KR20170029804A - Polyurethane resin composition and methode for manufacture thereof - Google Patents
Polyurethane resin composition and methode for manufacture thereof Download PDFInfo
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- KR20170029804A KR20170029804A KR1020150126852A KR20150126852A KR20170029804A KR 20170029804 A KR20170029804 A KR 20170029804A KR 1020150126852 A KR1020150126852 A KR 1020150126852A KR 20150126852 A KR20150126852 A KR 20150126852A KR 20170029804 A KR20170029804 A KR 20170029804A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
Abstract
Description
The present invention relates to a polyurethane resin composition and a process for producing the same. More specifically, the polyurethane resin composition is prepared by using a polyol compound having a relatively high average functionality of 2 to 2.4 in the production of polyurethane, thereby improving physical properties such as heat resistance and abrasion resistance of the polyurethane resin composition And a modified isocyanate compound having a relatively low isocyanate group at the same time, and a method for producing the polyurethane resin composition.
Generally, a polyurethane resin is a compound having a urethane bond in a molecule, and is a polymer compound synthesized mainly by the reaction of a diisocyanate with a polyol compound. The polyurethane resin is superior in abrasion resistance, oil resistance, solvent resistance and elasticity Adhesives, coating agents, injection materials, paints, inks, paints, foams, shoe parts, clothing, and medical polymers.
One of the most representative applications of such a polyurethane resin is an adhesive, and a polyurethane adhesive is mainly manufactured and used as a hot melt polyurethane adhesive. The properties of the hot-melt polyurethane adhesive vary depending on the application to be used. For example, in the textile field, since softness is important, a modulus soft type is preferable, while in the building materials field, a rigid type .
On the other hand, the polyurethane resin is classified into foam and non-foam according to the molding method, and the foam is classified into soft, hard and radial quality, and the bubble is usually called CASE, and the coating, adhesive, sealant, elastomer CASE Respectively. Here, CASE stands for Coating, Adhesive, Sealant, and Elastomer.
The polyurethane resin is also used as a good elastic adhesive. The elastic adhesive does not have curability enough to break the material, and since it is flexible and elastic in itself, it is deformed against an external force to uniformly disperse the stress generated in the joint portion And the like. It is a relatively new type classified as functional adhesive because it has elasticity different from conventional adhesive and can be used in the temperature range of US Federal Standard MMM -A -132A / TYPE 1 / LAS (-55 ~ + 85 ℃) 100%, hardness JISA 50 or more.
The materials used for the production of the elastic adhesive are representative of a modified resin system composed of a silicone resin, a modified silicone resin, a polysulfide resin, a polyurethane resin, an epoxy resin, etc. Recently, a modified silicone resin is reinforced with an epoxy resin It is also said.
However, in order to improve the physical properties such as heat resistance and abrasion resistance, such polyurethane resin is required to have a number of average functionalities of the polyol used in the production, which is smaller or larger than the average functionality of the polyol used in general polyurethane production There is a problem that the adhesive force as a pressure-sensitive adhesive is lowered.
Therefore, even when the average number of functionalities of the polyol to be used is changed so as to easily attain improvement in physical properties such as heat resistance and abrasion resistance of the polyurethane resin composition, the adhesive force inherent to the polyurethane resin composition is not deteriorated, There is a need to develop a technique capable of enhancing or enhancing the performance of the system.
It is an object of the present invention to provide a polyurethane resin composition that maintains or improves adhesion properties inherent to polyurethane resins while exhibiting excellent physical properties such as heat resistance and abrasion resistance, and a method for producing the same.
In order to achieve the above object, the polyurethane resin composition according to the present invention comprises a polyol compound (A) having an average functionality of 2 to 2.4 and an NCO / OH ratio of the polyol compound (A) and the isocyanate compound Wherein the isocyanate compound (B) comprises an isocyanate compound (B) having an MDI (methylene diphenyl diisocyanate) isocyanate compound (a) and a uretonimine group, and the isocyanate compound And a modified isocyanate compound (b) having an NCO content of 25 to 32%.
The NCO / OH ratio of the polyol compound (A) and the isocyanate compound (B) may be 0.8 to 1.2.
The polyol compound (A) may include a first polyol having an average molecular weight of 1400 to 2700, a second polyol having an average molecular weight of 4800 to 5200, a chain extender, and a gelling catalyst.
The chain extender may be selected from polyhydric alcohols, diols, amines, diamines, aminoalcohols and / or ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4- But are not limited to, glycerin, polyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, 1,3-butylene glycol, diethanolamine, 4,4'-methylene-bis (2-chloroaniline).
