KR101075373B1 - Reactive polyurethane-urea hot-melt adhesive with blocked polyisocyanate - Google Patents

Abstract

The present invention is a hot melt adhesive, the molecular weight is 5000 to 200000 (g / mole) of any one of the terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is composed of 50 to 90% by weight, the molecular weight is 500 to 20000 (g / mole) 4.49 to 40% by weight of the blocked polyisocyanate prepolymer, and 0.01 to 10% by weight of a chain extender composed of a polyfunctional amine.
As described above, the reactive polyurethane urea hot melt adhesive according to the present invention is a general thermoplastic hot melt by selectively using a terminal hydroxyl group urethane prepolymer or a terminal amine urethane prepolymer, and by mixing the blocked polyisocyanate prepolymer and the chain extender, respectively. It can be selectively produced in the form of a sheet or a film, such as an adhesive, and has an effect that can be converted into thermosetting by forming urea crosslinking within 10 to 300 seconds in melt compression.

Description

Reactive polyurethane-urea hot-melt adhesive with blocked polyisocyanate}

The present invention relates to a reactive polyurethane urea hot melt adhesive, which comprises a terminal hydroxyl group urethane prepolymer or a terminal amine urethane prepolymer, optionally comprising a chain extender formed of a polyisocyanate prepolymer and a polyfunctional amine blocked with reactivity, in the form of a film. The present invention relates to a reactive polyurethane urea hot melt adhesive which is converted into thermosetting by forming urea crosslinks in a few seconds to several minutes by melt-compression at a high temperature between a fabricable and adhesively necessary base.

In general, hot melt adhesives are mainly composed of thermoplastic resins, and are 100% solids, which are applied to the adherend in a molten state and then pressed and adhered to each other. Therefore, the adhesive process is easy and the solvent does not require environmental pollution. It is widely used in the world, and its use is continuously expanding. However, as a disadvantage, it has been used in limited applications for heat resistance. In order to solve this problem, moisture-curable hot melt adhesives have been reported.

The moisture curable hotmelt adhesive consists of a urethane prepolymer comprising isocyanate reactive groups that react with moisture on the surface or surroundings. These hot melt adhesives have a disadvantage in that the molecular weight is increased only by reacting with moisture to produce an immediate adhesive force.

In order to improve this, the present invention contains a nanoclay having a layered structure modified with polyether polyol, such as Korean Patent Publication No. 10-0896271, "Moisture-curable reactive polyurethane hot melt adhesive composition and its manufacturing method". One thermoplastic polyurethane resin, wherein the thermoplastic polyurethane resin containing the nanoclay is 50 to 90 parts by weight of polyester polyol, 10 to 40 parts by weight of isocyanate compound, 10 parts by weight or less of chain extender and 0.05 to It is formed into a layered structure modified with 5 parts by weight of polyether polyol.

However, in the prior art as described above, since the isocyanate-reactive group reacts with moisture at room temperature, the hot-melt film is changed to thermosetting, and thus it is difficult to store for a long time after the film is manufactured. There was a difficult problem.

In order to solve the problems as described above, in the present invention is selectively produced in the form of a sheet or film in the same manner as the thermoplastic hot melt adhesive and formed into a urea crosslinking within 10 to 300 seconds by melt compression by high temperature to be converted into thermosetting, It is an object to provide a reactive polyurethane urea hot melt adhesive in which a hydroxyl group urethane prepolymer or a terminal amine urethane prepolymer is optionally used and a mixture of blocked polyisocyanate prepolymer and polyfunctional amine is mixed.

The present invention is a hot melt adhesive, the molecular weight is 5000 to 200000 (g / mole) of any one of the terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is composed of 50 to 90% by weight, the molecular weight is 500 to 20000 (g / mole) 4.49 to 40% by weight of the blocked polyisocyanate prepolymer, and 0.01 to 10% by weight of a chain extender composed of a polyfunctional amine.

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In addition, the terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is composed of hydroxyl groups or amines at each end [hydroxyl group (OH) or amine group (NRH or NH ₂ )] / [isocyanate group (NCO)] = 2.5 / 1 It consists of an equivalent ratio in the range of 1.05 / 1.

