WO2021071079A1 - Hot-melt adhesive composition and manufacturing method therefor - Google Patents
Hot-melt adhesive composition and manufacturing method therefor Download PDFInfo
- Publication number
- WO2021071079A1 WO2021071079A1 PCT/KR2020/010682 KR2020010682W WO2021071079A1 WO 2021071079 A1 WO2021071079 A1 WO 2021071079A1 KR 2020010682 W KR2020010682 W KR 2020010682W WO 2021071079 A1 WO2021071079 A1 WO 2021071079A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copolymer
- isoprene
- hot melt
- derived
- adhesive composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 239000004831 Hot glue Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 141
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 85
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920001400 block copolymer Polymers 0.000 claims abstract description 65
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 62
- 238000005859 coupling reaction Methods 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 150000001993 dienes Chemical class 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000010168 coupling process Methods 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 239000012943 hotmelt Substances 0.000 claims description 36
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 35
- 239000003431 cross linking reagent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
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- 239000004033 plastic Substances 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
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- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
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- 230000000379 polymerizing effect Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- 239000012790 adhesive layer Substances 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 2
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
Definitions
- the present invention relates to a hot melt pressure-sensitive adhesive composition comprising a block copolymer composition and a method for producing the same.
- Hot melt adhesive is an adhesive that melts by heat using a thermoplastic resin, thereby forming an adhesive surface. Unlike conventional UV-curable adhesives, it does not use volatile solvents, so it is a hazardous substance during curing. Because of its low emission, it is preferred as an environmentally friendly high-functional adhesive.
- Hot melt adhesives are not only relatively cheaper than UV curable adhesives, but also because they exist in a liquid state at high temperatures, they are easy to apply and compress on a substrate or adherend, and then cool and solidify at room temperature within a few seconds to exhibit adhesion. Because it is, it is easy to use.
- hot melt adhesives are applied to the adherend in a molten state and then cooled to form a hard phase having cohesiveness, creep resistance, etc., so diapers, feminine hygiene products, industrial tapes, packaging tapes It is widely used in various industrial fields, such as pressure sensitive adhesive manufacturing electronic products, structural materials, etc.
- the hot melt adhesive contains a base resin and an additive, for reasons such as compatibility, phase separation and bleeding may occur, resulting in a problem of decreasing adhesion, and high viscosity, during melt processing for adhesion, Relatively high temperature conditions are required, and in particular, problems such as viscosity change, odor generation, and discoloration may occur under such processing temperature conditions, so that the demand for low-viscosity products with relatively lowered melting temperatures is increasing.
- the present invention has been devised to solve the problem of the technology behind the background of the present invention, and it is intended to provide a hot melt adhesive composition that can be applied at a high temperature with a high softening point and can improve adhesive properties.
- the present invention is a diblock copolymer comprising a styrene-based monomer-derived unit and a conjugated diene-based monomer-derived unit, and a tree which is a coupling polymer of the diblock copolymer.
- a block copolymer, and a crosslinked block copolymer comprising a crosslinking portion derived from a crosslinking agent crosslinked with at least two of the diblock copolymer and the triblock copolymer, and the unit derived from the conjugated diene-based monomer is an isoprene-derived unit and the following formula It provides a hot melt pressure-sensitive adhesive composition comprising an epoxidized isoprene unit represented by 1.
- the present invention comprises the steps of preparing a styrene-based monomer block by polymerizing a styrene-based monomer in the presence of a hydrocarbon solvent and a polymerization initiator (S10); Polymerizing the styrene-based monomer block and isoprene to prepare a diblock copolymer including a styrene-based monomer-derived unit and an isoprene-derived unit (S20); Preparing a triblock copolymer by coupling reaction of two or more diblock copolymers with a coupling agent to prepare a block copolymer composition comprising the triblock copolymer and the diblock copolymer (S30); Reacting some of the isoprene-derived units contained in the triblock copolymer and the diblock copolymer with a mixture of hydrogen peroxide and a carboxylic acid, thereby substituting some of the isoprene-derived units with epoxidized is
- the hot melt adhesive composition comprising a diblock copolymer, a triblock copolymer, and a crosslinked block copolymer thereof according to the present invention comprises a part of the conjugated diene-based monomer unit constituting the conjugated diene-based monomer block of the copolymer.
- By functionalizing with There is an effect of improving the performance required at high temperature, such as high temperature stability and viscosity maintaining characteristics at high temperature, and at the same time improving adhesion.
- the term'monomer-derived repeating unit' or'monomer-derived unit' may refer to a component, structure or substance itself derived from a monomer. It may mean a unit formed in a polymer. Furthermore, the monomer-derived unit is not only a unit in which two or more repeating units are repeated, but also a monomer-derived unit is one, and may be expressed as a monomer-derived repeat unit.
- the term'block' refers to a form of a polymer chain formed by block polymerization of monomers, and may refer to a form in which a plurality of monomer-derived units are continuously connected.
- the styrene-based monomer block may mean a polymer chain formed by block polymerization of a styrene-based monomer or an aggregate of units derived from a plurality of styrene-based monomers.
- the term'polymer block' may refer to a group of polymer chains formed by block polymerization of a monomer.
- the hot melt adhesive composition according to an embodiment of the present invention may include a diblock copolymer, a triblock copolymer, and a crosslinked block copolymer in which two or more of them are crosslinked by a crosslinking agent. More specifically, the hot-melt pressure-sensitive adhesive composition according to an embodiment of the present invention includes a diblock copolymer comprising a styrene-based monomer-derived unit and a conjugated diene-based monomer-derived unit, and a triblock which is a coupling polymer of the diblock copolymer. It may include a copolymer, and a crosslinked block copolymer comprising a crosslinking portion derived from a crosslinking agent crosslinked with at least two of the diblock copolymer and the triblock copolymer.