The gelling catalyst may be selected from the group consisting of triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpyrrole, 2- (dimethylamino- ethoxy) -ethanol, diazabicyclo- 2,2) -octane, esters of titanic acid, iron compounds, tin diacetates, tin dioctate, tin dilaurate, dibutyltin dilaurate and dialkyl tin salts of aliphatic carboxylic acids. Or more.
The polyol compound (A) may have an average functionality of 2 to 2.2.
The polyol compound (A) may comprise a polyol selected from the group consisting of a polyester-based polyol and a polyether-based polyol.
The MDI-based isocyanate compound (a) comprises 70 to 80% by weight of polymeric MDI and the modified isocyanate compound (b) is a monomeric MDI (Monameric MDI) and a carbodiimide modified MDI). ≪ / RTI >
The isocyanate having the uretonimine group may be uretonimine modified MDI.
The MDI-based isocyanate compound (a) may have an isocyanate group (NCO) content of 35 to 40%.
The present invention also relates to a process for preparing a polyol compound (A) which comprises preparing a polyol compound (A) having an average functionality of 2 to 2.4, preparing a polyol compound (A) comprising a methylene diphenyl diisocyanate (MDI) isocyanate compound (a) (A) and an isocyanate compound (B) containing an isocyanate group having an isocyanate group (Uretonimine) group and at the same time containing a modified isocyanate compound (b) having an isocyanate group (NCO) content of 25 to 32, (A) and an isocyanate compound (B) in a reactor to prepare an isocyanate compound (B) prepared so that the NCO / OH ratio of the polyol compound ≪ / RTI >
The polymerization step may include stirring at a stirring speed of 2500 to 3500 rpm so that the polyol compound (A) and the isocyanate compound (B) can be uniformly mixed with each other.
The polymerization step may be carried out at a temperature of from 55 to 75 < 0 > C.
The polymerization step may be carried out for 8 to 20 seconds.
According to the present invention, there is provided a polyurethane resin composition which can be used in various fields such as textile field, building material field, and electronic device field such as LCD, LED, etc. The polyurethane resin composition exhibits excellent physical properties such as heat resistance and abrasion resistance, An excellent adhesive force inherent to the resin can be maintained or improved.
1 is a graph showing the number of moles of isocyanate having an uretonimine group according to an isocyanate group content of a polyurethane resin composition according to an embodiment of the present invention.
2 is a graph showing changes in urethane bond and urea bond according to the number of moles of uretonimine and the average functional group (fav) of the polyol compound (A) in the polyurethane resin composition according to an embodiment of the present invention. 1620-1 wave number is a graph of infrared absorption spectroscopy (FT-IR) at (wavenumber).
3 is a graph showing changes in urethane bond and urea bond according to the number of moles of uretonimine and the average functional group (fav) of polyol compound (A) in a polyurethane resin composition according to an embodiment of the present invention. 15 is a graph by infrared absorption spectroscopy (FT-IR) at 1500 -1 Wavenumber.
4 is 1760-1620 wave number -1 showing a change amount of a urethane bond and urea bond according to the number of isocyanate group content (NCO%) and mole (mol) of urea tone migration from the polyurethane resin composition according to an embodiment of the present invention (FT-IR) at Wavenumber.
5 is 1560-1500 wave number -1 showing a change amount of a urethane bond and urea bond according to the number of isocyanate group content (NCO%) and mole (mol) of urea tone migration from the polyurethane resin composition according to an embodiment of the present invention (FT-IR) at Wavenumber.
6 is a graph showing changes in 90 degree peel strength depending on the number of moles of uretonimine and the average functional group (fav) of the polyol compound (A) in the polyurethane resin composition according to an embodiment of the present invention.
7 and 8 are cross-sectional views when the average functional group (fav) of the polyol compound (A) is 2 and the number of moles of uretonimine is 0.003842 in the polyurethane resin composition according to an embodiment of the
9 and 10 are cross-sectional views of a polyurethane resin composition according to an embodiment of the present invention when the average functional group (fav) of the polyol compound (A) is 2.4 and the number of moles of uretonimine is 0.004119 2 is a SEM (Scanning Electron Microscope) image.
The terms or words used in the present specification and claims are intended to mean that the inventive concept of the present invention is in accordance with the technical idea of the present invention based on the principle that the inventor can appropriately define the concept of the term in order to explain its invention in the best way Should be interpreted as a concept.