In addition, the equivalent of the hydroxyl group (OH) or the amine group (NRH or NH ₂ ) is larger than the equivalent of the isocyanate group (NCO).

In addition, the polyisocyanate prepolymer having blocked reactivity is blocked by the same equivalent blocking agent after the primary prepolymer is formed with isocyanate at the terminal, and the equivalent ratio of the isocyanate group and the hydroxyl group is [isocyanate group (NCO)] / [hydroxyl group (OH)] = 1.2 / 1 to 3/1.

In addition, the equivalent ratio of the isocyanate group of the reactive polyisocyanate prepolymer blocked with the hydroxyl group or the amine group included in the terminal amine urethane prepolymer and the chain extender is [isocyanate group (NCO)] / [(hydroxyl group (OH) + amine group). (NRH or NH ₂ )] = 0.95 / 1 to 1.05 / 1.

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As described above, the reactive polyurethane urea hot melt adhesive according to the present invention is a general thermoplastic hot melt by selectively using a terminal hydroxyl group urethane prepolymer or a terminal amine urethane prepolymer, and mixing the reactivity blocked polyisocyanate prepolymer and the chain extender, respectively. It can be selectively produced in the form of a sheet or a film, such as an adhesive, and has an effect that can be converted into thermosetting by forming urea crosslinking within 10 to 300 seconds in melt compression.

1 is a flow chart showing a method for producing a reactive polyurethane urea hot melt adhesive according to the present invention.

Hereinafter, a preferred embodiment of the reactive polyurethane urea hot melt adhesive according to the present invention will be described in detail.

The reactive polyurethane urea hot melt adhesive of the present invention is composed of 50 to 90% by weight of either the terminal hydroxyl group urethane prepolymer or the terminal amine urethane prepolymer having a molecular weight of 5000 to 200000 (g / mole), and includes a blocking agent and a polyisocyanate prepolymer. 4.49 to 40% by weight of a polymerized, blocked polyisocyanate prepolymer having a molecular weight of 500 to 20,000 (g / mole) and 0.01 to 10% by weight of a chain extender composed of a polyfunctional amine.

The terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is either polyester or polyether polyol is used alone or in combination, which is optionally used, organic diisocyanate and polyfunctional glycol component, polyfunctional amine component, ionic low molecular compound or Any of the nonionic hydrophilizing agents consists of a chain extender that is optionally configured.

The polyester polyol is polymerized by condensation polymerization of an aromatic or aliphatic carboxylic acid with a polyfunctional glycol component, and a molecular weight of about 500-3000 (g / mole) is used. Examples of the aromatic carboxylic acid include aromatic oxycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, p-oxy benzoic acid and p- (hydroxyethoxy) benzoic acid, trimellitic acid and pyromelli Any one of tri and tetra aromatic carboxylic acids such as triacid may be optionally used in combination.

As the aliphatic dicarboxylic acid, any one of succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid is optionally used.

As the polyfunctional glycol component, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 3-methyl-1, 5-pentanediol, 1,6-hexanediol , Neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, hydrogen and bisphenol A Ethylene oxide adducts and propylene oxide adducts may be optionally used, and any one may be optionally used in combination with tri and tetraols such as trimethylol ethane, trimethylolpropane, glycerin, pentaerythritol, and the like. .

On the other hand, the polyether polyol is formed by addition polymerization of alkylene oxide to the active hydrogen compound, the average functional group is 2 to 3, the molecular weight is a polyether polyol of about 500-3000 (g / mole), the alkylene oxide is ethylene It can be prepared by selectively mixing any one of oxide, propylene oxide, butylene oxide or a mixture of propylene oxide, butylene oxide and / or ethylene oxide.

As the chain extender, any one of a polyfunctional glycol component, a polyfunctional amine component, an ionic low molecular compound or a nonionic hydrophilizing agent is optionally used, and the polyfunctional glycol component is as described above.

