CN117795008A - (methyl) acrylic acid modified polyurethane composition and preparation method thereof - Google Patents

(methyl) acrylic acid modified polyurethane composition and preparation method thereof Download PDF

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CN117795008A
CN117795008A CN202280054312.3A CN202280054312A CN117795008A CN 117795008 A CN117795008 A CN 117795008A CN 202280054312 A CN202280054312 A CN 202280054312A CN 117795008 A CN117795008 A CN 117795008A
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meth
acrylic
modified polyurethane
lipophilic
polyurethane composition
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李栽训
柳熏
林俊燮
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Samyang Corp
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Samyang Corp
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Priority claimed from PCT/KR2022/011938 external-priority patent/WO2023018228A1/en
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Abstract

The present invention relates to a (meth) acrylic acid modified polyurethane composition and a method for preparing the same, and more particularly, to a (meth) acrylic acid modified polyurethane composition and a method for preparing the same, as follows: the (meth) acrylic-modified polyurethane composition contains a hydrophilic (meth) acrylic-modified polyurethane containing a polymerized unit derived from an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic (meth) acrylic-modified polyurethane containing a polymerized unit derived from a lipophilic polyol, and can provide an adhesive composition excellent in environmental protection, adhesion (in particular, adhesion between different materials) and oil resistance, and a hygroscopic coating composition suitable for antifogging use due to excellent hygroscopicity.

Description

(methyl) acrylic acid modified polyurethane composition and preparation method thereof
Technical Field
The present invention relates to a (meth) acrylic-modified polyurethane composition and a method for producing the same, and more particularly, to a (meth) acrylic-modified polyurethane composition containing a hydrophilic (meth) acrylic-modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct and a lipophilic (meth) acrylic-modified polyurethane comprising polymerized units derived from a lipophilic polyol, and which can provide an adhesive composition excellent in environmental protection, adhesion (especially adhesion between different materials) and oil resistance, and a hygroscopic coating composition suitable for antifogging use due to excellent hygroscopicity, and a method for producing the same.
Background
Polyols and isocyanates, which are essential components of polyurethane, are generally prepared from petroleum-based raw materials, and a method of partially or completely replacing the polyols and isocyanates prepared from petroleum-based raw materials with environmentally friendly components is required in the polyurethane field due to various reasons such as acceleration of exhaustion of petroleum resources, emission reduction requirements of greenhouse gases according to climate change, rising of raw material prices, and increasing of demand for renewable raw materials.
Polyols can be produced from renewable biomass of natural vegetable fats and oils, cellulose, lignin, etc., and biopolyols derived from natural vegetable fats and oils have been produced on a commercial scale. The physical properties of the produced biopolyol vary depending on the kind of biomass used in the preparation. Generally, castor oil, coconut oil, etc. are used for preparing soft polyurethane and hard polyurethane and polyol for synthesis, and soybean oil is used for preparing polyol for soft polyurethane. However, the biomass-based biopolyols prepared at present have the disadvantage of high viscosity.
Isocyanates based on natural vegetable oils are aliphatic in nature, which have the disadvantage of reduced reactivity compared to petroleum-based aromatic diisocyanates. Therefore, little research has been done on the preparation of diisocyanates using biomass.
Hydrogenated sugar (also referred to as "sugar alcohol") refers to a compound obtained by hydrogenation on a reducing end group of a sugar, typically of the formula HOCH 2 (CHOH) n CH 2 OH (where n is an integer of 2 to 5), and is classified into tetritol, pentitol, hexitol, and heptitol according to the number of carbon atoms (the number of carbon atoms is 4, 5, 6, and 7, respectively). Among them, hexitols having 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly useful substances.
Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the inside of hydrogenated sugar, and can be produced using a hexitol derived from starch in the form of a tetraol (tetraol) having four hydroxyl groups in the molecule when one water molecule is removed and a diol (diol) having two hydroxyl groups in the molecule when two water molecules are removed (for example, korean patent laid-open publication No. 10-1079518 and korean patent laid-open publication No. 10-2012-0066904). Since anhydrosugar alcohols are environmentally friendly substances derived from renewable natural resources, there has been a long-standing interest and research is being conducted on the preparation methods thereof. Among such anhydrosugar alcohols, isosorbide prepared from sorbitol is currently most widely used industrially.
Anhydrosugar alcohols are used in a wide variety of applications, such as drugs for treating heart and vascular diseases, adhesives for patches, oral cleaners, etc., solvents for compositions in the cosmetic industry, emulsifiers in the food industry, etc. In addition, anhydrosugar alcohols are useful in the plastic industry such as bioplastic because they can raise the glass transition temperature of high molecular substances such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and have the effect of improving the strength of these substances, and because they are environmentally friendly materials derived from natural resources. In addition, anhydrosugar alcohols are known to be useful as binders, environmentally friendly plasticizers, biodegradable polymers, environmentally friendly solvents for water-soluble paints.
As described above, anhydrosugar alcohols are attracting attention due to their wide applicability, and the utilization rate in the actual industry is also gradually increasing.
Disclosure of Invention
Technical problem to be solved
The object of the present invention is to provide a (meth) acrylic acid-modified polyurethane composition which has excellent environmental protection by using a derivative of anhydrosugar alcohol, and which can provide a composition for adhesion excellent in both adhesion (particularly adhesion between different materials) and oil resistance and a hygroscopic coating composition suitable for antifogging use due to excellent hygroscopicity, and a process for producing the same.
Technical proposal
In order to achieve the above object, the present invention provides a (meth) acrylic-modified polyurethane composition comprising: (1) A hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate; and (2) a lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
According to another aspect of the present invention, there is provided a method for preparing a (meth) acrylic-modified polyurethane composition, comprising the steps of: (1) Reacting a polyol component comprising a anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminus; and (2) reacting the intermediate obtained from said step (1) with a hydroxyalkyl (meth) acrylate.
According to another aspect of the present invention, there is provided a method for preparing a (meth) acrylic-modified polyurethane composition, comprising the steps of: mixing (i) a hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate, and (ii) a lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
According to another aspect of the present invention, there is provided an adhesive composition comprising the (meth) acrylic-modified polyurethane composition of the present invention.
According to another aspect of the present invention, there is provided an article to which the adhesive composition of the present invention is applied.
According to another aspect of the present invention, there is provided a hygroscopic coating composition comprising the (meth) acrylic modified polyurethane composition of the present invention.
Advantageous effects
The (meth) acrylic-modified polyurethane composition according to the present invention has excellent environmental protection, and when used in a composition for adhesion, can well improve all adhesion (particularly adhesion between different materials) and oil resistance, and when used in a hygroscopic coating composition, can provide a coating layer having excellent adhesion to a glass substrate even after moisture absorption, and also excellent antifogging property.
Detailed Description
The present invention will be described in more detail below.
In the present specification, the term "(meth) acrylic" includes acrylic acid, methacrylic acid, or a combination thereof, and the term "(meth) acrylate" includes acrylate, methacrylate, or a combination thereof.
The (meth) acrylic-modified polyurethane composition of the present invention comprises: (1) A hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate; and (2) a lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
In a specific embodiment, the (meth) acrylic-modified polyurethane composition may comprise 16 to 84 parts by weight of the hydrophilic (meth) acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth) acrylic-modified polyurethane, based on 100 parts by weight of the total (meth) acrylic-modified polyurethane composition. When the content of the hydrophilic (meth) acrylic modified polyurethane in the (meth) acrylic modified polyurethane composition is less than the above level (i.e., when the content of the lipophilic (meth) acrylic modified polyurethane is too much compared with the above level), the adhesion to metal of the composition prepared using the same may be reduced, but when the content of the hydrophilic (meth) acrylic modified polyurethane is too much compared with the above level (i.e., when the content of the lipophilic (meth) acrylic modified polyurethane is too small compared with the above level), the adhesion to organic materials of the composition prepared using the same may be reduced.
More specifically, in the total 100 parts by weight of the (meth) acrylic-modified polyurethane composition, the hydrophilic (meth) acrylic-modified polyurethane and the lipophilic (meth) acrylic-modified polyurethane may be contained in amounts of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, respectively, and the hydrophilic (meth) acrylic-modified polyurethane and the lipophilic (meth) acrylic-modified polyurethane may be contained in amounts of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, respectively, but are not limited thereto.