- the diblock copolymer is a diblock copolymer comprising a styrene-based monomer-derived unit and a conjugated diene-based monomer-derived unit, and the conjugated diene-based monomer-derived unit is an isoprene-derived unit and an epoxidized isoprene unit represented by the following formula (1).
- the diblock copolymer includes a styrene-based monomer block (S) including a styrene-based monomer-derived unit, and a conjugated diene-based monomer block (I) including an isoprene-derived unit,
- S styrene-based monomer block
- I conjugated diene-based monomer block
- a block copolymer in the form of partially functionalized with an epoxy group and substituted with an epoxidized isoprene unit (EI) represented by Formula 1 it may be a diblock copolymer in the form of (S)-(I-EI).
- the triblock copolymer is a coupling polymer prepared by a coupling reaction of two or more diblock copolymers, and is typically a triblock copolymer in the form of (S)-(I-EI)-(S). have. Meanwhile, the triblock copolymer may further include a unit derived from a coupling agent between the conjugated diene-based monomer block (I-EI) and the styrene-based monomer block (S) according to a coupling agent or a coupling method.
- the crosslinked block copolymer is a block copolymer wherein at least two of the diblock copolymer and the triblock copolymer are crosslinked block copolymers crosslinked by a crosslinking agent, and the crosslinking agent and the diblock copolymer or the triblock copolymer A cross-linking portion derived from a cross-linking agent may be included at the cross-linking site of and.
- the crosslinking agent includes two or more functional groups capable of crosslinking reaction with the epoxidized isoprene unit represented by Formula 1 included in the triblock copolymer and the diblock copolymer, and hydroxy groups or amine groups at both ends of the crosslinking agent It may be to include.
- the crosslinking agent may be polyalkylene glycol, alkylene glycol, alkylenediamine, and specifically polyethylene glycol or ethylene glycol.
- the styrene-based monomer for forming the unit derived from the styrene-based monomer may be styrene, alpha-methylstyrene, para-methylstyrene, vinyl toluene, vinyl naphthalene, para-butyl styrene, or a combination thereof, and specifically styrene. .
- the unit derived from the styrene-based monomer may be generated by polymerization of the styrene-based monomer, and the unit derived from the styrene-based monomer included in the hot melt adhesive composition is a block copolymer including the diblock copolymer and the triblock copolymer It may be included in 10 to 20 parts by weight, specifically 13 to 18 parts by weight, based on the total 100 parts by weight.
- the styrene-based monomer Since the styrene-based monomer has a glass transition temperature (Tg) value higher than room temperature, a hard segment unit having a relatively hard property is formed in the copolymer. Therefore, when the content of the unit derived from the styrene-based monomer is 10 parts by weight or more, mechanical properties such as hardness of the hot melt adhesive composition including the same can be improved, and heat resistance can be maintained at the same time. In addition, when the content of the unit derived from the styrene-based monomer is 20 parts by weight or less, it is possible to increase processability by suppressing an excessive increase in viscosity of the hot-melt pressure-sensitive adhesive composition, and at the same time, it is possible to prevent the problem of lowering the adhesive strength.
- Tg glass transition temperature
- the conjugated diene-based monomer contains isoprene in the unit derived from the conjugated diene-based monomer of the present invention
- the conjugated diene-based monomer contains 1,3-butadiene
- higher adhesion and peeling as an adhesive formulation It is advantageous in terms of adhesion performance because it has the advantage of being able to implement strength.
- a hot melt adhesive composition comprising a unit derived from a conjugated diene-based monomer in which a part of the isoprene-derived unit is substituted with an epoxidized isoprene unit represented by Formula 1,
- the epoxidized isoprene unit included in the hot melt pressure-sensitive adhesive composition is 0.5 to 5 parts by weight, specifically 1 to 3 parts by weight, based on the total 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit.
- the content of the epoxidized isoprene unit is 5 parts by weight or less based on the total 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit, the viscosity increases during high-temperature storage, thereby preventing deterioration of storage and high-temperature stability. .
- the content of the epoxidized isoprene unit is 0.5 parts by weight or more based on the total 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit, there is an effect of preventing a decrease in the viscosity of the pressure-sensitive adhesive when stored at a high temperature for a long time.
- the diblock copolymer may be 15 to 25 parts by weight based on 100 parts by weight of the diblock copolymer and the triblock copolymer.
- the triblock copolymer may be prepared by performing a coupling reaction with respect to the diblock copolymer including the styrene-based monomer-derived unit and the conjugated diene-based monomer-derived unit. In this process, a diblock copolymer that does not participate in the coupling reaction remains and may be included in the hot melt pressure-sensitive adhesive composition. That is, the hot melt adhesive composition of the present invention may include a triblock copolymer and a diblock copolymer remaining without participating in the coupling reaction.
- the triblock copolymer according to an embodiment of the present invention may be a coupling polymer of a diblock copolymer, and the coupling agent is dimethyldichlorosilane, tetrachlorosilane, dimethyldiethoxysilane, dimethyldimethoxysilane, tetra Silane derivatives, such as ethoxysilane and tetramethoxysilane, can be illustrated.
- the hot melt pressure-sensitive adhesive composition according to an embodiment of the present invention may further include a blend for one or more hot melt pressure-sensitive adhesives selected from the group consisting of a tackifier, a plastic oil, and an antioxidant.
- the block copolymer including the diblock copolymer, the triblock copolymer, and the crosslinked block copolymer may be included in an amount of 10 to 40 parts by weight based on 100 parts by weight of the hot melt adhesive composition.
- the tackifier included in the hot melt pressure-sensitive adhesive composition may include at least one of a hydrogenated rosin ester-based compound and at least a partially hydrogenated dicyclopentadiene-based polymerized petroleum resin.
- rosin refers to abietic acid, dehydro abietic acid from which hydrogen has been removed from abietic acid, and dihydro to which 2 or 4 hydrogens are added, or tetrahydroa.
- Dihydro abietic acid (Tetrahydro abietic acid) is a concept that includes both abietic acid and two hydrogens.