Hereinafter, the polyurethane resin composition according to the present invention will be described in detail. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Is provided to fully inform the user.
The polyurethane resin composition of the present invention comprises a polyol compound (A) having an average functionality of 2 to 2.4 and an isocyanate compound (B) having an NCO / OH ratio of from 0.5 to 1.5 of the polyol compound (A) Wherein the isocyanate compound (B) comprises an isocyanate compound having a methylene diphenyl diisocyanate (MDI) isocyanate compound (a) and a uretonimine group, and at the same time, an isocyanate group (NCO) To (32), which is a modified isocyanate compound (b).
Generally, a polyurethane adhesive composition is prepared by forming a urethane group by a chemical reaction between an isocyanate compound having a polyfunctional group and a polyol. Since an isocyanate group (-N═C═O) tends to be very easily bonded (urethane bond) to a hydroxyl group (-OH), when a polyol having two hydroxyl groups is reacted with a diisocyanate, a linear polymer is formed And the polymer thus formed is polyurethane.
The polyurethane can be produced in a wide variety of ways and forms depending on the intended use and purpose, and it is a polyurethane adhesive resin composition reinforced with heat resistance and abrasion resistance, which increases the average number of functionalities of the added polyol ≪ / RTI > However, when the average number of functionalities of the polyol is increased in order to improve the physical properties such as heat resistance and abrasion resistance of the polyurethane, the degree of crosslinking and cohesive force of the polyurethane resin composition increases, The anchoring effect on the adhesive interface is deteriorated and consequently the adhesive force of the polyurethane adhesive resin composition is lowered.
The polyurethane resin composition according to the present invention can increase the number of Average Functionality of the polyol compound (A) to a value in the range of 2 to 2.4, which is larger than the average functional group number of the polyol in the general polyurethane resin composition, Even when the physical properties such as heat resistance and abrasion resistance of the polyurethane resin composition are improved, it is possible to appropriately control the polyurethane resin composition so as to suppress excessive crosslinking and increase in cohesive force, .
That is, the polyurethane resin composition according to the present invention achieves a smooth urethane-forming reaction with the polyol compound (A) through an MDI (methylene diphenyl diisocyanate) isocyanate compound (a) (A) having an average number of functional groups through a modified isocyanate compound (b) containing an isocyanate group having a uretonimine group and having an isocyanate group (NCO) content of 25 to 32 at the same time The degree of crosslinking and cohesive force of the polyurethane resin composition which can be excessively increased by the reaction can be controlled to maintain the wettability of the polyurethane resin composition and the anchoring effect on the adhesive interface It is possible to realize an excellent adhesive force peculiar to the polyurethane resin composition.
The polyurethane resin composition according to the present invention contains an isocyanate compound such that the NCO / OH ratio of the polyol compound (A) and the isocyanate compound (B) is 0.5 to 1.5, so that the polyol compound (A) And the ratio of the isocyanate group (-N = C = O) functional group and the hydroxyl group (-OH) of the isocyanate compound is controlled to be minimized to minimize the amount of the unreacted polyol compound (A) or isocyanate compound, It is possible to obtain a physical property and further improve the adhesive force. The polyol compound (A) and the isocyanate compound (B) preferably have an NCO / OH ratio of 0.8 to 1.2, more preferably 1: 1, to further improve the physical properties and adhesion of the polyurethane resin composition have.
The polyol compound (A) is not particularly limited as long as it is a polyol compound (A) having an average functionality of 2 to 2.4, preferably a first polyol having an average molecular weight of 1400 to 2700, an average molecular weight of 4800 to 5200 A second polyol, a chain extender, and a gelling catalyst.
The first polyol having an average molecular weight of 1400 to 2700 may be prepared by preparing a first low molecular weight polyol having an average molecular weight of 1400 to 1500 and a second low molecular weight polyol having an average molecular weight of 2600 to 2700, Among these low molecular weight polyols, the first low molecular weight polyol having an average molecular weight of 1,400 to 1,500 has an OH value of 108 to 116 mgKOH / g, which is a very high value of OH value. Therefore, the polyurethane resin composition contains a urethane group Or allophanate bond is increased so that the bonding by the van der Waals attractive force on the surface of the adherend is strengthened so that the polyurethane resin composition exhibits excellent adhesion.
The second polyol having an average molecular weight of 4800 to 5200 is a high molecular weight polyol which serves to increase the average number of functional groups of the polyurethane resin composition and to impart mechanical properties such as heat resistance and abrasion resistance of the polyurethane resin composition .