Anhydrosugar alcohol-alkylene oxide adducts
The anhydrosugar alcohol-alkylene oxide adduct (or, also referred to as "anhydrosugar alcohol-alkylene glycol") contained as a polymerized unit in the hydrophilic (meth) acrylic acid modified polyurethane is an adduct obtained by reacting hydroxyl groups of both ends or one end (preferably both ends) of an anhydrosugar alcohol with alkylene oxide, and refers to a compound in which hydrogen of hydroxyl groups of both ends or one end (preferably both ends) of an anhydrosugar alcohol is substituted with hydroxyalkyl groups of a ring-opened form of alkylene oxide.
In a specific embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.
The anhydrosugar alcohol may be prepared by subjecting hydrogenated sugar derived from a natural product to a dehydration reaction. Hydrogenated sugar (also referred to as "sugar alcohol") refers to a compound obtained by hydrogenation on a reducing end group of a sugar, typically of the formula HOCH 2 (CHOH) n CH 2 OH (where n is an integer of 2 to 5), and is classified into tetritol, pentitol, hexitol, and heptitol according to the number of carbon atoms (the number of carbon atoms is 4, 5, 6, and 7, respectively). Among them, hexitols having 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, and the like, and in particular, sorbitol and mannitol are very useful substances.
The anhydrosugar alcohol may be a monoanhydrosugar alcohol, a dianhydrosugar alcohol, or a mixture thereof, and although not particularly limited, a dianhydrosugar alcohol may be used.
The monoanhydrosugar alcohol is a anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol (tetraol) form having four hydroxyl groups in the molecule. In the present invention, the type of the monoanhydrohexitol is not particularly limited, but may be preferably a monoanhydrohexitol, more specifically a 1, 4-anhydrohexitol, a 3, 6-anhydrohexitol, a 2, 5-anhydrohexitol, a 1, 5-anhydrohexitol, a 2, 6-anhydrohexitol, or a mixture of two or more thereof.
Dianhydrosugar alcohols are anhydrosugar alcohols formed by removing two water molecules from the inside of hydrogenated sugar, and have a diol (diol) form having two hydroxyl groups in the molecule, and can be produced using hexitols derived from starch. Dianhydrosugar alcohols are environmentally friendly materials derived from renewable natural resources and have therefore been of great interest for a long time and research on methods for preparing dianhydrosugar alcohols is still ongoing. Among such dianhydroalditols, isosorbide, which is currently prepared from sorbitol, has the most widespread industrial application.
In the present invention, the kind of the dianhydrohexitol is not particularly limited, but may be preferably a dianhydrohexitol, more specifically a 1,4:3, 6-dianhydrohexitol. The 1,4:3, 6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.
In a specific embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be a compound represented by the following chemical formula 1 or a mixture of two or more thereof.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 and R is 2 Each independently represents a linear alkylene group having 2 to 8 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms,
m and n each independently represent an integer of 0 to 15,
m+n represents an integer of 1 to 30.
More preferably, in the chemical formula 1,
R 1 and R is 2 Each independently represents ethylene, propylene or isopropylene, preferably R 1 And R is 2 Are identical to each other in that,
m and n each independently represent an integer of 0 to 14,
wherein m+n is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.
In a specific embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be an anhydrosugar alcohol-propylene oxide adduct represented by the following chemical formula 1-1, an anhydrosugar alcohol-ethylene oxide adduct represented by the following chemical formula 1-2, or a mixture thereof.
[ chemical formula 1-1]
In the chemical formula 1-1 described above,
a and b each independently represent an integer of 0 to 15,
a+b represents an integer of 1 to 30.
More preferably, in the chemical formula 1-1,
a and b each independently represent an integer of 0 to 14,
wherein a+b is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.
[ chemical formulas 1-2]
In the chemical formula 1-2 described above,
c and d each independently represent an integer of 0 to 15,
c+d represents an integer of 1 to 30.
More preferably, in the chemical formula 1-2,
c and d each independently represent an integer of 0 to 14,
wherein c+d is an integer of 1 or more, 2 or more, or 3 or more, and is an integer of 25 or less, 20 or less, 15 or less, or 12 or less, for example, an integer of 1 to 25, preferably an integer of 2 to 20, more preferably an integer of 3 to 15.
In a specific embodiment, the anhydrosugar alcohol-alkylene oxide adduct may be prepared by a preparation process comprising the steps of: (1) treating the anhydrosugar alcohol with an acid component; and (2) subjecting the anhydrosugar alcohol treated with the acid component obtained in the step (1) and alkylene oxide to an addition reaction.
More specifically, the anhydrosugar alcohol-alkylene oxide adduct may be prepared by a preparation method comprising the steps of: (1) treating the anhydrosugar alcohol with an acid component; (2) Subjecting the anhydrosugar alcohol treated with an acid component obtained in the step (1) and an alkylene oxide to an addition reaction; and (3) subjecting the product obtained in the step (2) and alkylene oxide to an addition reaction in the presence of a base catalyst.
The acid component is not particularly limited, and an acid component selected from phosphoric acid, sulfuric acid, acetic acid, formic acid, heteropolyacid or a mixture thereof may be used. In a specific embodiment, the heteropolyacid may be phosphotungstic acid (phosphotungstic acid), phosphomolybdic acid (phosphomolybdic acid), silicotungstic acid (silicotungstic acid) or silicomolybdic acid (silicomolybdic acid), etc., and as an acid component which may be used in addition thereto, a commercially available acid component such as Amberlyst 15 (Dow Chemical company) may be used.
In a specific embodiment, in the acid treatment, 0.1 to 10 moles, preferably 0.1 to 8 moles, more preferably 0.1 to 5 moles of an acid component may be used with respect to 1 mole of the anhydrosugar alcohol, and the reaction may be performed under a nitrogen atmosphere at an elevated temperature (e.g., 80 to 200 ℃ or 90 to 180 ℃) and then vacuum-depressurized to remove moisture in the reactor, but is not limited thereto.
The acid component used in the acid treatment is used to promote the ring opening of the alkylene oxide in the addition reaction of the alkylene oxide described below.
In general, the addition reaction of an alcohol with an alkylene oxide is carried out under the condition of a base catalyst, and in the case of a anhydrosugar alcohol, the rate of addition with an alkylene oxide and the rate of ring opening and decomposition of the ring structure of the anhydrosugar alcohol under the action of a base catalyst compete due to structural characteristics. Therefore, not only the anhydrosugar alcohol but also the decomposition product of the anhydrosugar alcohol reacts with the alkylene oxide, and a reaction product between the decomposition product of the anhydrosugar alcohol decomposed by the base catalyst and the alkylene oxide may become a factor that reduces the quality and storage stability of the product. However, if the anhydrosugar alcohol is treated with an acid component and then subjected to an addition reaction with the alkylene oxide, the acid component promotes ring opening of the alkylene oxide and does not produce decomposition products of the anhydrosugar alcohol by the base catalyst, and therefore an anhydrosugar alcohol-alkylene oxide adduct can be easily formed by the addition reaction of the anhydrosugar alcohol and the alkylene oxide. Therefore, the conventional problems can be solved when the addition reaction is carried out using the acid-treated anhydrosugar alcohol and alkylene oxide.
In a specific embodiment, the addition reaction of the anhydrosugar alcohol treated with the acid component and the alkylene oxide may be performed by slowly adding the alkylene oxide to the anhydrosugar alcohol treated with the acid component and at an elevated temperature (e.g., 100 to 180 ℃ or 120 to 160 ℃) for, for example, 1 to 8 hours or 2 to 4 hours, but is not limited thereto. The molar ratio of the anhydrosugar alcohol to the alkylene oxide may be, for example, 1 mol or more and 2 mol or more, and may be 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, for example, 1 to 30 mol, preferably 2 to 20 mol, per 1 mol of anhydrosugar alcohol, but is not limited thereto.
In a specific embodiment, the further addition reaction of the product obtained by the addition reaction of the alkylene oxide with the additional alkylene oxide may be carried out, for example, in the presence of a base catalyst (for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or an alkaline earth metal hydroxide such as calcium hydroxide) in a high-pressure reactor which can be pressurized (for example, to 3MPa or more), at an elevated temperature (for example, 100 to 180 ℃ or 120 to 160 ℃) for, for example, 1 to 8 hours or 2 to 4 hours, but is not limited thereto. The molar ratio of the anhydrosugar alcohol to the alkylene oxide may be, for example, 1 mol or more, 2 mol or more, or 3 mol or more, and 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, for example, 1 to 30 mol, preferably 2 to 20 mol, more preferably 3 to 15 mol, per 1 mol of anhydrosugar alcohol, but is not limited thereto. The acid component used in the treatment may be removed by filtration before the base catalyst is added.