- Dihydroabietic acid is a concept that contains all of the various isomers depending on the position of the double bond. Is used.
- the rosin ester-based compound is esterified by reacting the carboxyl group of abietic acid with the OH group of an alcohol or polyol based on the above-described abietic acid or hydrogenated abietic acid structure, and this is also a natural rosin Or all esterified products of modified rosin.
- the alcohol or polyol is, for example, an aliphatic alcohol having 1 to 20 carbon atoms, and may be in the form of a mono alcohol, diol, triol, tetraol, pentaol, and more specifically, for example, methanol, ethanol, Glycerol, ethylene glycol, diethylene glycol, or pentaerythritol.
- abietic acid may cause an esterification reaction with all or part of the hydroxyl groups of the polyol, and thus, polyhydric esters, such as monoesters, diesters, ternary esters, or quaternary esters, are Can be formed.
- the dicyclopentadiene-based polymerized petroleum resin is produced as a by-product in the naphtha cracking process, which decomposes Naphtha obtained by refining crude oil at high temperature, that is, C9-dish produced from cyclopentadiene fraction. It means a petroleum resin containing clopentadiene.
- Cyclopentadiene generated in the naphtha cracking process in most cases, is dimerized and exists in a dicyclopentadiene structure.
- Cyclopentadiene and its dimer, dicyclopentadiene are Diels-Alder reaction and Retro Diels- Interconversion is possible by Alder reaction, and in particular, cyclopentadiene can be polymerized to dicyclopentadiene by thermal polymerization or catalytic polymerization.
- the tackifier used in the present invention includes at least a partially hydrogenated dicyclopentadiene-based polymer petroleum resin, at least among the dicyclopentadiene-based compounds contained in the above-described dicyclopentadiene-based polymerized petroleum resin. Hydrogen is added to some of the dicyclopentadiene, which may mean that both dicyclopentane and dicyclopentadiene are included.
- the tackifier is about 200 to about 400 parts by weight based on 100 parts by weight of the entire block copolymer including the diblock copolymer, the triblock copolymer, and the crosslinked block copolymer. Alternatively, it may be included in an amount of about 250 to about 350 parts by weight.
- the tackifier effect is insufficient, and in the hot melt adhesive composition, there may be a problem in that adhesion-related physical properties are not sufficiently exhibited, and when too much tackifier is included, the cohesive strength of the adhesive component is reduced. It is degraded, too, it is possible to cause a problem in that the adhesion-related physical properties are deteriorated.
- the plastic oil included in the hot melt adhesive composition may include a petroleum mineral oil.
- Petroleum-based mineral oil is a liquid by-product produced in the process of refining crude oil into petroleum, and is also called liquid paraffin, and is typically based on paraffinic oil and cycloalkanes based on n-alkanes.
- the petroleum mineral oil is a concept including all of the above-described oil and oil modified therefrom.
- the petroleum mineral oil is preferably a paraffinic oil, and a white oil modified by hydrotreated and/or dewaxed in the presence of a catalyst, etc. It may be more desirable.
- the plastic oil is about 50 to about 150 parts by weight, preferably about 70 to about 130 parts by weight based on 100 parts by weight of the total block copolymer including the diblock copolymer, triblock copolymer and crosslinked block copolymer. It may be included in parts by weight, or from about 90 to about 110 parts by weight.
- the content of the plastic oil is too small, there may be a problem that fluidity and low-temperature workability are deteriorated, and when the content of the plastic oil is too large, the viscosity increases too much and the adhesive performance is rather deteriorated.
- the hot melt pressure-sensitive adhesive composition according to an embodiment of the present invention may further include additives such as known light stabilizers, fillers, and ultraviolet absorbers, if necessary. These additions may be included in an amount of about 0.1 to about 10% by weight relative to the total of the hot melt adhesive composition in terms of preventing a decrease in adhesive properties, processability, and mechanical properties after adhesion.
- an adhesive member including a substrate and an adhesive layer formed on at least one surface of the substrate and formed by a hot melt adhesive composition according to an embodiment of the present invention.
- the adhesive member may be in the form of a film or tape, and the substrate may be a film having a single layer or a laminated structure of two or more layers.
- the manufacturing method of the hot melt pressure-sensitive adhesive composition of the present invention comprises the step of polymerizing a styrene-based monomer to prepare a styrene-based monomer block in the presence of a hydrocarbon solvent and a polymerization initiator (S10), by polymerizing the styrene-based monomer block and isoprene, Preparing a diblock copolymer comprising a styrene-based monomer-derived unit and an isoprene-derived unit (S20), by coupling reaction of two or more diblock copolymers with a coupling agent to prepare a triblock copolymer, and the triblock Preparing a block copolymer composition comprising the copolymer and the diblock copolymer (S30), some of the isoprene-derived units included in the triblock copolymer and the diblock copolymer, and a mixture of hydrogen peroxide and carboxylic acid By reacting, substituting some of the is
- S10 is a step of polymerizing a styrene-based monomer to prepare a styrene-based monomer block, and the type of the styrene-based monomer may be the same as the type of the styrene-based monomer for forming the unit derived from the styrene-based monomer described above.
- the hydrocarbon solvent is not particularly limited as long as it does not react with a polymerization initiator and is usually used in a polymerization reaction, and examples thereof include linear or branched hydrocarbon compounds such as butane, n-pentane, n-hexane, n-heptane or isooctane; Alkyl substituted or unsubstituted cyclic hydrocarbon compounds such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane, and methyl cycloheptane; And it may be one or more selected from the group consisting of alkyl substituted or unsubstituted aromatic hydrocarbon compounds such as benzene, toluene, xylene, and naphthalene.
- the hydrocarbon solvent may contain a polar additive to control the vinyl content and improve the polymerization rate
- the polar additive is, for example, at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethyl ethylene diamine, and benzofuran. I can.