The chain extender is a material used in a chain stretching reaction for modifying a hydrophilic polymer. The chain extender is not limited in its kind, and another polyol of the same kind as the first polyol or the second polyol may be used as a chain extender. Such chain extender may be, for example, polyhydric alcohols having a molecular weight of from 50 to 500, diols, amines, diamines, aminoalcohols and / or ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, Butylene glycol, dipropylene glycol, dibutylene glycol, 1,3-butylene glycol, diethanolamine, triethanolamine, 1,5-butylene glycol, Naphthalene diamine, and 4,4'-methylene-bis (2-chloroaniline).
The gelling catalyst may be a known polyurethane catalyst which is used for synthesizing a polyurethane resin composition. It is preferably 0.01 to 0.15 parts by weight based on 100 parts by weight of the polyol compound (A). When the content of the catalyst is less than the above-mentioned range, the reaction rate is low, and when the content is in excess of the range defined above, the reaction yield may be lowered due to the abrupt reaction.
The catalyst may be selected from the group consisting of triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpyrrole, 2- (dimethylamino-ethoxy) -ethanol, diazabicyclo- , 2,2-octane, esters of titanic acid, iron compounds, tin diacetate, tin dioctate, tin dilaurate, dibutyltin dilaurate or dialkyltin salts of aliphatic carboxylic acids, etc. At least one compound selected from the group consisting of
The average number of functional groups of the polyol compound (A) may be controlled within a range of from 2 to 2.4, depending on the use of the polyurethane resin composition to be produced, and preferably from 2 to 2.2, (A) can be used. The polyurethane resin composition having an average number of functional groups of the polyol within this range exhibits excellent heat resistance and abrasion resistance, and at the same time can exhibit the most excellent adhesive force as compared with a polyurethane resin composition having an average number of functional groups of a polyol in a different range.
The type of polyol contained in the polyol compound (A) is not limited, and for example, polyester polyol or polyether polyol may be used.
Specific examples of the polyester polyol include diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- (Hereinafter abbreviated as 'NPG'), 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, Pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2- Called low molecular weight glycols such as 1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A, Condensation reaction of dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naphthylenedicarboxylic acid, their acid esters and acid anhydrides Terminal hydroxyl group Those having a polyester is preferred.
Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polyoxypropylene triol, and polytetramethylene glycol.
The polyether polyol can be prepared by reacting at least one alkylene oxide containing from 2 to 4 carbon atoms in an alkylene radical with a starting material containing a hydrogen atom bonded to two active groups. Suitable alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide, preferably ethylene oxide, propylene oxide and 1,2- - Mixtures of propylene oxide and ethylene oxide are preferred. Suitable examples of starting materials are water, aminoalcohols such as N-alkyl-diethanolamine (for example N-methyl-diethanolamine) and diols (for example ethylene glycol, 1,3-propylene glycol, , 4-butanediol and 1,6-hexanediol).
Other suitable polyether diols are the polymerization products of tetrahydrofuran containing hydroxyl groups. A trifunctional polyether in a proportion of from 0 to 30 parts by weight relative to the bifunctional polyether may be used, but the maximum amount should be such that a thermoplastically processable product is obtained. These linear polyether polyols can be used singly or in the form of a mixture of two or more thereof.
The MDI-based isocyanate compound (a) preferably contains 70 to 80% by weight of polymeric MDI and the modified isocyanate compound (b) is a monomeric MDI (Monameric MDI) and a carbodiimide-modified MDI (Carbodiimide Modified MDI).
The polyurethane resin composition of the present invention comprises a polymeric MDI (polymeric MDI) represented by the following general formula (1) in an amount of 70 to 80% by weight based on the whole MDI-based isocyanate compound (a) The same monomeric MDI (Monomeric MDI) can be contained in an amount of 30 to 20% by weight based on the whole MDI-based isocyanate compound (a).
[Chemical Formula 1] < EMI ID =
Wherein n is from 3 to 6
The MDI-based isocyanate compound (a) improves the adhesion of the polyurethane resin composition by providing an appropriate degree of crosslinking and cohesive force to the polyurethane resin composition by a high polymeric MDI (MDI) content of 70 to 80% by weight .
The modified isocyanate compound (b) may further comprise monomeric MDI and Carbodiimide Modified MDI (MDI) as shown below in addition to an isocyanate having a uretonimine group. have. The isocyanate having a uretonimine group is preferably Uretonimine Modified MDI (Urethane imine modified MDI) represented by the following chemical formula (4).