The structure of the product obtained by the addition reaction of the anhydrosugar alcohol and the alkylene oxide using the acid treatment (i.e., the compound in the form of addition of the anhydrosugar alcohol to the alkylene oxide) is very stable, and therefore the ring structure of the anhydrosugar alcohol is not easily opened or decomposed at high temperature even in the presence of a base catalyst. Thus, further addition reaction of alkylene oxide is very advantageous. If the acid catalyst is continuously used in the further addition reaction of the alkylene oxide, the reaction rate decreases as the number of addition moles of the alkylene oxide increases, although the acid catalyst helps to promote the ring opening of the alkylene oxide. That is, the addition rate of the alkylene oxide competes with the ring opening rate of the alkylene oxide itself, at which time the addition rate of the alkylene oxide becomes slow, and the self-condensation reaction between the ring-opened alkylene oxides and the formation of by-products occur, and thus there is a possibility that the quality may be deteriorated. Thus, the further addition reaction of alkylene oxide is carried out under base catalyst conditions.
Thereafter, a step of removing the metal ions released from the base catalyst used may be further performed, and for this purpose, for example, a metal ion adsorbent such as Ambosol MP20 (magnesium silicate component) may be used.
Lipophilic polyols
The lipophilic polyol contained as the polymerized unit in the lipophilic (meth) acrylic modified polyurethane is a polyol having low surface energy characteristics, and specifically may be selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof, but is not limited thereto.
In a specific embodiment, the number average molecular weight (Mn) of the lipophilic polyol is not particularly limited, but may be specifically 200 to 3000g/mol, more specifically 500 to 2500g/mol, still more specifically 700 to 2300g/mol, and more specifically 1000 to 2000g/mol. When the number average molecular weight of the lipophilic polyol is too low compared to the above level, the shear strength of the adhesive test piece using the different material comprising the adhesive composition for the (meth) acrylic-modified polyurethane composition prepared using the same is lowered, and thus the adhesion may be deteriorated, and when the number average molecular weight of the lipophilic polyol is too high compared to the above level, the oil resistance of the adhesive test piece using the different material comprising the adhesive composition for the (meth) acrylic-modified polyurethane composition prepared using the same may be lowered.
Polyisocyanates
The polyisocyanate contained as a polymerization unit in the hydrophilic and lipophilic (meth) acrylic modified polyurethane may be an aromatic polyisocyanate such as diphenylmethane diisocyanate (MDI) (e.g., diphenylmethane-2, 4-diisocyanate or diphenylmethane-4, 4 '-diisocyanate), xylylene Diisocyanate (XDI), tetramethyl-m-xylylene diisocyanate or tetramethyl-p-xylylene diisocyanate (TMXDI), toluene Diisocyanate (TDI), dialkyl diphenylmethane diisocyanate or tetraalkyl diphenylmethane diisocyanate, 3' -dimethyl-4, 4 '-biphenyl diisocyanate (TODI), phenylene diisocyanate (e.g., 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate), naphthalene diisocyanate (naphthalene diisocyanate, NDI) or 4,4' -dibenzyl diisocyanate; aliphatic polyisocyanates such as hydrogenated MDI (H12 MDI), 1-methyl-2, 4-diisocyanatocyclohexyl, 1, 12-dodecyl diisocyanate, 1, 6-diisocyanato-2, 4-trimethylhexane, 1, 6-diisocyanato-2, 4-trimethylhexane, isophorone diisocyanate (isophorone diisocyanate, IPDI), tetramethoxybutane-1, 4-diisocyanate, butane-1, 4-diisocyanate, hexamethylene Diisocyanate (HDI) (e.g., 1, 6-hexamethylene diisocyanate), dimerized fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g., cyclohexane-1, 4-diisocyanate), or ethylene diisocyanate; or combinations thereof, but is not limited thereto.
In another embodiment, the polyisocyanate may be methylene diphenyl diisocyanate (MDI), ethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 12-dodecyl diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate (HMDI), 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, toluene diisocyanate mixed with 2, 6-toluene diisocyanate (2, 4-/2, 6-isomer ratio=80/20), diphenylmethane-2, 4' -diisocyanate, diphenylmethane-4, 4' -diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1, 5-diisocyanate, or combinations thereof.
More specifically, the polyisocyanate may be diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.
Hydroxyalkyl (meth) acrylate
The hydroxyalkyl (meth) acrylate contained as a polymerized unit in the hydrophilic (meth) acrylic modified polyurethane and the lipophilic (meth) acrylic modified polyurethane may be, for example, a linear or branched alkyl acrylate having a hydroxyl group, a linear or branched alkyl methacrylate having a hydroxyl group, or a combination thereof, more specifically, may be hydroxy-C (meth) acrylate 1-8 Alkyl esters, i.e. linear acrylic acid C having hydroxyl groups 1-8 Alkyl esters, branched acrylic acid C having hydroxyl groups 3-8 Alkyl esters, straight-chain methacrylic acid C with hydroxyl groups 1-8 Alkyl esters, branched methacrylic acid C having hydroxyl groups 3-8 The alkyl ester or a combination thereof may be more specifically, but not limited to, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, 2-hydroxyethylhexyl acrylate, 2-hydroxyethylhexyl methacrylate, 2-hydroxyethylbutyl acrylate, 2-hydroxyethylbutylmethacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, or a combination thereof.
More specifically, the hydroxyalkyl (meth) acrylate may be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, or a combination thereof, but is not limited thereto.
Hydrophilic (meth) acrylic modified polyurethane
In one embodiment, the hydrophilic (meth) acrylic-modified polyurethane may be represented by the following chemical formula 2:
[ chemical formula 2]
In the chemical formula 2 described above, a compound having a structure of,
r1 is each independently an alkylene group, in particular a C2-C8 linear alkylene group or a C3-C8 branched alkylene group, more in particular a C2-C6 linear alkylene group or a C3-C6 branched alkylene group,
r2 is each independently an alkylene, cycloalkylene or arylene group, in particular a C2-C20 straight-chain alkylene or a C3-C20 branched alkylene, a C3-C20 cycloalkylene or a C6-C20 arylene group,
r3 is each independently an alkylene group, in particular a C1-C8 linear alkylene group or a C3-C8 branched alkylene group, more in particular a C2-C6 linear alkylene group or a C3-C6 branched alkylene group,
r4 is each independently a hydrogen atom or an alkyl group, in particular a hydrogen atom or a C1-C4 straight-chain alkyl group or a C3-C4 branched alkyl group,
m is a divalent organic group derived from anhydrosugar alcohol, specifically a divalent organic group derived from isosorbide, isomannide or isoidide, more specifically M is selected from the following formulas,
m and n each independently represent an integer of 0 to 15,
m+n represents an integer of 1 to 30, more specifically an integer of 1 to 25, further specifically an integer of 1 to 20, still further specifically an integer of 3 to 15, still further specifically an integer of 5 to 15.
More specifically, the hydrophilic (meth) acrylic-modified polyurethane may be represented by any one of the following chemical formulas, but is not limited thereto:
in the chemical formula, m, n, and m+n are each independently the same as defined in the chemical formula 2.
The hydrophilic (meth) acrylic modified polyurethane may be obtained by reacting a anhydrosugar alcohol-alkylene oxide adduct with a polyisocyanate followed by a reaction with a hydroxyalkyl (meth) acrylate.
More specifically, the hydrophilic (meth) acrylic-modified polyurethane may be prepared by a method comprising the steps of: (a) Reacting a anhydrosugar alcohol-alkylene oxide adduct and a polyisocyanate to produce an intermediate having an isocyanate terminus; and (b) reacting the intermediate obtained in step (a) with a hydroxyalkyl (meth) acrylate.
According to one specific embodiment, 1 equivalent of a anhydrosugar alcohol (example: isosorbide (ISB)) -alkylene oxide adduct and 2 equivalents of a diisocyanate may be reacted to prepare an intermediate having an isocyanate end, and then the isocyanate end of the intermediate and 2 equivalents of hydroxyalkyl (meth) acrylate (example: 2-hydroxyethyl methacrylate) are reacted to prepare a hydrophilic (meth) acrylic modified polyurethane.