- the polymerization initiator is not particularly limited as long as it is usually used for anionic polymerization, but, for example, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyl It may be one or more selected from the group consisting of lithium, vinyl lithium, phenyl lithium, and benzyl lithium.
- a step (S20) of preparing a diblock copolymer including a styrene-based monomer-derived unit and an isoprene-derived unit by polymerizing the styrene-based monomer block and isoprene prepared as described above may be performed.
- the styrene-based monomer block and isoprene may be polymerized in the presence of a hydrocarbon solvent and a polymerization initiator, wherein the hydrocarbon solvent and the polymerization initiator may be the same as the type of the hydrocarbon solvent and the polymerization initiator used in step S10.
- a step of preparing a triblock copolymer by performing a coupling reaction between two or more of the diblock copolymers and a coupling agent may be performed.
- a diblock copolymer that does not participate in the coupling reaction remains and may be included in the hot melt pressure-sensitive adhesive composition.
- the hot melt adhesive composition of the present invention may include a block copolymer composition including a triblock copolymer and a diblock copolymer remaining without participating in the coupling reaction.
- the coupling agent induces a coupling reaction between the diblock copolymers
- the coupling agent includes a vinyl group-containing hydrocarbon compound such as divinylbenzene as a polyfunctional coupling agent; Ester compounds such as diethyl adipate and glycidyl methacrylate; It may be a silane compound such as dimethyldichlorosilane, tetrachlorosilane, dimethyldiethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, and tetramethoxysilane.
- the coupling reaction may be performed under, for example, a temperature of 30° C. to 150° C., or 60° C. to 130° C., and a pressure condition of 0.1 bar to 10 bar, or 0.5 bar to 5 bar, within this range
- the coupling reaction can be made stably.
- a step (S40) of substituting some of the isoprene-derived units included in the triblock copolymer and the diblock copolymer with an epoxidized isoprene unit may be performed.
- This may be performed by reacting a mixture of hydrogen peroxide and a carboxylic acid with an isoprene-derived unit included in the triblock copolymer and the diblock copolymer.
- the carboxylic acid may be one or more selected from the group consisting of formic acid, acetic acid, trifluoroacetic acid, benzyloxyformic acid, dinitrobenzoic acid, and metachlorobenzoic acid.
- the hydrogen peroxide and carboxylic acid mixture may include hydrogen peroxide and carboxylic acid in a molar ratio of 1:0.8 to 1:3, 1:1 to 1:2, or 1:1.2 to 1:1.7. Within this range, epoxidation of some isoprene-derived units among the isoprene-derived units can be easily performed.
- the hydrogen peroxide and carboxylic acid mixture is 0.01 mol to 0.4 mol, specifically 0.02 mol to 0.15 mol or 0.05 mol based on 1 mol of isoprene-derived units contained in the triblock copolymer and the diblock copolymer. It may be used in an amount of 0.1 mol, and within this range, crosslinking reaction between polymer block chains does not occur, so that physical properties are prevented from deteriorating, and some isoprene-derived units can be easily epoxidized, and the epoxidation rate to be epoxidized can be reduced. By controlling within an appropriate range, the high temperature stability of the hot melt adhesive composition can be improved.
- the appropriate range of the epoxidation rate is a range in which the epoxidized isoprene unit contained in the diblock copolymer and the triblock copolymer is included in 0.5 to 5 parts by weight based on the total 100 parts by weight of the isoprene-derived unit and the epoxy and isoprene units. I can. Within this range, there is an effect of preventing a phenomenon in which the viscosity of the hot melt pressure-sensitive adhesive composition is excessively decreased or excessively increased when the hot melt pressure-sensitive adhesive composition is stored at high temperature for a long time.
- a step (S50) of preparing a crosslinked block copolymer by crosslinking at least two of the triblock copolymer and diblock copolymer including the epoxidized isoprene unit with a crosslinking agent may be performed.
- the step S50 may be performed by introducing the crosslinking agent during the blending process of the hot melt pressure-sensitive adhesive formulation and the block copolymer composition completed in step S40. More specifically, the timing of addition of the crosslinking agent is 30 from the time when 70% has passed, 80% has passed, or 85% has elapsed from the start of the mixing process with respect to the total time. It may be a time point before %, a time point before 20%, or a time point before 15%.
- the blending process may be carried out for a total of 1 hour to 2 hours, 1.2 to 1.8 hours, or 1.4 to 1.6 hours, and the timing of adding the crosslinking agent is 30 minutes before completion of the blending process, 15 It can be minutes before, or 10 minutes before.
- the crosslinking agent when added at the beginning of the blending of the hot melt adhesive formulation and the block copolymer composition that has finished step S40, that is, before 50% elapses from the start point, the crosslinking reaction starts too early. As a result, an excessively large number of crosslinked products may be formed, and when the hot melt adhesive composition is stored at a high temperature for a long time, the viscosity may be excessively decreased or excessively increased.
- the formulation for the hot melt adhesive may include at least one selected from the group consisting of a tackifier, a plastic oil, and an antioxidant.
- the formulation for the hot melt pressure-sensitive adhesive may include all of a tackifier, a plastic oil, and an antioxidant.
- the hot-melt pressure-sensitive adhesive formulation is 100 to 250 °C, 120 to 200 °C, or 150 to The process of mixing at 180° C. may be further performed.
- the crosslinking agent is as described above, and may be used in a molar ratio of 0.1 to 1, or a molar ratio of 0.3 to 0.7 with respect to 1 mol of epoxidized isoprene units contained in the block copolymer. Within this range, there is an effect of preventing a phenomenon in which the viscosity of the hot melt pressure-sensitive adhesive composition is excessively decreased or increased when stored at a high temperature for a long time.
- a 10 L reactor substituted with argon (Ar) was set to a temperature of 50° C. and a pressure of 1.0 bar, and cyclohexane (5000 g) and styrene (110 g) were added and stirred. After stirring for 10 minutes, n-butyl lithium (25 g) was added to initiate polymerization. 15 minutes after the polymerization temperature of the styrene monomer reached the maximum temperature, isoprene monomer (558 g) was added to perform polymerization. Dimethyldichlorosilane (1.0 g) as a coupling agent was added 10 minutes after the isoprene polymerization temperature reached the maximum temperature.