(3)
[Chemical Formula 4]
Here, the uretonimine modified MDI may be contained in an amount of 20 to 30% by weight based on the total amount of the modified isocyanate compound (b), and the monomeric MDI (monameric MDI) and the carbodiimide modified MDI Carbodiimide Modified MDI) may be contained in an amount of 80 to 70% by weight based on the whole of the modified isocyanate compound (b).
The Uretonimine Modified MDI (MDI) and Carbodiimide Modified MDI (MDI), when the average number of functional groups of the polyol compound increases in the polyurethane resin composition and the crosslinking degree and the cohesive force are excessively increased, A proper spacing space is formed so as to lower the binding probability of Van der waals bonding and hydrogen bonding between molecules constituting the polyurethane such as the polyol compound, the polymeric MDI and the monomeric MDI, The fluidity of the polymer main chain of the polymeric MDI (Polymeric MDI) can be increased and the degree of crosslinking and cohesive force of the polyurethane resin composition can be appropriately controlled. Accordingly, the polyurethane resin can realize the wettability and the anchoring effect on the adhesive interface that can exhibit the optimum adhesive force.
The MDI-based isocyanate compound (a) preferably has an isocyanate group (NCO) content of 35 to 40%, and the modified isocyanate compound (b) preferably has an isocyanate group (NCO) content of 27 to 30% . Since the MDI-based isocyanate compound (a) mainly plays a role in cross-linking by bonding with polyol compounds in a polyurethane resin composition, it has a relatively high content of isocyanate group (NCO) of 35 to 40 The modified isocyanate compound (b) serves to form a constant spacing space between the molecules constituting the MDI-based isocyanate compound (a) to provide the fluidity of the polymer main chain. Thus, a relatively low isocyanate of 27 to 30 Gt; (NCO) < / RTI >
The present invention also relates to a process for preparing a polyol compound (A) which comprises preparing a polyol compound (A) having an average functionality of 2 to 2.4, preparing a polyol compound (A) comprising a methylene diphenyl diisocyanate (MDI) isocyanate compound (a) (A) and an isocyanate compound (B) containing an isocyanate group having an isocyanate group (Uretonimine) group and at the same time containing a modified isocyanate compound (b) having an isocyanate group (NCO) content of 25 to 32, (A) and an isocyanate compound (B) in a reactor to prepare an isocyanate compound (B) prepared so that the NCO / OH ratio of the polyol compound A method for preparing a composition is provided.
The process for producing a polyurethane resin composition according to the present invention increases the number of Average Functionality of the polyol compound (A) in the range of 2 to 2.4, which is larger than the average number of functional groups of the polyol, in the general polyurethane resin composition, Even when a polyurethane resin composition having improved physical properties such as heat resistance and abrasion resistance of a urethane resin composition is produced, the polyurethane resin composition is suitably controlled so as to suppress excessive crosslinking and an increase in cohesive force of the polyurethane resin composition to improve heat resistance and wear resistance It is possible to produce a polyurethane resin composition having excellent adhesive strength while improving physical properties.
That is, the polyurethane resin composition according to the present invention achieves a smooth urethane-forming reaction with the polyol compound (A) through an MDI (methylene diphenyl diisocyanate) isocyanate compound (a) (A) having an average number of functional groups through a modified isocyanate compound (b) containing an isocyanate group having a uretonimine group and having an isocyanate group (NCO) content of 25 to 32 at the same time The degree of crosslinking and cohesive force of the polyurethane resin composition which can be excessively increased by the reaction can be controlled to improve the wettability of the polyurethane resin composition and the anchoring effect on the adhesive interface, And abrasion resistance of the polyurethane resin composition, It can be manufactured in a simple way.
The process for producing a polyurethane resin composition according to the present invention is a process of mixing and polymerizing an isocyanate compound (B) so that the polyol compound (A) and the isocyanate compound (B) have an NCO / OH ratio of from 0.5 to 1.5 (A) and the isocyanate group (-N═C═O) functional groups of the polyol compound (A) and the isocyanate compound (B) within the polyurethane resin composition, Or the amount of the isocyanate compound (A) can be minimized, so that uniform physical properties can be obtained throughout the polyurethane adhesive composition and the adhesive strength can be further improved.
The polymerization step may include stirring at a stirring speed of 2500 to 3500 rpm so that the polyol compound (A) and the isocyanate compound (B) can be mixed uniformly, more preferably 2900 to 3100 rpm And stirring the mixture at a stirring speed.