According to a specific embodiment, the reaction of the anhydrosugar alcohol-alkylene oxide adduct and polyisocyanate may be carried out at normal or elevated temperature (e.g., 50-100 ℃, preferably 50-70 ℃) in the presence of any catalyst (e.g., tin-based catalyst such as dibutyltin dilaurate (DBTDL)) for a suitable period of time (e.g., 0.1-5 hours, preferably 0.5-2 hours).
According to a specific embodiment, the reaction of the reaction product of anhydrosugar alcohol-alkylene oxide adduct and polyisocyanate (i.e. the intermediate obtained from step (a)) and hydroxyalkyl (meth) acrylate may be carried out in the presence of any catalyst, for example dibutyltin dilaurate (tin-based catalyst such as DBTDL), at elevated temperature (for example, 50-100 ℃, preferably 50-70 ℃) for a suitable time (for example, 0.1-5 hours, preferably 0.5-2 hours).
Lipophilic (meth) acrylic modified polyurethane
In a specific embodiment, the lipophilic (meth) acrylic modified polyurethane may be represented by the following chemical formula 3:
[ chemical formula 3]
In the chemical formula 3 described above, the chemical formula,
r1 is each independently alkylene, cycloalkylene or arylene,
each R2 is independently an alkylene group,
R3 is each independently a hydrogen atom or an alkyl group,
l is a divalent organic group derived from a lipophilic polyol,
the lipophilic polyol has a number average molecular weight of 200-3000g/mol.
More specifically, in the chemical formula 3,
r1 is each independently C2-C20 straight-chain or alkylene C3-C20 branched alkylene, C3-C20 cycloalkylene or C6-C20 arylene,
r2 is each independently a C1-C8 straight-chain alkylene or a C3-C8 branched alkylene,
r3 is each independently a hydrogen atom or a C1-C4 straight-chain alkyl group or a C3-C4 branched alkyl group,
l is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyols or combinations thereof,
the lipophilic polyol has a number average molecular weight of 500-2500g/mol.
The lipophilic (meth) acrylic modified polyurethane can be obtained by reacting a polyisocyanate with a lipophilic polyol and then with a hydroxyalkyl (meth) acrylate.
More specifically, the lipophilic (meth) acrylic modified polyurethane may be prepared by a method comprising the steps of: (c) Reacting a lipophilic polyol with a polyisocyanate to produce an intermediate having isocyanate ends; and (d) reacting the intermediate obtained from said step (c) with a hydroxyalkyl (meth) acrylate.
According to one embodiment, the lipophilic (meth) acrylic modified polyurethane may be prepared by reacting 2 equivalents of diisocyanate with 1 equivalent of a lipophilic polyol (e.g., polytetrahydrofuran, polypropylene glycol, or polydimethylsiloxane glycol having a number average molecular weight of 200-3000 g/mol) to prepare an intermediate having isocyanate ends, and then reacting the isocyanate ends of the intermediate with 2 equivalents of hydroxyalkyl (meth) acrylate (e.g., 2-hydroxyethyl methacrylate).
According to a specific embodiment, the reaction of the lipophilic polyol and polyisocyanate may be carried out in the presence of any catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)) at ambient or elevated temperatures (e.g., 50-100 ℃, preferably 50-70 ℃) for a suitable period of time (e.g., 0.1-5 hours, preferably 0.5-2 hours).
According to a specific embodiment, the reaction of the reaction product of the lipophilic polyol and polyisocyanate, i.e. the intermediate obtained in step (c), with the hydroxyalkyl (meth) acrylate may be carried out at an elevated temperature, e.g. 50-100 c, preferably 50-70 c, for a suitable time, e.g. 0.1-5 hours, preferably 0.5-2 hours, in the presence of any catalyst, e.g. tin-based catalyst such as dibutyltin dilaurate (DBTDL).
Method for producing (meth) acrylic-modified polyurethane compositions
According to another aspect of the present invention, there is provided a method for producing a (meth) acrylic-modified polyurethane composition (first production method), comprising the steps of: (1) Reacting a polyol component comprising a anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminus; and (2) reacting the intermediate obtained from said step (1) with a hydroxyalkyl (meth) acrylate.
According to another aspect of the present invention, there is provided a method for producing a (meth) acrylic-modified polyurethane composition (second production method) comprising the steps of: reacting (i) a hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate, and (ii) a lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
In the first and second production methods of the (meth) acrylic acid-modified polyurethane composition, the anhydrosugar alcohol-alkylene oxide adduct, the lipophilic polyol, the polyisocyanate, and the hydroxyalkyl (meth) acrylate are as described above.
According to a specific embodiment, in the first preparation method of the (meth) acrylic modified polyurethane composition, the polyol component may contain 16 to 84 parts by weight of the anhydrosugar alcohol-alkylene oxide adduct and 16 to 84 parts by weight of the lipophilic polyol based on 100 parts by weight of the total polyol component, more specifically, the anhydrosugar alcohol-alkylene oxide adduct and the lipophilic polyol may be contained in amounts of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, respectively, and the anhydrosugar alcohol-alkylene oxide adduct and the lipophilic polyol may be contained in amounts of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or 80 parts by weight or less, respectively, in 100 parts by weight of the total polyol component, but is not limited thereto.
According to a specific embodiment, in the first preparation method of the (meth) acrylic modified polyurethane composition, the reaction of the polyol component and the polyisocyanate in the step (1) may be performed at a normal temperature or elevated temperature (e.g., 50 to 100 ℃, preferably 50 to 70 ℃) for a suitable time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours) in the presence of an arbitrary catalyst (e.g., tin-based catalyst such as dibutyltin dilaurate (DBTDL)), and the reaction product of the polyol component and the polyisocyanate in the step (2) (i.e., the intermediate obtained from the step (1)) may be performed at an elevated temperature (e.g., 50 to 100 ℃, preferably 50 to 70 ℃) for a suitable time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours) in the presence of an arbitrary catalyst (e.g., tin-based catalyst such as dibutyltin dilaurate (DBTDL)).
According to a specific embodiment, in the second preparation method of the (meth) acrylic-modified polyurethane composition, (i) 16 to 84 parts by weight of a hydrophilic (meth) acrylic-modified polyurethane and (ii) 16 to 84 parts by weight of a lipophilic (meth) acrylic-modified polyurethane, more specifically, (i) a hydrophilic (meth) acrylic-modified polyurethane and (ii) a lipophilic (meth) acrylic-modified polyurethane may be mixed in amounts of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, respectively, based on the total 100 parts by weight of the prepared (meth) acrylic-modified polyurethane composition, and the hydrophilic (meth) acrylic-modified polyurethane and the lipophilic (meth) acrylic-modified polyurethane may be mixed in amounts of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, respectively, but are not limited thereto.
The respective preparation methods of (i) hydrophilic (meth) acrylic-modified polyurethane and (ii) lipophilic (meth) acrylic-modified polyurethane mixed in the second preparation method of the (meth) acrylic-modified polyurethane composition are as described above.
The (meth) acrylic-modified polyurethane composition according to the present invention has excellent environmental protection, and can improve both its adhesion (particularly adhesion between different materials) and oil resistance excellently when used in an adhesive composition.
Thus, according to another aspect of the present invention, there is provided an adhesive composition comprising the (meth) acrylic-modified polyurethane composition of the present invention and an article to which the adhesive composition is applied.
In a specific embodiment, the adhesive composition is used for adhesion between different materials, for example, adhesion between a metal material and a material other than metal (for example, an organic material such as a plastic material), and the article may contain those different materials that are adhered to each other by the adhesive composition.
In a specific embodiment, the adhesive composition may further comprise a (meth) acrylic monomer and/or an epoxy resin.
In a specific embodiment, the adhesive composition may further comprise additives that may be generally used for adhesives, for example, a curing accelerator, a polymerization initiator, and/or a polymerization inhibitor.
According to another aspect of the present invention, there is provided a hygroscopic coating composition comprising the (meth) acrylic modified polyurethane composition of the present invention.
In a particular embodiment, the hygroscopic coating composition may be particularly suitable for anti-fog use.
In a specific embodiment, the hygroscopic coating composition may further comprise a (meth) acrylic monomer.