As the chain extender, the polyfunctional amine component is used alone or in combination with aromatics or aliphatics. In particular, the aliphatic amine compound may be ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5 -Pentane diamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1, 6-diamino-hexane, 1,11 -Diaminoundecane, 1,12-diaminododecane, 1,3- and / or 1,4-cyclohexane diamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclo Hexane, 2,4- and / or 2,6-hexahydrotoluylene diamine, 2,4'-diaminodicyclohexyl methane, 4,4'-diaminodicyclohexyl methane and 3,3'-di Alkyl-4,4'-diaminodicyclohexyl methane (eg, 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane; ancarmine and 3,3'-diethyl-4,4 '-Diaminodicyclohexyl methane), 2,4- and / or 2,6-diaminotoluene and 2,4'- and / or 4,4'- Any one of the amino-diphenyl methane or a mixture thereof, but is optionally include, and the like. Additionally, JEFFAMINE D-230, Zephamine D-400, Zephamine D-2000 and Zephamine D-4000, available from Huntsman Corporation, may optionally be used.

On the other hand, the chain extender may be optionally used either an ionic low molecular compound or a nonionic hydrophilizing agent. The ionic low molecular weight compound is a reaction product of dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, acrylic acid and polyamine (see German Patent No. 19750186) or a sulfonate group-containing polyol component as 2-butenediol and sodium bisulfite Either of the propoxylated adducts of, or polyesters described in EP 064331 and formed from salts of sulfoisophthalic acid can optionally be used. In addition, as the nonionic hydrophilizing agent, a polyether polyol having a molecular weight of 500-3000 (g / mole) having an ethylene oxide group of 50% or more by weight is used.

In addition, the organic diisocyanate is 2,4-trilene diisocyanate, 2,6-trilene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexane methylene diisocyanate, tetramethylene di Isocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 2,4'-naphylene diisocyanate, 1,5'-naphthalene diisocyanate, p-xylene diisocyanate, m-xylenedi Isocyanate, 1, 3- diisocyanate methylcyclohexane, 1, 4- diisocyanate methylcyclohexane 4,4'- diisocyanate dicyclohexane 4,4'- diisocyanate dicyclohexyl methane, isopron diisocyanate, etc., These may be used selectively either one or in combination of two or more.

In addition, the terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is a polyester polyol or a polyether polyol is used alone or mixed, either one is selectively used, and a polyfunctional glycol component, a polyfunctional amine component as an organic diisocyanate and a chain extender, It is composed of an ionic low molecular compound or a nonionic hydrophilizing agent, and the equivalent ratio of a hydroxyl group or an amine group and an isocyanate group formed at the end of the hydroxyl group or the amine is [hydroxyl group (OH) or amine group (NRH or NH ₂ )] / [isocyanate Group (NCO)] = 2.5 / 1 ~ 1.05 / 1, the equivalent of the hydroxyl group (OH) or amine group (NRH or NH ₂ ) is formed larger than the equivalent of the isocyanate group (NCO).

In addition, the polyisocyanate prepolymer in which the reactivity is blocked has an average molecular weight of 500-20000 (g / mole), and a primary prepolymer is prepared from an excess of isocyanate at the terminal. At this time, any one of the above-described polyester polyol and polyether polyol may be used alone or in combination. The glycol component, ionic low molecular compound or nonionic hydrophilizing agent mentioned in organic diisocyanate and chain extender may be used to contain isocyanate groups. A hydroxyl equivalent ratio is manufactured in the range of [isocyanate group (NCO)] / [hydroxyl group (OH)] = 1.2 / 1-3/1. In the second stage, the remaining active isocyanate is blocked by the same equivalents with a blocking agent. At this time, the equivalent ratio of the amine or alcohol, which is a reactive group of the terminal isocyanate and the blocking agent, to the active isocyanate is synthesized from [NCO] / [OH or NH ₂ ] = 0.95 / 1 to 1.05 / 1. The blocking agents used here are alcohols, lactams, oximes, malonates, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines such as butanone oxime, diisopropylamine, 1,2,4-triazole , Dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetone oxime, 3,5-dimethylpyrazole, ε-caprolactam may optionally be used.