When the stirring speed is 2500 rpm or less, the possibility of generating unreacted materials in the polyol compound (A) and the isocyanate compound (B) increases, and the physical properties and adhesive force of the finally prepared polyurethane resin composition can be lowered. Is not less than 3500 rpm, bubbles may be generated in the mixture of the polyol compound (A) and the isocyanate compound (B) to lower the physical properties of the polyurethane resin composition.
The polymerization conditions in the above polymerization step are preferably carried out under conditions that the polymerization of the polyol compound (A) and the isocyanate compound (B) can be optimized. For example, the polymerization step is preferably performed at a temperature of 55 to 75 캜 for 8 to 20 seconds so that polymerization of the polyol compound (A) and the isocyanate compound (B) can proceed smoothly.
When the reaction temperature is lower than 55 ° C, the reaction rate becomes too slow and the reaction yield is lowered. When the reaction temperature is higher than 75 ° C, the polyol compound (A) and the isocyanate compound (B) may be decomposed or modified . The polymerization time in the range of 8 to 20 seconds is a polymerization reaction time condition in which almost all the polyol compound (A) and the isocyanate compound (B) are polymerized and the generation of bubbles can be minimized.
< Example 1>
The polyurethane resin composition according to Example 1 of the present invention was produced by using the polyol compound (A) and the isocyanate compound (B) materials shown in Tables 1 and 2 and the conditions as shown in Table 3.
[Table 1]
[Table 2]
[Table 3]
A polyurethane resin composition sample prepared according to the above conditions is cast between a sillicon coated PET film and an OHP film (polyester) using tempered glass. (Sillicon sheet thickness 1mm). The adhesive was dried in convection oven (50 ~ 60 ℃) for 1 hour and then passed through a 90 degree peel test (Crosshead speed: 300mm / min) using UTM (Ametek. (8 scan, 4000-400 cm -1 ) analysis using a FT-IR (Perkinelmer) Frontier product to analyze the change in urethane bond or urea bond content in the synthesized material. Respectively.
FIG. 1 is a graph showing the number of moles of isocyanate having a uretonimine group according to an isocyanate group content of a polyurethane resin composition according to an embodiment of the present invention.
2 is a graph showing changes in urethane bond and urea bond according to the number of moles of uretonimine and the average functional group (fav) of a polyol compound (A) in a polyurethane resin composition according to an embodiment of the present invention. (FT-IR) at 1620 -1 Wavenumber, and FIG. 3 is a graph showing the average functional group of the polyol compound (A) in the polyurethane resin composition according to an embodiment of the present invention IR spectroscopy (FT-IR) at 1560 to 1500 -1 Wavenumber showing the change in urethane bond and urea bond according to the number of moles of urethane bond and urethane bond.
4 shows 1760-1620 -1 wave number illustrating a change amount of a urethane bond and urea bond according to the number of isocyanate group content (NCO%) and mole (mol) of urea tone migration from the polyurethane resin composition according to an embodiment of the present invention (FT-IR) at a Wavenumber (Wavenumber), and FIG. 5 is a graph showing the relationship between an isocyanate group content (NCO%) and a mole of uretonimine in a polyurethane resin composition according to an embodiment of the present invention (FT-IR) at 1560 to 1500 -1 Wavenumber, which shows the amount of change of urethane bond and urea bond according to the number of carbon atoms (mol).
6 is a graph showing changes in 90 degree peel strength depending on the number of moles of uretonimine and the average functional group (fav) of the polyol compound (A) in the polyurethane resin composition according to an embodiment of the present invention have.
7 and 8 show cross-sectional views when the average functional group (fav) of the polyol compound (A) is 2 and the number of moles of uretonimine is 0.003842 in the polyurethane resin composition according to an embodiment of the
The analysis results of the polyurethane resin composition prepared in Example 1 will be described with reference to these drawings.
As can be seen from the graph showing the number of moles of isocyanate having a uretonimine group according to the isocyanate group content of Fig. 1, when the isocyanate group content (NCO%) is low in the isocyanate compound (B) It can be confirmed that the content of isocyanate having an imine group is large and the content of isocyanate having a uretonimine group is small as the content of isocyanate group (NCO%) is increased. Therefore, it can be seen that the modified isocyanate compound (b) in the polyurethane resin composition according to the present invention having an isocyanate group content (NCO%) of 25 to 32 has an isocyanate content having a relatively high uretonimine group. It can be confirmed that similar results are obtained even when the average functionality of the polyol compound (A) used is changed.