In a specific embodiment, the hygroscopic coating composition may further comprise additives that may be generally used for hygroscopic coating agents (e.g., antifogging agents, etc.), such as polymerization initiators (e.g., thermal polymerization initiators, photopolymerization initiators, etc.), and/or polymerization inhibitors.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.
Examples (example)
< preparation of anhydrosugar alcohol-alkylene oxide adduct >
Preparation example A1: preparation of isosorbide-ethylene oxide 5 mole adduct
146g of isosorbide was charged into a pressurizable reactor, and 0.15g of phosphoric acid (85%) as an acid component was added, then the inside of the reactor was replaced with nitrogen and heated to 100 ℃, and the moisture in the reactor was removed by vacuum depressurization. 88g of ethylene oxide were then slowly added to the reactor for the first time and reacted at a temperature of 100-140℃for 2-3 hours. At this time, the reaction temperature was adjusted so that the reaction temperature did not exceed 140 ℃. After that, the internal temperature of the reactor was cooled to 50 ℃, then 0.3g of potassium hydroxide was added to the reactor, the inside of the reactor was replaced with nitrogen and heated to 100 ℃, and the moisture in the reactor was removed by vacuum depressurization. Next, 132g of ethylene oxide was slowly added for the second time and reacted at 100-140℃for 2-3 hours. After the completion of the reaction, the internal temperature of the reactor was cooled to 50℃and 4.0g of Ambosol MP20 as an adsorbent was added, and the mixture was heated again and stirred at a temperature of 100-120℃for 1-5 hours to remove metal ions (at this time, the reactor interior was replaced with nitrogen and/or vacuum reduced). When it was confirmed that no metal ions were detected, the reactor internal temperature was cooled to 60 to 90℃and then residual byproducts were removed, thereby obtaining 362g of a transparent liquid isosorbide-ethylene oxide 5-mole adduct.
Preparation example A2: preparation of an isosorbide-ethylene oxide 10 mole adduct
551g of a transparent liquid isosorbide-ethylene oxide 10 mole adduct was obtained by the same method as in preparation example A1, except that the second addition amount of ethylene oxide was changed from 132g to 352 g.
Preparation example A3: preparation of isosorbide-propylene oxide 5 mole adduct
Propylene oxide was used instead of ethylene oxide as a raw material for the addition reaction. Specifically, the same procedure as in preparation A1 was conducted except that 116g of propylene oxide was added for the first time in place of 88g of ethylene oxide and 174g of propylene oxide was added for the second time in place of 132g of ethylene oxide, thereby obtaining 423g of a transparent liquid isosorbide-propylene oxide 5-mole adduct.
Preparation example A4: preparation of 10 mole adducts of isosorbide-propylene oxide
Propylene oxide was used instead of ethylene oxide as a raw material for the addition reaction. Specifically, the same procedure as in preparation A1 was conducted except that 116g of propylene oxide was added for the first time in place of 88g of ethylene oxide and 465g of propylene oxide was added for the second time in place of 132g of ethylene oxide, thereby obtaining 698g of a transparent liquid isosorbide-propylene oxide 10 mole adduct.
Preparation of (meth) acrylic modified polyurethane composition
Example A1: using polypropylene glycol (80 parts by weight based on 100 parts by weight of total polyol) and isosorbide Alcohol-ethylene oxide 5 molar adduct (20 parts by weight based on 100 parts by weight of total polyol) as a polyolAlcohol, isophora Alkene diisocyanate (IPDI) as polyisocyanate and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth) acrylate Preparation of (meth) acrylic modified polyurethane compositions
600g of isophorone diisocyanate (IPDI) and 0.6g of dibutyltin dilaurate (DBTDL) as a reaction catalyst were charged into a three-port glass reactor equipped with a stirrer, and a crosslinking reaction was carried out by slowly adding 800g of polypropylene glycol (number average molecular weight: 1000g/mol, jinhu petrochemistry) as a polyol and 200g of the isosorbide-ethylene oxide 5 mole adduct obtained in preparation A1 while mixing at ordinary temperature. After the addition of the polyol component was completed, aging was performed at 50℃with stirring for 1 hour, and then 350g of 2-hydroxyethyl methacrylate was slowly added and an acrylic acid modification reaction was performed. After completion of the addition of 2-hydroxyethyl methacrylate, aging was stirred at 50℃for 1 hour, and then the reaction product was cooled to normal temperature, thereby obtaining 1950g of a (meth) acrylic acid modified polyurethane composition comprising 390g of a (meth) acrylic acid modified polyurethane of the following chemical formula A-1 and 1560g of a (meth) acrylic acid modified polyurethane of the following chemical formula A-2.
[ formula A-1]
[ formula A-2]
Example A2: polytetrahydrofuran (50 parts by weight based on 100 parts by weight of total polyol) and Isshan are used 10 mol of a sorbitol-ethylene oxide adduct (50 parts by weight based on 100 parts by weight of total polyol) as polyol, Hexamethylene Diisocyanate (HDI) as polyisocyanate and 2-hydroxyethyl acrylate as hydroxyalkyl (meth) acrylateBase group Ester preparation of (meth) acrylic modified polyurethane compositions
By the same procedure as in example A1 except that 270g of Hexamethylene Diisocyanate (HDI) was used as the polyisocyanate in place of isophorone diisocyanate (IPDI), 365g of polytetrahydrofuran (number average molecular weight: 2000g/mol, aldrich) and 365g of the isosorbide-ethylene oxide 10 molar adduct obtained in preparation example A2 were used as the polyol in place of polypropylene glycol (number average molecular weight: 1000g/mol, nylon lake petrochemistry) and 186g of 2-hydroxyethyl acrylate was used as the hydroxyalkyl (meth) acrylate in place of 2-hydroxyethyl methacrylate, 5g of (meth) acrylic polyurethane composition comprising 593g of the (meth) acrylic modified polyurethane of the following chemical formula B-1 and 592g of the 1185g of the (meth) acrylic modified polyurethane of the following chemical formula B-2 was obtained.
[ chemical formula B-1]
[ chemical formula B-2]
Example A3: the polydimethyl siloxane diol (20 wt. based on 100 parts of total polyol Parts) and isosorbide-propylene oxide 5 molar adduct (80 parts by weight based on 100 parts by weight total polyol) Polyol, diphenylmethane diisocyanate (MDI) as polyisocyanate, 2-hydroxyethyl methacrylate as (meth) propane Preparation of (meth) acrylic modified polyurethane compositions from hydroxyalkyl alkenoates
The same procedure as in example A1 was repeated except that 700g of diphenylmethane diisocyanate (MDI) was used as the polyisocyanate in place of isophorone diisocyanate (IPDI), 140g of polydimethylsiloxane diol (number average molecular weight: 1000g/mol, aldrich) and 560g of the isosorbide-propylene oxide 5 molar adduct obtained in preparation A3 were used as the polyol in place of polypropylene diol (number average molecular weight: 1000g/mol, jinhu petrochemistry) and the isosorbide-ethylene oxide 5 molar adduct obtained in preparation A1, and the content of 2-hydroxyethyl methacrylate was changed from 350g to 364g, thereby obtaining 1763g of a (meth) acrylic modified polyurethane composition comprising 1410g of the (meth) acrylic modified polyurethane of the following formula C-1 and 353g of the (meth) acrylic modified polyurethane of the following formula C-2.
[ chemical formula C-1]
[ chemical formula C-2]
Example A4: polytetrahydrofuran (30 parts by weight based on 100 parts by weight of total polyol) and Isshan are used 10 mol of the sorbitol-propylene oxide adduct (70 parts by weight, based on 100 parts by weight of total polyol) as polyol, isophorone diisocyanate (IPDI) was used as polyisocyanate and 2-hydroxyethyl methacrylate was used as (meth) propane Preparation of (meth) acrylic modified polyurethane compositions from hydroxyalkyl alkenoates
The same procedure as in example A1 was conducted except that as the polyol, 324g of polytetrahydrofuran (number average molecular weight: 1000g/mol, aldrich Co.) and 746g of the isosorbide-propylene oxide 10 mol adduct obtained in preparation example A4 were used instead of polypropylene glycol (number average molecular weight: 1000g/mol, nylon lake petrochemistry) and the isosorbide-ethylene oxide 5 mol adduct obtained in preparation example A1, thereby obtaining 2020g of (meth) acrylic acid modified polyurethane composition comprising 1414g of (meth) acrylic acid modified polyurethane of the following chemical formula D-1 and 606g of (meth) acrylic acid modified polyurethane of the following chemical formula D-2.