- the polymerization was terminated by adding methanol, which is a polymerization terminator, to prepare a composition including a diblock copolymer and a triblock copolymer.
- methanol which is a polymerization terminator
- an antioxidant was added.
- distilled water was added to a glass reactor equipped with a stirrer, and the temperature was maintained at 90°C by a circulator.
- the prepared polymer was slowly added using a dropping funnel to remove cyclohexane.
- the resulting crumb was dried at low temperature to prepare a block copolymer composition including a diblock copolymer and a triblock copolymer.
- the block copolymer composition prepared in Comparative Example 1 was slowly added dropwise and stirred at a speed of 100 rpm for 1.5 hours to completely dissolve the block copolymer composition, thereby preparing a hot melt pressure-sensitive adhesive composition.
- a mixture of hydrogen peroxide and formic acid was added, and the diblock copolymer and the triblock copolymer at 70° C. for 2 hours.
- a hot melt adhesive composition was carried out in the same manner as in Comparative Example 1, except that sodium dimethyldithiocarbamate hydrate (SDD) and an antioxidant were added, after reacting with some of the isoprene-derived units contained in and after stirring for 10 minutes.
- SDD sodium dimethyldithiocarbamate hydrate
- hydrogen peroxide and formic acid were used as the total amount of formic acid and hydrogen peroxide based on 1 mol of isoprene, 0.035 mol, and hydrogen peroxide and formic acid were used in a molar ratio of 1:1.5.
- a hot melt adhesive composition was prepared in the same manner as in Comparative Example 2, except that 0.07 moles of formic acid and hydrogen peroxide were used in the total amount of formic acid and hydrogen peroxide based on 1 mole of isoprene used in Comparative Example 2.
- a hot melt adhesive composition was prepared in the same manner as in Comparative Example 2, except that 0.175 moles of formic acid and hydrogen peroxide were used in the total amount of formic acid and hydrogen peroxide based on 1 mole of isoprene used in Comparative Example 2.
- Comparative Example 2 a hot melt adhesive composition was prepared in the same manner as in Comparative Example 2, except that 0.35 moles of formic acid and hydrogen peroxide were used in the total amount of formic acid and hydrogen peroxide based on 1 mole of isoprene used.
- a hot melt adhesive composition was prepared in the same manner as in Comparative Example 3, except that a block copolymer composition including a crosslinked block copolymer was prepared by crosslinking the block copolymer composition, and a hot melt adhesive composition was prepared using the same.
- PEG polyethylene glycol
- the content of the diblock copolymer By analyzing the content of the diblock copolymer, the styrene content, the vinyl content, the TSV viscosity, and the content of epoxidized isoprene units of the block copolymer composition including each diblock copolymer and triblock copolymer prepared in the above comparative example. It is shown in Table 1 below.
- the content of the diblock copolymer contained in the block copolymer composition was expressed in parts by weight based on the total 100 parts by weight of the diblock copolymer and the triblock copolymer.
- GPC was used as a waters 2707 autosampler, a Waters 2414 Refractive index detector, and a Waters 1515 Isocratic HPLC pump.
- the developing solvent for GPC was tetrahydrofuran (Fisher T425-4), and the sample was prepared by completely dissolving it using a shaker.
- the prepared sample was introduced using an autosampler, and the isocratic flow was 1 ml/min.
- the column temperature was set to 40°C both inside and outside. Among the two peaks on the GPC, a portion having a small molecular weight was analyzed and measured.
- the total content of units derived from styrene monomers based on 100 parts by weight of the diblock copolymer and the triblock copolymer was measured and expressed in parts by weight. Analysis was performed using Varian VNMRS 500 Mhz NMR, and 1,1,2,2-tetrachloroethane D2 from Cambridge Isotope was used as a solvent. The styrene content was determined by the value of the area measured by integrating the peak between NMR 7.4 ⁇ 6.0 ppm.
- the block copolymer composition was dissolved in toluene at a concentration of 25% by weight and measured using a rotary viscometer in a thermostat maintained at 25°C.
- the vinyl content in the diblock copolymer and the triblock copolymer was measured through a 500MHz NMR apparatus of Varian. It is expressed in weight percent based on the total weight of the diblock copolymer and the triblock copolymer.
- the content of the epoxidized isoprene unit contained in the diblock copolymer and the triblock copolymer was measured as a total amount of 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit.
- Example 1 the block copolymer composition prepared in Example 1 was slowly added dropwise and stirred at a speed of 100 rpm for 1.5 hours to completely dissolve the block copolymer composition to prepare a hot melt pressure-sensitive adhesive composition. At this time, the same amount of moles relative to the number of moles of epoxidized isoprene units contained in the triblock copolymer and diblock copolymer prepared in Example 1 10 minutes before the stirring of the block copolymer composition of Example 1 was completed.
- Example 1 a hot melt pressure-sensitive adhesive composition including a crosslinked block copolymer was prepared in the same manner as in Example 1, except that the amount of polyethylene glycol was used in a 0.5 molar ratio with respect to the number of moles of epoxidized isoprene units.
- Example 1 a hot melt adhesive composition including a crosslinked block copolymer was prepared in the same manner as in Example 1, except that the amount of polyethylene glycol was used in a molar ratio of 0.33 to the number of moles of epoxidized isoprene units.
- Example 1 a hot melt adhesive composition including a crosslinked block copolymer was prepared in the same manner as in Example 1, except that ethylene glycol was used instead of polyethylene glycol.
- a hot melt adhesive composition including a crosslinked block copolymer was prepared in the same manner as in Example 1, except that the block copolymer composition prepared in Comparative Example 4 was used.