The change in the adhesive strength of the polyurethane resin composition when the average functionality (average functionality) of the polyol compound (A) was changed can be confirmed by the change in 900 peel strength according to the content of uretonimine in FIG. That is, as the average number of functional groups of the polyol compound (A) decreases, the adhesion of the polyurethane resin composition increases. As the average number of functional groups of the polyol compound (A) is decreased, the degree of crosslinking is lowered, and the fluidity of the polymer main chain such as polymeric MDI increases in the synthesized polyurethane resin composition, thereby increasing the wettability of the polyurethane resin adhesive to the surface of the adherend , the anchoring effect is increased, and as a result, the adhesion of the polyurethane resin composition is increased.
In addition, when the fav is increased, the distance between the functional groups (-OH) of the polyol compound (A) becomes closer to increase the probability of hydrogen bonding between the urethane bond and the urea bond in the resulting polyurethane resin composition. Therefore, it can be expected that free urethane and free urea decrease in the polyurethane resin composition. In the FT-IR analysis graph, it can be confirmed that the absorbance of free urethane, free urea and amide II decreases as fav increases (graph of FIG. 2, 1760-1620 cm -1 , graph of FIG. 3, 1560-1500 cm -1 ).
In addition, Cosmonate LL, which is an isocyanate with low NCO% and 25% of uretonimine molecular content, and Cosmonate CG3701S, an isocyanate with a high NCO% and a uretonimine molecular weight of 0%, was changed to change the equivalent ratio of NCO% and uretonimine to poly When the urethane resin composition was synthesized, it was confirmed that the adhesive force was improved as the content of uretonimine increased and the% NCO of the isocyanate compound used in the synthesis decreased.
As the content of uretonimine increases, the uretonimine molecule content increases. The uretonimine group-containing isocyanate has a molecular length shorter than that of the polymeric MDI, which accounts for approximately 75% of Cosmonate CG3701S, thereby imparting fluidity to the polymer backbone of the finally synthesized polyurethane, Is increased.
In addition, since the NCO / OH lndex of all the samples is 1, the content of Cosmonate LL having a low NCO% is increased. As a result, the carbodiimide MDI and the monomeric MDI having relatively short molecular length are increased to increase the polymer backbone of the polyurethane resin Thereby further increasing the fluidity.
As a result, the distance between the functional groups of uretonimine is decreased, and the probability of hydrogen bonding between the urethane bond and the urea bond is lowered, and it is expected that free urethane and free urea (amide II) will increase.
This can be confirmed by the fact that in the FT-IR analysis graph, as the content of uretonimine increases, the absorbance of free urethane and free urea and aminde II increases with decreasing NCO% of isocyanate used in polyurethane pressure-sensitive adhesive composition there (see
On the other hand, some samples of peel strength data could not be measured at the 90 degree peel strength change of the polyurethane resin composition according to the content of Uretonimine in FIG. These unmeasurable groups can be broadly divided into two groups: the first group is a group with low fav of polyol compounds and a high content of Cosmonate LL, and a large number of carbodiimide MDI. When the content of Cosmonate LL is high and the fav of the polyol compound is low, the degree of crosslinking of the polyurethane resin composition becomes very low, and the sample is slackened during the measurement, and cohesive failure occurs due to such sagging, do.
The second group is expected to have a high degree of crosslinking of the polyurethane resin composition due to high fav of the polyol compound, so that no cohesive failure is expected. The molecular weight of P-Y3553 (Triol) added to increase fav is very high, And the bubbles are generated by mechanical stirring.
That is, as shown in the cross-sectional photographs of the polyurethane resin composition using a scanning electron microscope (SEM) (FIGS. 7, 8, 9 and 10), a very large cavitiy was produced in the synthesized polyurethane resin composition This large cavitiy reduces the cohesive force of the polyurethane resin composition and tears the polyurethane resin composition during the 90 degree peel test. That is, when the peel strength is measured at 90 degrees, cohesive failure occurs.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible.
Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the equivalents of the claims, as well as the claims.
Claims (14)
An isocyanate compound (B) such that the NCO / OH ratio of the polyol compound (A) and the isocyanate compound (B) is 0.5 to 1.5,
The isocyanate compound (B)
MDI (methylene diphenyl diisocyanate) isocyanate compounds (a) and
A modified isocyanate compound (b) containing an isocyanate group having a uretonimine group and having an isocyanate group (NCO) content of 25 to 32 at the same time,
And a polyurethane resin composition.