[ chemical formula D-1]
[ chemical formula D-2]
Example A5: preparation of hydrophilic (meth) acrylic modified polyurethane and lipophilic (meth) acrylic modified polyurethane, respectively After polyurethanes, they are mixed to prepare (meth) acrylic-modified polyurethane compositions
The same procedure as in example A1 was conducted except that polypropylene glycol (number average molecular weight: 1000g/mol, jinhu petrochemistry) was not used as a polyol component, and only 981g of the isosorbide-ethylene oxide 5-mole adduct obtained in preparation example A1 was used, thereby obtaining 1930g of (meth) acrylic acid modified polyurethane of the following chemical formula A-1.
[ formula A-1]
Further, the same procedure as in example A1 was conducted except that the isosorbide-ethylene oxide 5-mole adduct obtained in preparation A1 was not used as a polyol component, and 1349g of polypropylene glycol (number average molecular weight: 1000g/mol, jinhu petrochemical) was used alone, to thereby obtain 2250g of a (meth) acrylic acid-modified polyurethane of the following chemical formula A-2.
[ formula A-2]
200g of the above-obtained (meth) acrylic acid-modified polyurethane of the formula A-1 and 800g of the above-obtained (meth) acrylic acid-modified polyurethane of the formula A-2 were simply mixed to obtain 1000g of a (meth) acrylic acid-modified polyurethane composition.
Example A6: preparation of hydrophilic (meth) acrylic modified polyurethane and lipophilic (meth) acrylic modified polyurethane, respectively After polyurethanes, they are mixed to prepare (meth) acrylic-modified polyurethane compositions
The (meth) acrylic acid-modified polyurethane of the chemical formula A-1 and the (meth) acrylic acid-modified polyurethane of the chemical formula A-2 were simply mixed by the same method as in example A5 except that the content of the (meth) acrylic acid-modified polyurethane of the chemical formula A-1 obtained above was changed from 200g to 500g and the content of the (meth) acrylic acid-modified polyurethane of the chemical formula A-2 obtained above was changed from 800g to 500g to obtain 1000g of a (meth) acrylic acid-modified polyurethane composition.
Example A7: preparation of hydrophilic (meth) acrylic modified polyurethane and lipophilic (meth) acrylic modified polyurethane, respectively After polyurethanes, they are mixed to prepare (meth) acrylic-modified polyurethane compositions
The (meth) acrylic acid-modified polyurethane of the chemical formula A-1 and the (meth) acrylic acid-modified polyurethane of the chemical formula A-2 were simply mixed by the same method as in example A5 except that the content of the (meth) acrylic acid-modified polyurethane of the chemical formula A-1 obtained above was changed from 200g to 800g and the content of the (meth) acrylic acid-modified polyurethane of the chemical formula A-2 obtained above was changed from 800g to 200g to obtain 1000g of a (meth) acrylic acid-modified polyurethane composition.
Comparative example A1: use of isosorbide-ethylene oxide 5 mole adduct as polyol, use of isophorone diiso Cyanate ester [ ]IPDI) as polyisocyanate and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth) acrylate Preparation of (meth) acrylic modified polyurethane
The same procedure as in example A1 was conducted except that polypropylene glycol (number average molecular weight: 1000g/mol, nylon lake petrochemistry) was not used as the polyol, and only 981g of the isosorbide-ethylene oxide 5-mole adduct obtained in preparation example A1 was used, thereby obtaining 1930g of (meth) acrylic acid modified polyurethane of the following chemical formula A-1.
[ formula A-1]
Comparative example A2: use of polypropylene glycol as polyol and isophorone diisocyanate (IPDI) as polyiso-polymer Cyanate esters, preparation of (meth) acrylic modified polyamines using 2-hydroxyethyl methacrylate as hydroxyalkyl (meth) acrylate Esters of
2250g of (meth) acrylic acid-modified polyurethane of the following chemical formula A-2 was obtained by the same method as in example A1 except that the isosorbide-ethylene oxide 5-mole adduct obtained in preparation A1 was not used as the polyol, and only 1349g of polypropylene glycol (number average molecular weight: 1000g/mol, inward petrochemical) was used.
[ formula A-2]
< preparation of composition for bonding different materials >
Examples B1 to B7 and comparative examples B1 to B2: standard preparation method
The (meth) acrylic acid-modified polyurethane composition, the (meth) acrylic acid monomer, the epoxy resin, the epoxy curing accelerator, the thermal polymerization initiator and the polymerization inhibitor were added in the weight ratio described in the following table 1 in a mixing reactor controlled at 60 ℃ or less, and they were mixed while stirring at a temperature of 60 ℃ or less, thereby preparing a composition for bonding different materials in a liquid phase.
At this time, the total content of the (meth) acrylic acid-modified polyurethane composition, the (meth) acrylic acid monomer, the epoxy resin, the epoxy curing accelerator, the thermal polymerization initiator, and the polymerization inhibitor is 100 parts by weight in total.
< description of ingredients >
(1) (meth) acrylic-modified polyurethane component ((meth) acrylic-modified PU component)
Example A1: (meth) acrylic-modified polyurethane composition obtained in example A1
Example A2: (meth) acrylic-modified polyurethane composition obtained in example A2
Example A3: (meth) acrylic-modified polyurethane composition obtained in example A3
Example A4: (meth) acrylic-modified polyurethane composition obtained in example A4
Example A5: (meth) acrylic-modified polyurethane composition obtained in example A5
Example A6: (meth) acrylic-modified polyurethane composition obtained in example A6
Example A7: (meth) acrylic-modified polyurethane composition obtained in example A7
Comparative example A1: (meth) acrylic-modified polyurethane of the formula A-1 obtained in comparative example A1
Comparative example A2: (meth) acrylic-modified polyurethane of the formula A-2 obtained in comparative example A2
(2) (meth) acrylic acid monomer
-2-HEMA: 2-hydroxyethyl methacrylate (Samchun Pure Chemical)
-4-HBA: acrylic acid 4-hydroxybutyl ester (Samchun Pure Chemical)
-BA: butyl acrylate (Samchun Pure Chemical)
PETTA: pentaerythritol tetraacrylate (Meiyuan business)
-P-2M: 2-methacryloxyethyl phosphate (Co., ltd.)
BDDA:1, 4-butanediol diacrylate (Aldrich Co.)
(3) Epoxy resin
DGEBA: bisphenol A epoxy resin (Guotou chemical)
-YDF-170: bisphenol F series epoxy resin (Guotou chemical)
-1,4-BDGE:1, 4-butanediol diglycidyl ether (national chemistry)
(4) Epoxy curing accelerator
-dic y: dicyandiamide (win-creation company ()
UR2T:1,1' - (4-methyl m-phenylene) bis (3, 3-dimethylurea) (Yingzhang Co., ltd.)
(5) Thermal polymerization initiator
-V-65:2,2' -azobis (2, 4-dimethylvaleronitrile) (Fuji film Co., ltd.)
-V-40:1,1' -azobis (cyclohexane-1-carbonitrile) (Fuji film Co., ltd.)
Perolytcp: bis (4-t-butylcyclohexyl) peroxydicarbonate (Nichiyu Co.)
(6) Polymerization inhibitor
MEHQ: hydroquinone monomethyl ether (Aldrich)
TABLE 1
TABLE 1 (continuation)
< evaluation of physical Properties of composition for bonding different materials >
The compositions for bonding different materials prepared in examples B1 to B7 and comparative examples B1 to B2 were coated on the surfaces of a rolled steel plate cut to a size of 2.5cm×12cm and a Carbon Fiber Reinforced Plastic (CFRP) cut to a size of 2.5cm×12cm in an area of 2.5cm×1.25cm, respectively, and after the thickness was adjusted using 0.2mm glass beads, the coated parts were overlapped and fixed, and then heated and cured at 100 ℃ for 2 minutes to prepare bonding test pieces of different materials. The adhesion, oil resistance and storage stability of each test piece were evaluated by the following physical property measurement methods, and the results thereof are shown in table 2 below.
< method for measuring physical Properties >
(1) Adhesion to
To evaluate the adhesion of the compositions to the different materials, the shear strength (Lap shear strength, unit: MPa) of the adhesion test pieces of each of the different materials was measured at room temperature (23 ℃) using UTM (Instron 5967 product, instron) and the adhesion test pieces of each of the different materials was measured after heating to 100℃using a hot air dryer. Specifically, the average value was calculated after measuring the shear strength for a total of 5 times for each of the adhesive test pieces of different materials. The higher the shear strength means the more excellent the adhesion.