- a hot melt adhesive composition including a crosslinked block copolymer was prepared in the same manner as in Example 1, except that the block copolymer composition prepared in Comparative Example 5 was used.
- a hot melt adhesive composition was prepared in the same manner as in Example 1, except that the block copolymer composition prepared in Comparative Example 1 was used.
- the hot melt pressure-sensitive adhesive composition prepared in the above Examples and Comparative Examples was melted on a roll of a hot melt coater at 120° C. for 5 minutes, and coated on a PET film by passing through a roller of a hot melt coater so that the thickness of the adhesive layer becomes 50 ⁇ m.
- An adhesive member was prepared.
- the hot melt adhesive composition was sufficiently put in a ring, left for 1 hour, and then a ball (diameter: 9.525mm, weight: 3.5g) was placed. The sample was heated while raising the temperature at a rate of 5° C./min, and the temperature when the ball sagged 1 inch was measured (related standard: ASTM D36).
- the adhesive member prepared above was measured for adhesiveness using the LT-1000 Loop Tack Tester.
- the adhesive member sample was cut to a width of 1 inch and a length of 150 mm, and after fixing it by folding it in half on a measuring instrument holder at room temperature, the adhesive force when it was adhered to a metal plate and dropped off was measured (Related Regulation ASTM: D 6195B)
- the adhesive member prepared above was measured for adhesive force in a 180°-peel method using a Texture Analyzer (TA).
- TA Texture Analyzer
- the adhesive member sample was cut to a width of 1 inch and a length of 150 mm, and was measured at a speed of 0.3 m/min at room temperature (related standards: ASTM D1876,
- the hot melt adhesive composition was put into a sample chamber, and a viscosity of 180° C. was measured for 30 minutes using a Brookfield viscometer (DV2+ Model, Spindle Number 27). Thereafter, the hot melt pressure-sensitive adhesive composition was allowed to stand at 180° C. for 24 hours, and then the viscosity was measured by the same method, and the viscosity at 180° C. was measured (related standard: ASTM D4402).
- Example 1 Example 2 Example 3 Example 4 Example 5 Epoxy content (parts by weight) 2 2 2 2 5 Crosslinking agent addition amount (molar ratio) One 0.5 0.33 One One Softening point (°C) 83.7 83.3 82.9 83.5 83.3 Adhesiveness (g/in 2 ) (loop tack) 1990 1998 1989 1994 2001 Peel strength(g/in)(180°peel strength) 1.089 1.090 1.088 1.089 1.098 Initial viscosity (cps) (180°C, 0h) 5483 5479 5472 5473 5600 Viscosity after 24 hours (cps) (180°C, 24h) 3850 4223 4271 3660 5994
- Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Epoxy content (parts by weight) 0 One 2 5 10 2 10 0 Crosslinking agent addition amount (molar ratio) 0 0 0 0 0 0 One 0 One Softening point (°C) 82.8 82.4 83.4 83.1 83.8 - 84.1 87.7 Adhesiveness (g/in 2 ) (loop tack) 1973 1994 1985 1997 2003 - 2006 1975 Peel strength(g/in)(180°peel strength) 1.041 1.072 1.081 1.088 1.095 - 1.102 1.051 Initial viscosity (cps) (180°C, 0h) 5463 5350 5471 5590 5687 - 5699 5470 Viscosity after 24 hours (cps) (180°C, 24h) 1425 1475 1590 1775 1890 - 6523 1430
- Examples of the present invention including a block copolymer and a crosslinked block copolymer obtained by crosslinking at least two of the triblock copolymers were excellent in terms of adhesion and peel strength with an adherend while maintaining a high softening point.
- the property of maintaining the viscosity during high temperature storage is improved, and thus it is suitable for use as an adhesive (Examples 1 to 5).
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Abstract
Description
구분division | 디블록 공중합체의 함량(중량부)Content of diblock copolymer (parts by weight) | 스티렌 함량(중량부)Styrene content (parts by weight) | 비닐 함량(중량 %)Vinyl content (% by weight) | TSV 점도(cst)TSV viscosity (cst) | 에폭시 함량(중량부)Epoxy content (parts by weight) |
비교예 1Comparative Example 1 | 19.019.0 | 15.015.0 | 10.410.4 | 12251225 | 00 |
비교예 2Comparative Example 2 | 19.019.0 | 15.015.0 | 10.410.4 | 12251225 | 1One |
비교예 3Comparative Example 3 | 19.019.0 | 15.015.0 | 10.410.4 | 12251225 | 22 |
비교예 4Comparative Example 4 | 19.019.0 | 15.015.0 | 10.410.4 | 12251225 | 55 |
비교예 5Comparative Example 5 | 19.019.0 | 15.015.0 | 10.410.4 | 12251225 | 1010 |