Reactive polyisocyanate prepolymers are also introduced as products, such as "ADIPRENE BL 11", "ADIPRENE BL 16", "ADIPRENE BL 31", "ADIPRENE BL 40" and "ADIPRENE BL 45" from Uniroyal Chemical Company. , "ADIPRENE BL 46", "ADIPRENE BLM 500", "ADIPRENE BLP 60", or "ADIPRENE BLP 65", and "TRIXENE" by Baxenden Chemicals, Ltd. (eg, "TRIXENE BI 7986", "TRIXENE BI 7985 "," TRIXENE BI 7951 "," TRIXENE BI 7950 "," TRIXENE BI 7960 ", or" TRIXENE BI 7770 ".

In particular, the equivalent ratio of the hydroxyl group or the amine group of the reactivated isocyanate group and the chain extender or the terminal amine urethane prepolymer of the reactive polyisocyanate prepolymer is [isocyanate group (NCO) / hydroxyl group (OH) or amine group ( NRH or NH ₂ )] = 0.95 / 1 to 1.05 / 1.

The method for preparing a reactive polyurethane urea hot melt adhesive of the present invention selectively removes a terminal hydroxyl group urethane prepolymer and a terminal amine urethane prepolymer, a blocked polyisocyanate prepolymer, and a chain extender below the active temperature of the blocked polyisocyanate prepolymer. Dilution or mixing or selective mixing (S10) in the water phase containing the ionic low molecular weight compound or nonionic hydrophilizing agent.

The terminal hydroxyl group urethane prepolymer and the terminal amine urethane prepolymer are polyester or polyether polyols which are used alone or in combination, and optionally, organic isocyanates, and polyfunctional glycol components, polyfunctional amine components, and ionic low molecules. Consisting of a chain extender optionally configured with either a compound or a nonionic hydrophilizing agent [hydroxyl group (OH) or amine group (NRH or NH ₂ ) / isocyanate group (NCO)] = 2.5 / 1 to 1.05 / 1 ( OH or NRH, NH ₂ ]> [NCO]).

The blocked polyisocyanate prepolymer has an average molecular weight of 500-20000 (g / mole), and a primary prepolymer is prepared with an excess of isocyanate at the end. The components may be used either alone or in combination of polyester polyols and polyether polyols, and contain polyfunctional glycol components, ionic low molecular compounds or nonionic hydrophilizing agents mentioned in organic diisocyanates and chain extenders. Thus, an isocyanate group and hydroxyl group equivalent ratio are manufactured in the range of [isocyanate group (NCO)] / [hydroxyl group (OH)] = 1.2 / 1-3/1. In the second stage, the remaining active isocyanate is blocked by the same equivalents with a blocking agent.

In the present invention, the blocked polyisocyanate prepolymer and the terminal hydroxyl group urethane prepolymer or the terminal amine urethane prepolymer are prepared by mixing with each other in a solvent type or water dispersion type dissolved in a solvent. Toluene, benzene, xylene, methyl ethyl ketone, acetone, ethyl acetate, etc. may be optionally used in the solvent type, and the water dispersion type is a chain extender and contains an ionic low molecular compound or a nonionic hydrophilizing agent. Are synthesized. For a detailed description of the production method of the water-dispersed polyurethane can be referred to the contents of US Patent No. 6,017,998 or Korean Patent Publication No. 10-2007-101149.

The terminal hydroxyl group urethane prepolymer and the terminal amine urethane prepolymer are each used alone or in combination, and any one of 50 to 95% by weight is used, and 4.49 to 40% by weight of the blocked polyisocyanate prepolymer, polyfunctional amine or polyfunctional glycol 0.01 to 10% by weight of a chain extender composed of any one is mixed, and diluted or mixed with solvents to facilitate processing below the active temperature of the blocked polyisocyanate prepolymer, or an ionic low molecular weight compound or a nonionic hydrophilizing agent is added. It is optionally mixed in the moisture phase contained.