(2) Oil resistance
The adhesive test pieces of the different materials were immersed in mineral oil (Daejung Chemicals), heated at 90℃for 50 hours, and then the shear strength of each of the immersed adhesive test pieces of the different materials was measured 5 times by the above-mentioned (1) adhesion measuring method, and the average value thereof was calculated. Thereafter, the reduction (%) in shear strength after impregnation compared with the shear strength before impregnation was calculated for each of the adhesive test pieces of different materials. The lower the reduction rate of the shear strength means the more excellent the oil resistance.
Shear strength decrease rate (%) = (shear strength before impregnation-shear strength after impregnation) ×100/shear strength before impregnation
(3) Storage stability
The compositions for bonding different materials prepared in examples B1 to B7 and comparative examples B1 to B2 were placed in transparent glass bottles, respectively, and sealed, and then left at normal temperature (23 ℃) for 3 days, and then visually confirmed whether to cure.
TABLE 2
As shown in the above table 2, in the case of the adhesive compositions of examples B1 to B7 prepared using the (meth) acrylic-modified polyurethane composition according to the present invention, the shear strength at normal temperature (23 ℃) was 23MPa or more, the adhesion between the different materials was excellent, the excellent adhesion of 17MPa or more was also maintained at high temperature (100 ℃) and the shear strength decrease rate was also less than 20% after being immersed in mineral oil for 50 hours at 90 ℃, the adhesive force was well maintained, and thus the oil resistance was also excellent.
However, in the case of the adhesive composition of comparative example B1, to which the (meth) acrylic-modified polyurethane composition prepared without using the lipophilic polyol was applied, the adhesive force with Carbon Fiber Reinforced Plastic (CFRP) was lowered, and thus, low shear strength was exhibited at both normal temperature and high temperature. In addition, in the case of the adhesive composition of comparative example B2 using the (meth) acrylic modified polyurethane composition prepared without using the anhydrosugar alcohol-alkylene oxide adduct, the adhesive force with the metal (rolled steel sheet) is lowered, and thus the adhesive test piece of the different material exhibits low shear strength at both normal temperature and high temperature, and after completion of heating in an oil-immersed state, the adhesive test piece of the different material is naturally peeled off, and thus the oil resistance is poor.
As described above, in the case of the adhesive composition comprising the (meth) acrylic-modified polyurethane composition according to the present invention, the adhesion between different materials at normal temperature is excellent, and the adhesion is maintained even when heated to high temperature or in oil at high temperature, thereby having excellent high-temperature adhesion and oil resistance.
< preparation of hygroscopic coating composition >
Examples C1 to C7 and comparative examples C1 to C2: standard preparation method
The (meth) acrylic acid-modified polyurethane composition, the (meth) acrylic acid monomer, the thermal polymerization initiator and the polymerization inhibitor were added in the weight ratio described in the following table 3 in a mixing reactor controlled at 60 ℃ or less, and they were mixed while stirring at a temperature of 60 ℃ or less, thereby preparing a hygroscopic coating composition in a liquid phase.
At this time, the total content of the (meth) acrylic acid-modified polyurethane composition, the (meth) acrylic acid monomer, the thermal polymerization initiator, and the polymerization inhibitor is 100 parts by weight in total.
< description of ingredients >
(1) (meth) acrylic-modified polyurethane component ((meth) acrylic-modified PU component)
Example A1: (meth) acrylic-modified polyurethane composition obtained in example A1
Example A2: (meth) acrylic-modified polyurethane composition obtained in example A2
Example A3: (meth) acrylic-modified polyurethane composition obtained in example A3
Example A4: (meth) acrylic-modified polyurethane composition obtained in example A4
Example A5: (meth) acrylic-modified polyurethane composition obtained in example A5
Example A6: (meth) acrylic-modified polyurethane composition obtained in example A6
Example A7: (meth) acrylic-modified polyurethane composition obtained in example A7
Comparative example A1: (meth) acrylic-modified polyurethane of the formula A-1 obtained in comparative example A1
Comparative example A2: (meth) acrylic-modified polyurethane of the formula A-2 obtained in comparative example A2
(2) (meth) acrylic acid monomer
-2-HEMA: 2-hydroxyethyl methacrylate (Samchun Pure Chemical)
-4-HBA: acrylic acid 4-hydroxybutyl ester (Samchun Pure Chemical)
-BA: butyl acrylate (Samchun Pure Chemical)
PETTA: pentaerythritol tetraacrylate (Meiyuan business)
-P-2M: 2-methacryloxyethyl phosphate (Co., ltd.)
(3) Thermal polymerization initiator
-V-40:1,1' -azobis (cyclohexane-1-carbonitrile) (Fuji film Co., ltd.)
Perolytcp: bis (4-t-butylcyclohexyl) peroxydicarbonate (Nichiyu Co., ltd.)
(4) Polymerization inhibitor
MEHQ: hydroquinone monomethyl ether (Aldrich)
TABLE 3
TABLE 3 (continuation)
< evaluation of physical Properties of hygroscopic coating composition >
(1) Hygroscopicity
In order to evaluate the hygroscopicity of the hygroscopic coating compositions, the hygroscopic coating compositions prepared in examples C1 to C7 and comparative examples C1 to C2 were respectively filled into frames made of polytetrafluoroethylene having dimensions of 5cm×5cm×2cm (width×length×height), and then cured by heat treatment at 100 ℃ for 20 minutes, thereby preparing test pieces for evaluating hygroscopicity.
After measuring the weight of the test piece for evaluating hygroscopicity, the test piece for evaluating hygroscopicity was immersed in water at room temperature (15-25 ℃) for 10 hours to perform moisture absorption. Thereafter, the test piece for evaluating hygroscopicity was taken out of water, then the entire surface of the test piece for evaluating hygroscopicity was wiped with a dry ultrafine fiber cloth, then the weight of the test piece was measured, and the hygroscopicity was calculated by the following formula.
Moisture absorption (%) = [ (weight of test piece after impregnation-weight of test piece before impregnation)/weight of test piece before impregnation ] ×100
(2) Adhesion to glass
The hygroscopic coating compositions prepared in examples C1 to C7 and comparative examples C1 to C2 were coated on a transparent glass at a coating speed of about 35 to mm/sec using a Bar (Bar) coating method, and then heat-treated at 100 ℃ for 20 minutes to prepare a hygroscopic coated test piece.
To evaluate the adhesion of the hygroscopicity-coated test pieces, moisture absorption was performed by immersing in water at room temperature (15-25 ℃) for 10 hours, and then scratches were left on the coating film of the test pieces in crossing lines using a dicing blade (Cross hatch cutter) according to ASTM D3359, which is an adhesion test standard of the coating agent, thereby manufacturing 100 mesh blocks having dimensions of 10mm×10mm (width×length). Then, an adhesive tape was attached to the mesh block and rubbed with a uniform force, and then the adhesive tape was peeled off, and the number of mesh blocks peeled off from the coating film of the test piece and attached to the peeled adhesive tape was counted. The degree of adhesion was shown as a number of 0 to 5B below according to the number of lattice pieces of the coated glass from the test piece, and the smaller the number of lattice pieces peeled off from the coated film of the test piece, the more excellent the adhesion of the coated film to glass (a grade of 3B or more is required).
[ transverse cutting classification Standard (ASTM D3359) ]
Grade Standard of
5B The grid block is not peeled off from the coating film at all
4B The number of the grid blocks peeled from the coating film is 1-5
3B The number of the grid blocks peeled from the coating film is 6-15
2B The number of the grid blocks peeled from the coating film is 16-35
1B The number of the grid blocks peeled from the coating film is 36-65
0B The number of grid blocks peeled from the coating film is 66 or more
(3) Antifogging property
The hygroscopic coating compositions prepared in examples C1 to C7 and comparative examples C1 to C2 were coated on a transparent glass at a coating speed of about 35 to mm/sec using a 10-bar according to a bar coating method, and then heat-treated at 100 ℃ for 20 minutes to prepare a hygroscopic coated test piece.
To evaluate the anti-fog properties of the hygroscopicity coated test pieces, the presence or absence of fog was confirmed by placing the coated side of the hygroscopicity coated test pieces at the inlet of a beaker filled with water at 50 ℃. During 1 minute exposure, when no fogging was observed, the anti-fogging test was evaluated as "acceptable", and even weak fogging was evaluated as "unacceptable".