실시예1Example 1 | 실시예2Example 2 | 실시예3Example 3 | 실시예4Example 4 | 실시예5Example 5 | |
에폭시 함량(중량부)Epoxy content (parts by weight) | 22 | 22 | 22 | 22 | 55 |
가교제 첨가량(몰비)Crosslinking agent addition amount (molar ratio) | 1One | 0.50.5 | 0.330.33 | 1One | 1One |
연화점(℃)Softening point (℃) | 83.783.7 | 83.383.3 | 82.982.9 | 83.583.5 | 83.383.3 |
점착성(g/in 2) (loop tack)Adhesiveness (g/in 2 ) (loop tack) | 19901990 | 19981998 | 19891989 | 19941994 | 20012001 |
박리강도(g/in)(180°peel strength)Peel strength(g/in)(180°peel strength) | 1.0891.089 | 1.0901.090 | 1.0881.088 | 1.0891.089 | 1.0981.098 |
초기점도(cps)(180℃, 0h)Initial viscosity (cps) (180℃, 0h) | 54835483 | 54795479 | 54725472 | 54735473 | 56005600 |
24시간 후 점도(cps)(180℃, 24h)Viscosity after 24 hours (cps) (180℃, 24h) | 38503850 | 42234223 | 42714271 | 36603660 | 59945994 |
비교예 1Comparative Example 1 | 비교예 2Comparative Example 2 | 비교예 3Comparative Example 3 | 비교예 4Comparative Example 4 | 비교예 5Comparative Example 5 | 비교예 6Comparative Example 6 | 비교예 7Comparative Example 7 | 비교예 8Comparative Example 8 | |
에폭시 함량(중량부)Epoxy content (parts by weight) | 00 | 1One | 22 | 55 | 1010 | 22 | 1010 | 00 |
가교제 첨가량(몰비)Crosslinking agent addition amount (molar ratio) | 00 | 00 | 00 | 00 | 00 | 1One | 00 | 1One |
연화점(℃)Softening point (℃) | 82.882.8 | 82.482.4 | 83.483.4 | 83.183.1 | 83.883.8 | -- | 84.184.1 | 87.787.7 |
점착성(g/in 2) (loop tack)Adhesiveness (g/in 2 ) (loop tack) | 19731973 | 19941994 | 19851985 | 19971997 | 20032003 | -- | 20062006 | 19751975 |
박리강도(g/in)(180°peel strength)Peel strength(g/in)(180°peel strength) | 1.0411.041 | 1.0721.072 | 1.0811.081 | 1.0881.088 | 1.0951.095 | -- | 1.1021.102 | 1.0511.051 |
초기점도(cps)(180℃, 0h)Initial viscosity (cps) (180℃, 0h) | 54635463 | 53505350 | 54715471 | 55905590 | 56875687 | -- | 56995699 | 54705470 |
24시간 후 점도(cps)(180℃, 24h)Viscosity after 24 hours (cps) (180℃, 24h) | 14251425 | 14751475 | 15901590 | 17751775 | 18901890 | -- | 65236523 | 14301430 |
Claims (15)
- 스티렌계 단량체 유래 단위 및 공액디엔계 단량체 유래 단위를 포함하는 디블록 공중합체, A diblock copolymer comprising a styrene-based monomer-derived unit and a conjugated diene-based monomer-derived unit,상기 디블록 공중합체의 커플링 중합체인 트리블록 공중합체, 및A triblock copolymer, which is a coupling polymer of the diblock copolymer, and상기 디블록 공중합체 및 상기 트리블록 공중합체 중 2 이상과 가교된 가교제 유래 가교부를 포함하는 가교 블록 공중합체를 포함하며, And a crosslinked block copolymer comprising a crosslinking portion derived from a crosslinking agent crosslinked with at least two of the diblock copolymer and the triblock copolymer,상기 공액디엔계 단량체 유래 단위는 이소프렌 유래 단위 및 하기 화학식 1로 표시되는 에폭시화 이소프렌 단위를 포함하는 핫 멜트 점착제 조성물: The conjugated diene-based monomer-derived unit includes an isoprene-derived unit and an epoxidized isoprene unit represented by the following formula (1):[화학식 1] [Formula 1]
- 제1항에 있어서, The method of claim 1,상기 핫 멜트 점착제 조성물에 포함된 상기 에폭시화 이소프렌 단위는 상기 이소프렌 유래 단위 및 상기 에폭시화 이소프렌 단위의 전체 100 중량부에 대하여 0.5 내지 5 중량부인 핫 멜트 점착제 조성물.The epoxidized isoprene unit contained in the hot melt adhesive composition is 0.5 to 5 parts by weight based on the total 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit.
- 제1항에 있어서,The method of claim 1,상기 핫 멜트 점착제 조성물에 포함된 스티렌계 단량체 유래 단위는 상기 디블록 공중합체 및 트리블록 공중합체의 전체 100 중량부에 대하여 10 내지 20 중량부인 핫 멜트 점착제 조성물.The unit derived from the styrene-based monomer included in the hot melt adhesive composition is 10 to 20 parts by weight based on 100 parts by weight of the diblock copolymer and the triblock copolymer.
- 제1항에 있어서,The method of claim 1,상기 디블록 공중합체는 상기 디블록 공중합체 및 트리블록 공중합체 전체 100 중량부에 대하여 15 내지 25 중량부인 핫 멜트 점착제 조성물.The diblock copolymer is a hot melt adhesive composition of 15 to 25 parts by weight based on 100 parts by weight of the total of the diblock copolymer and the triblock copolymer.
- 제1항에 있어서,The method of claim 1,상기 가교제 유래 가교부는 폴리알킬렌글리콜 및 에틸렌글리콜로 이루어진 군에서 선택되는 1종 이상인 핫 멜트 점착제 조성물.The crosslinking agent-derived crosslinking part is at least one hot melt adhesive composition selected from the group consisting of polyalkylene glycol and ethylene glycol.
- 제1항에 있어서,The method of claim 1,상기 핫 멜트 점착제 조성물은 점착 부여제, 가소성 오일 및 산화 방지제로이루어진 군으로부터 선택된 1종 이상의 핫 멜트 점착제용 배합물을 더 포함하는 핫 멜트 점착제 조성물.The hot melt pressure-sensitive adhesive composition further comprises a blend for one or more hot melt pressure-sensitive adhesives selected from the group consisting of a tackifier, a plastic oil, and an antioxidant.