In particular, the equivalent ratio of the isocyanate group, chain extender or terminal hydroxyl group urethane prepolymer and terminal amine urethane prepolymer to the isocyanate group (NCO) / hydroxyl group (OH) or amine of the polyisocyanate prepolymer having blocked reactivity is Group (NRH or NH ₂ )] = 0.95 / 1 to 1.05 / 1.

After going through the mixing step (S10), using a conventional applicator (Applicator) on the base of the release film, plastic, metal, wood, fiber, etc., the dried solids are manufactured to a thickness of 0.1 ~ 0.5mm, After the drying step (S20) at 40 ~ 100 ℃ to obtain a hot melt adhesive on the laminating film or laminating sheet. After the drying step (S20) consists of a hot melt adhesive on the film or sheet selectively released between the release film, plastic, metal, wood, fibers to melt bonding step (S30) to melt bonding at 120 ~ 200 ℃.

The adhesive layer cured through the rapid urea reaction of the polyisocyanate, terminal hydroxyl urethane prepolymer, terminal amine urethane prepolymer, and amine and alcohol, which are functional groups of polyfunctional amine or polyfunctional glycol, which are reactivated by going through the melt bonding step (S30) as described above. Is no longer melted, and exhibits excellent adhesion strength and at the same time a rapid solidification rate that solidifies within 10 to 300 seconds.

As described above, the reactive polyurethane urea hot melt adhesive adhesive composition according to the present invention is optionally used either of a terminal hydroxyl group urethane prepolymer or a terminal amine urethane prepolymer, by mixing a blocked polyisocyanate prepolymer and a chain extender, respectively. It can be selectively produced in sheet or film form like a general thermoplastic hot melt adhesive and can be converted into thermosetting by forming urea crosslinking within 10 to 300 seconds.

The present invention is not limited to the preferred embodiments of the above-described features, and various modifications can be made by those skilled in the art without departing from the gist of the present invention as claimed in the claims. Of course, such changes will fall within the scope of the claims.

Claims (7)

In the hot melt adhesive composition,
A terminal hydroxyl group urethane prepolymer having a molecular weight of 5000 to 200000 (g / mole) or a terminal amine urethane prepolymer is composed of 50 to 90% by weight, and a reactive blocked polya having a molecular weight of 500 to 20000 (g / mole). A reactive polyurethane urea hot melt adhesive, comprising 4.49 to 40% by weight of isocyanate prepolymer and 0.01 to 10% by weight of a chain extender composed of a polyfunctional amine. delete The method of claim 1,
The terminal hydroxyl group urethane prepolymer or terminal amine urethane prepolymer is composed of hydroxyl group and amine terminal respectively [hydroxyl group (OH) or amine group (NRH or NH ₂ )] / [isocyanate group (NCO)] = 2.5 / 1 ~ 1.05 Reactive polyurethane urea hot melt adhesive, characterized in that consisting of an equivalent ratio of / 1 range. The method of claim 3,
Reactive polyurethane urea hot melt adhesive, characterized in that the equivalent of the hydroxyl group (OH) or amine group (NRH or NH ₂ ) is greater than the equivalent of the isocyanate group (NCO). The method of claim 1,
The reactivity blocked polyisocyanate prepolymer is blocked by the same equivalent blocking agent after the primary prepolymer is formed with isocyanate at the terminal, the equivalent ratio of the isocyanate group and the hydroxyl group is [isocyanate group (NCO)] / [hydroxyl group (OH) )] = Reactive polyurethane urea hot melt adhesive, characterized in that the range of 1.2 / 1 to 3/1. The method of claim 1,
The equivalent ratio of the isocyanate group, the terminal hydroxyl group urethane prepolymer, the terminal amine urethane prepolymer, and the hydroxyl group or amine group included in the chain extender of the blocked polyisocyanate prepolymer is [isocyanate group (NCO)] / [(hydroxyl group (OH ) + Amine group (NRH or NH ₂ )] = 0.95 / 1 ~ 1.05 / 1 Reactive polyurethane urea hot melt adhesive, characterized in that configured in the range. delete

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