TABLE 4
As shown in the table 4, in the case of the hygroscopic coating compositions of examples C1 to C7 prepared using the (meth) acrylic-modified polyurethane composition according to the present invention, the hygroscopic coating composition exhibited 10 to 40% of the hygroscopic rate when immersed in water for 10 hours at room temperature (15 to 25 ℃) and thus exhibited excellent hygroscopicity, and after hygroscopic, the adhesion to a glass plate was also 3B or more, thus exhibiting excellent adhesiveness, and also achieved excellent antifogging properties.
However, in the case of the hygroscopic coating composition of comparative example C1, which was prepared using the (meth) acrylic modified polyurethane composition without using the lipophilic polyol, excessive swelling occurred due to the moisture absorption rate higher than 40%, so the adhesion to the glass plate was 1B, and very poor adhesion was exhibited.
In the case of the hygroscopic coating composition of comparative example C2, which applied the (meth) acrylic modified polyurethane composition prepared without using the anhydrosugar alcohol-alkylene oxide adduct, the hygroscopic rate was too low, and the adhesion to the glass plate was 2B, exhibiting poor adhesion, and poor antifogging property.
As described above, in the case of the hygroscopic coating composition comprising the (meth) acrylic-modified polyurethane composition according to the present invention, it is known that the adhesive force to a glass plate is excellent even after moisture absorption, and the antifogging property is also excellent.

Claims (20)

1. A (meth) acrylic modified polyurethane composition comprising:
(1) A hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate; and
(2) A lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
2. The (meth) acrylic-modified polyurethane composition according to claim 1, wherein 16 to 84 parts by weight of the hydrophilic (meth) acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth) acrylic-modified polyurethane are contained based on 100 parts by weight of the (meth) acrylic-modified polyurethane composition in total.
3. The (meth) acrylic-modified polyurethane composition according to claim 1, wherein the anhydrosugar alcohol-alkylene oxide adduct is obtained by reacting hydroxyl groups of both ends or one end of an anhydrosugar alcohol with an alkylene oxide, wherein the alkylene oxide is a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms.
4. The (meth) acrylic modified polyurethane composition of claim 3, wherein the anhydrosugar alcohol is isosorbide, isomannide, isoidide, or a combination thereof.
5. The (meth) acrylic modified polyurethane composition of claim 1, wherein the polyisocyanate is diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.
6. The (meth) acrylic-modified polyurethane composition according to claim 1, wherein the hydroxyalkyl (meth) acrylate is hydroxy-C (meth) acrylate 1-8 Alkyl esters.
7. The (meth) acrylic-modified polyurethane composition according to claim 1, wherein the hydrophilic (meth) acrylic-modified polyurethane is represented by the following chemical formula 2:
[ chemical formula 2]
In the chemical formula 2 described above, a compound having a structure of,
each R1 is independently an alkylene group,
r2 is each independently alkylene, cycloalkylene or arylene,
each R3 is independently an alkylene group,
r4 are each independently a hydrogen atom or an alkyl group,
m is a divalent organic group derived from anhydrosugar alcohol,
m and n each independently represent an integer of 0 to 15,
m+n represents an integer of 1 to 30.
8. The (meth) acrylic-modified polyurethane composition according to claim 7, wherein in the chemical formula 2,
r1 is each independently a C2-C8 straight-chain alkylene or a C3-C8 branched alkylene,
R2 is each independently C2-C20 linear alkylene or C3-C20 branched alkylene, C3-C20 cycloalkylene or C6-C20 arylene,
r3 is each independently a C1-C8 straight-chain alkylene or a C3-C8 branched alkylene,
r4 is each independently a hydrogen atom or a C1-C4 straight-chain alkyl group or a C3-C4 branched alkyl group,
m is a divalent organic group derived from isosorbide, isomannide or isoidide,
m and n each independently represent an integer of 0 to 15,
m+n represents an integer of 1 to 25.
9. The (meth) acrylic modified polyurethane composition of claim 1, wherein the lipophilic polyol is selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof.
10. The (meth) acrylic-modified polyurethane composition according to claim 1, wherein the lipophilic (meth) acrylic-modified polyurethane is represented by the following chemical formula 3:
[ chemical formula 3]
In the chemical formula 3 described above, the chemical formula,
r1 is each independently alkylene, cycloalkylene or arylene,
each R2 is independently an alkylene group,
r3 is each independently a hydrogen atom or an alkyl group,
l is a divalent organic group derived from a lipophilic polyol,
the lipophilic polyol has a number average molecular weight of 200-3000g/mol.
11. The (meth) acrylic-modified polyurethane composition according to claim 10, wherein in the chemical formula 3,
r1 is each independently C2-C20 linear alkylene or C3-C20 branched alkylene, C3-C20 cycloalkylene or C6-C20 arylene,
r2 is each independently a C1-C8 straight-chain alkylene or a C3-C8 branched alkylene,
r3 is each independently a hydrogen atom or a C1-C4 linear alkyl group or a C3-C4 branched alkyl group,
l is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyols or combinations thereof,
the lipophilic polyol has a number average molecular weight of 500-2500g/mol.
12. A process for preparing a (meth) acrylic modified polyurethane composition comprising the steps of:
(1) Reacting a polyol component comprising a anhydrosugar alcohol-alkylene oxide adduct and a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminus; and
(2) Reacting the intermediate obtained in step (1) with a hydroxyalkyl (meth) acrylate.
13. The method for producing a (meth) acrylic-modified polyurethane composition according to claim 12, wherein the polyol component contains 16 to 84 parts by weight of the anhydrosugar alcohol-alkylene oxide adduct and 16 to 84 parts by weight of the lipophilic polyol, based on 100 parts by weight of the total polyol component.
14. A process for preparing a (meth) acrylic modified polyurethane composition comprising the steps of: mixing (i) a hydrophilic (meth) acrylic modified polyurethane comprising polymerized units derived from an anhydrosugar alcohol-alkylene oxide adduct, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate, and (ii) a lipophilic (meth) acrylic modified polyurethane comprising polymerized units derived from a lipophilic polyol, polymerized units derived from a polyisocyanate, and polymerized units derived from a hydroxyalkyl (meth) acrylate.
15. The method for producing a (meth) acrylic-modified polyurethane composition according to claim 14, wherein,
the (i) hydrophilic (meth) acrylic-modified polyurethane is prepared by a process comprising the steps of: (a) Reacting a anhydrosugar alcohol-alkylene oxide adduct and a polyisocyanate to produce an intermediate having an isocyanate terminus; and (b) reacting the intermediate obtained from step (a) with a hydroxyalkyl (meth) acrylate,
the (ii) lipophilic (meth) acrylic modified polyurethane is prepared by a process comprising the steps of: (c) Reacting a lipophilic polyol with a polyisocyanate to produce an intermediate having isocyanate ends; and (d) reacting the intermediate obtained from step (c) with a hydroxyalkyl (meth) acrylate.
16. The method for producing a (meth) acrylic-modified polyurethane composition according to claim 14, wherein 16 to 84 parts by weight of the hydrophilic (meth) acrylic-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth) acrylic-modified polyurethane are mixed based on 100 parts by weight of the total (meth) acrylic-modified polyurethane composition.
17. An adhesive composition comprising the (meth) acrylic-modified polyurethane composition according to any one of claims 1 to 11.
18. An article employing the adhesive composition of claim 17.
19. A hygroscopic coating composition comprising the (meth) acrylic modified polyurethane composition of any one of claims 1 to 11.
20. The hygroscopic coating composition of claim 19 wherein the hygroscopic coating composition is for anti-fog use.
CN202280054312.3A 2021-08-11 2022-08-10 (methyl) acrylic acid modified polyurethane composition and preparation method thereof Pending CN117795008A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2021-0105850 2021-08-11
KR1020210183781A KR102610226B1 (en) 2021-08-11 2021-12-21 (Meth)acryl-modified polyurethane composition and method for preparing the same
KR10-2021-0183781 2021-12-21
PCT/KR2022/011938 WO2023018228A1 (en) 2021-08-11 2022-08-10 (meth)acrylic-modified polyurethane composition and preparation method therefor

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CN117795008A true CN117795008A (en) 2024-03-29

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