the present invention is characterized in that it comprises polyalkylene carbonate and APAO. Amorphous polyalphaolefin resins (APAO) can be coplymers consisting of two conpoenets, such as amorphous propylene / ethylene (APE), amorphous propylene / butene (APB), or amorphous propylene / hexene (APH), and are made of propylene / ethylene / hexene. It may be a terpolymer consisting of three components.
In the present invention, it is preferable that the amorphous polyalphaolefin resin (APAO) has a crystallinity of less than 40%, and the lower the degree of amorphous crystallinity, the higher the desired physical properties. In addition, the amorphous polyalphaolefin resin (APAO) has a softening point of 90 to 150 ℃, the glass transition temperature is preferably -40 to -18 ℃. Examples of such amorphous polyalphaolefins (APAO) include REXtac 2215, REXtac 2304, REXtac 2780, E-101, and the like.
In the present invention, the amorphous polyalphaolefin resin includes a copolymer or terpolymer comprising propylene, any one or more selected from ethylene, butene and hexene.
In the present invention, the amount of polyalkylene carbonate / APAO can be appropriately increased or decreased depending on the intended use, the weight mixing ratio of the polyalkylene carbonate resin and APAO is preferably in the ratio of 5:95 to 95: 5, more preferably Including the ratio of 10:90 to 40:60 or 90:10 to 60:40 is effective because it improves adhesion and shortens the open time to the added amount without inhibiting compatibility. When the ratio of either of the two components is less than 10 parts by weight, the effect of improving the adhesion is insignificant, and when either ratio is between 40 and 60 parts by weight, compatibility is deteriorated and mechanical strength is lowered.
Hot melt adhesive composition according to an embodiment of the present invention can be seen that the adhesion is excellent on both the surface having a different surface energy than the polyalkylene carbonate, APAO, and the Open Time is shortened.
In addition, the hot melt adhesive composition includes a tackifying resin, a plasticizer, a wax, an antioxidant, an elastomer, a pigment, a dye, a filler, a sunscreen, an antistatic agent, an antiblocking agent, a slip agent, an inorganic filler, a kneading agent, a stabilizer, a modifying resin, a leveling agent It may further include one or more additives selected from fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers and lubricants, and any additives that are obviously used in the art may be used without limitation.
Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.
Polypropylene carbonate resin (SK Energy, GreenPolTM) having a weight average molecular weight of 30,000 g / mol and different types of APAO were stirred for 7 minutes at 160 ° C. in a Brabender mixer at a composition ratio as shown in Table 1 below to prepare a hot melt adhesive. .
After the preparation, a 25 mm x 100 mm hot melt sample was bonded between two adherends having a size of 25 mm x 100 mm at a temperature of 160 ° C. for 30 seconds to measure shear adhesion using UTM. Test speed was measured in 50mm / min, the results are shown in Table 2 below.
In addition, after heating the temperature of the prepared adhesive composition to 180 ℃ and under the atmospheric conditions (25 ℃), the adhesive was applied on the paper 100mm long with a width of about 2mm on a piece of paper and a piece of paper (20mm each vertically) every 5 seconds. After attaching, after 10 minutes after the adhesion, when the peeled off pieces of paper, the portion of the paper is destroyed by half or more to record the open time as shown in Table 3 below.
TABLE 1
TABLE 2
Table 3
As can be seen from Tables 2 to 3, Examples 1 to 5 according to the present invention, when compared to Comparative Examples 1 to 4, when the blended polypropylene carbonate and various types of APAO all the adhesion to the surface having a variety of surface energy It can be seen that this has been improved. It can also be seen that the Open Time is shorter than in each case.
Accordingly, the present invention can provide a hot melt adhesive composition that can be applied to a field that requires high processing speed by blending polyalkylene carbonate and APAO with excellent adhesion to all surfaces having different polarities while reducing open time.
Claims (10)
Hot-melt adhesive composition, characterized in that the weight mix ratio of the polyalkylene carbonate resin and the amorphous polyalphaolefin resin is 5:95 to 95: 5.
Hot-melt adhesive composition characterized in that the weight mix ratio of the polyalkylene carbonate resin and the amorphous polyalphaolefin resin is 10:90 to 40:60 or 90:10 to 60:40.
The amorphous polyalphaolefin resin is a hot melt adhesive composition, characterized in that the copolymer or terpolymer comprising any one or more selected from ethylene, butene and hexene in propylene.
The polyalkylene carbonate resin has a weight average molecular weight of 10,000 to 100,000 g / mol, hot melt adhesive composition, characterized in that selected from polypropylene carbonate or polyethylene carbonate.
The polyalkylene carbonate resin has a glass transition temperature of 0 to 45 ℃ hot melt adhesive composition.
The hot melt adhesive composition may be a tackifier resin, a plasticizer, a wax, an antioxidant, an elastomer, a pigment, a dye, a filler, a sunscreen, an antistatic agent, an antiblocking agent, a slip agent, an inorganic filler, a kneading agent, a stabilizer, a modified resin, a leveling agent, A hot melt adhesive composition further comprising one or two or more additives selected from fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers or lubricants.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100284065B1 (en) * | 1992-08-06 | 2001-03-02 | 한스 크리스토프 빌크 | Thermoplastic Hot Melt Adhesive |
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| KR101174019B1 (en) * | 2010-03-17 | 2012-08-16 | 주식회사 오공 | Hotmelt adhesive composition |
| KR101351363B1 (en) * | 2010-12-28 | 2014-01-22 | 에스케이이노베이션 주식회사 | Composition of the eco-friendly hot melt adhesive |
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