Wherein the polyol compound (A) and the isocyanate compound (B) have an NCO / OH ratio of 0.8 to 1.2.
The polyol compound (A) comprises a first polyol having an average molecular weight of 1400 to 2700, a second polyol having an average molecular weight of 4800 to 5200, a chain extender, and a gelling catalyst.
The chain extender may be selected from polyhydric alcohols, diols, amines, diamines, aminoalcohols and / or ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4- But are not limited to, glycerin, polyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, 1,3-butylene glycol, diethanolamine, And 4,4'-methylene-bis (2-chloroaniline).
The gelling catalyst may be selected from the group consisting of triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpyrrole, 2- (dimethylamino- ethoxy) -ethanol, diazabicyclo- 2,2) -octane, esters of titanic acid, iron compounds, tin diacetates, tin dioctate, tin dilaurate, dibutyltin dilaurate and dialkyl tin salts of aliphatic carboxylic acids. Polyurethane resin composition.
The polyol compound (A) has an Average Functionality of 2 to 2.2.
Wherein the polyol compound (A) comprises a polyol selected from the group consisting of a polyester-based polyol and a polyether-based polyol.
The MDI-based isocyanate compound (a) comprises 70 to 80% by weight of polymeric MDI and the modified isocyanate compound (b) is a monomeric MDI (Monameric MDI) and a carbodiimide modified MDI). ≪ / RTI >
Wherein the isocyanate having the uretonimine group is uretonimine modified MDI (Uretonimine Modified MDI).
The MDI-based isocyanate compound (a) has an isocyanate group (NCO) content of 35 to 40%.
MDI (methylene diphenyl diisocyanate) isocyanate compounds (a) and
A modified isocyanate compound (b) containing an isocyanate group having a uretonimine group and having an isocyanate group (NCO) content of 25 to 32 at the same time,
Preparing an isocyanate compound (B) which is prepared so that the NCO / OH ratio of the polyol compound (A) and the isocyanate compound (B) is 0.5 to 1.5; And
A polymerization step of putting both the polyol compound (A) and the isocyanate compound (B) into a reactor to polymerize;
By weight of the polyurethane resin composition.
Wherein the polymerization step comprises stirring at a stirring speed of 2500 to 3500 rpm so that the polyol compound (A) and the isocyanate compound (B) can be uniformly mixed with each other.
Wherein the polymerization step is carried out at a temperature of 55 to 75 占 폚.
Wherein the polymerization step is performed for 8 to 20 seconds.
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| KR20190077150A (en) * | 2017-12-22 | 2019-07-03 | 하대환 | Fast curing and 2-component Polyurethane resin composition for pultrusion |
| WO2022211223A1 (en) * | 2021-04-01 | 2022-10-06 | 주식회사 케이씨씨 | Urethane-based adhesive composition |
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| KR101991663B1 (en) * | 2018-08-09 | 2019-06-21 | 김창준 | Eco-friendly Polymer grouting-accelerating agent for polymer grouting, Manufacturing method thereof, Eco-friendly Polymer grout agent composition using the same and Eco-friendly Polymer grouting method |
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| KR20100079866A (en) | 2008-12-31 | 2010-07-08 | 조광페인트주식회사 | Polyurethane adhesive composition and process for preparing the same |
| KR20110008775A (en) | 2009-07-21 | 2011-01-27 | 애경화학 주식회사 | Aqueous polyurethane resin with excellent adhesive strength and workability and the method for manufacturing thereof, and aqueous hot-melt adhesive containing the same |
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| KR20100079866A (en) | 2008-12-31 | 2010-07-08 | 조광페인트주식회사 | Polyurethane adhesive composition and process for preparing the same |
| KR20110008775A (en) | 2009-07-21 | 2011-01-27 | 애경화학 주식회사 | Aqueous polyurethane resin with excellent adhesive strength and workability and the method for manufacturing thereof, and aqueous hot-melt adhesive containing the same |
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| KR20190077150A (en) * | 2017-12-22 | 2019-07-03 | 하대환 | Fast curing and 2-component Polyurethane resin composition for pultrusion |
| WO2022211223A1 (en) * | 2021-04-01 | 2022-10-06 | 주식회사 케이씨씨 | Urethane-based adhesive composition |
| KR20220136820A (en) * | 2021-04-01 | 2022-10-11 | 주식회사 케이씨씨 | Urethane-based adhesive composition |
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