- 탄화수소 용매 및 중합 개시제의 존재 하에, 스티렌계 단량체를 중합하여 스티렌계 단량체 블록을 제조하는 단계(S10);Preparing a styrene-based monomer block by polymerizing a styrene-based monomer in the presence of a hydrocarbon solvent and a polymerization initiator (S10);상기 스티렌계 단량체 블록과 이소프렌을 중합하여, 스티렌계 단량체 유래 단위 및 이소프렌 유래 단위를 포함하는 디블록 공중합체를 제조하는 단계(S20);Polymerizing the styrene-based monomer block and isoprene to prepare a diblock copolymer including a styrene-based monomer-derived unit and an isoprene-derived unit (S20);2 이상의 상기 디블록 공중합체와 커플링제를 커플링 반응시켜 트리블록 공중합체를 제조하여, 상기 트리블록 공중합체 및 상기 디블록 공중합체를 포함하는 블록 공중합체 조성물을 제조하는 단계(S30);Preparing a triblock copolymer by coupling reaction of two or more diblock copolymers with a coupling agent to prepare a block copolymer composition comprising the triblock copolymer and the diblock copolymer (S30);상기 트리블록 공중합체 및 상기 디블록 공중합체에 포함된 이소프렌 유래 단위 중 일부와 과산화수소 및 카르복실산 혼합물을 반응시켜, 상기 이소프렌 유래 단위 중 일부를 에폭시화 이소프렌 단위로 치환하는 단계(S40); 및Reacting some of the isoprene-derived units contained in the triblock copolymer and the diblock copolymer with a mixture of hydrogen peroxide and a carboxylic acid, thereby substituting some of the isoprene-derived units with epoxidized isoprene units (S40); And상기 에폭시화 이소프렌 단위를 포함하는 트리블록 공중합체 및 디블록 공중합체 중 2 이상을 가교제로 가교시켜 가교 블록 공중합체는 제조하는 단계(S50)을 포함하는 핫 멜트 점착제 조성물의 제조방법.A method of producing a hot melt adhesive composition comprising the step (S50) of preparing a crosslinked block copolymer by crosslinking at least two of the triblock copolymer and diblock copolymer including the epoxidized isoprene unit with a crosslinking agent.
- 제7항에 있어서,The method of claim 7,상기 단계 S40에서의 상기 과산화수소 및 카르복실산은 상기 트리블록 공중합체 및 상기 디블록 공중합체에 포함된 이소프렌 유래 단위 1몰을 기준으로 0.01 몰 내지 0.4 몰로 사용하는 핫 멜트 점착체 조성물의 제조방법.The hydrogen peroxide and carboxylic acid in the step S40 are 0.01 mol to 0.4 mol based on 1 mol of isoprene-derived units contained in the triblock copolymer and the diblock copolymer.
- 제7항에 있어서,The method of claim 7,상기 카르복실산은 포름산, 아세트산, 트리플로로아세트산, 벤질옥시포름산, 디니트로벤조익산 및 메타클로로벤조익산으로 이루어진 군에서 선택되는 1종 이상인 핫 멜트 점착제 조성물의 제조방법.The carboxylic acid is at least one selected from the group consisting of formic acid, acetic acid, trifluoroacetic acid, benzyloxyformic acid, dinitrobenzoic acid and metachlorobenzoic acid.
- 제7항에 있어서,The method of claim 7,상기 과산화수소와 카르복실산 혼합물은 과산화수소와 카르복실산을 1:0.8 내지 1:3의 몰비로 포함하는 것인 핫 멜트 점착제 조성물의 제조방법.The hydrogen peroxide and carboxylic acid mixture is a method for producing a hot melt pressure-sensitive adhesive composition comprising hydrogen peroxide and a carboxylic acid in a molar ratio of 1:0.8 to 1:3.
- 제7항에 있어서, The method of claim 7,상기 디블록 공중합체 및 트리블록 공중합체에 포함된 상기 에폭시화 이소프렌 단위는 상기 이소프렌 유래 단위 및 상기 에폭시화 이소프렌 단위의 전체 100 중량부에 대하여 0.5 내지 5 중량부인 핫 멜트 점착제 조성물의 제조방법.The epoxidized isoprene unit contained in the diblock copolymer and the triblock copolymer is 0.5 to 5 parts by weight based on the total 100 parts by weight of the isoprene-derived unit and the epoxidized isoprene unit.
- 제7항에 있어서,The method of claim 7,상기 단계 S50은 핫 멜트 점착제용 배합물 및 상기 단계 S40을 마친 블록 공중합체 조성물의 배합 과정 중에 상기 가교제를 투입하여 수행되는 것인 핫 멜트 점착제 조성물의 제조방법.The step S50 is a method for producing a hot melt pressure-sensitive adhesive composition that is performed by adding the crosslinking agent during the blending process of the hot-melt pressure-sensitive adhesive formulation and the block copolymer composition after step S40.
- 제12항에 있어서,The method of claim 12,상기 핫 멜트 점착제용 배합물은 점착 부여제, 가소성 오일 및 산화 방지제로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 핫 멜트 점착제 조성물의 제조방법.The formulation for the hot melt pressure-sensitive adhesive is a method for producing a hot melt pressure-sensitive adhesive composition comprising at least one selected from the group consisting of a tackifier, a plastic oil, and an antioxidant.
- 제7항에 있어서,The method of claim 7,상기 가교제는 상기 디블록 공중합체 및 트리블록 공중합체 내 포함된 에폭시화 이소프렌 단위 1몰에 대하여 0.1 내지 1의 몰비로 사용되는 핫 멜트 점착제 조성물의 제조방법.The crosslinking agent is used in a molar ratio of 0.1 to 1 per 1 mole of the epoxidized isoprene unit contained in the diblock copolymer and the triblock copolymer.
- 제7항에 있어서,The method of claim 7,상기 가교제는 폴리알킬렌글리콜 및 에틸렌글리콜로 이루어진 군에서 선택되는 1종 이상인 핫 멜트 점착제 조성물의 제조방법.The crosslinking agent is a method of producing a hot melt adhesive composition of at least one selected from the group consisting of polyalkylene glycol and ethylene glycol.
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ZHAO ZHONGFU, LIU PEIYING, ZHANG CHUNQING, LIU WEI, DING YIFU, ZHANG YANDONG, MENG FANZHI, TANG TAO: "Synthesis and structure–property relationships of SIS-g-PB copolymers and their application in hot-melt pressure-sensitive adhesives", RSC ADVANCES, vol. 7, no. 70, 1 January 2017 (2017-01-01), pages 44068 - 44075, XP055800882, DOI: 10.1039/C7RA08180D * |
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