Polyurea polymer, polyurea composition, and method for producing same

Abstract

Provided are: a polyurea polymer which is a reaction product of the following (a), (b) and (c): (a) an amino-group-containing organopolysiloxane having an amine equivalent weight of more than 1500 g / mol and 7500 g / mol or less represented by the following general formula (1); (b) an aliphatic diisocyanate compound having two isocyanate groups in one molecule; and (c) an amine compound having two or more amino groups in one molecule. (In the formula, R1 independently represents a monovalent hydrocarbon group having 1-20 carbon atoms and having a primary or secondary amino group, R2 independently represents a monovalent hydrocarbon group having 1-20 carbon atoms, and n represents a value satisfying the above-mentioned amine equivalents)

Description

Technical Field

[0001] This invention relates to polyurea polymers, polyurea compositions, and methods for manufacturing the same. Background Technology

[0002] Polyurea resins possess tensile strength, flexural strength, abrasion resistance, and oil resistance. Depending on their composition, they can be made into thermoplastic or thermosetting resins, thus allowing them to be processed into a wide variety of shapes.

[0003] Polyamines, isocyanates, chain extenders, etc. are used as raw materials for polyurea resins. In recent years, as a polyamine, a scheme to copolymerize reactive siloxanes such as amino-containing siloxanes has been proposed (Patent Document 1). In Patent Document 1, a method for manufacturing siloxane-modified polyurea fibers and its manufacturing process is proposed.

[0004] However, when using diamine as the chain extender described in Patent Document 1, the reaction solidifies and cannot be stirred if carried out in a solvent-free environment, resulting in an inhomogeneous polymer. Therefore, it is also possible to add the solvent described in Patent Document 1 for polymerization, but the solvents that can maintain the molten state during polymerization are highly polar solvents such as DMF and DMAc. In addition, as described in Patent Document 1, alcohol solvents (monohydric alcohols) are used as the terminal terminating agents for isocyanates and are therefore not used as solvents. Based on this, high-boiling-point solvents such as DMF and DMAc are used.

[0005] However, highly polar solvents have high boiling points and poor volatility, making them difficult to use. Therefore, there is a strong need for solvents to replace them. In addition, after synthesis using DMF and DMAc solvents, it is possible to replace them with low-boiling-point solvents, but this is time-consuming and uneconomical. Therefore, it is necessary to be able to use low-boiling-point solvents for synthesis from the synthesis stage.

[0006] On the other hand, Patent Document 2 proposes a method that uses a chlorinated solvent as a reaction solvent, but there are various restrictions on the use and disposal of chlorinated solvents, making them difficult to use.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2016 / 158967

[0010] Patent Document 2: Japanese Patent Application Publication No. 63-3029 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The present invention was made in view of the above-mentioned circumstances, and its object is to provide a polyurea polymer soluble in a low-boiling-point, easily volatile solvent and with a low strain rate, a polyurea composition comprising the thereof, and a method for manufacturing the same.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that a polyurea polymer obtained from an organopolysiloxane having a specified amine equivalent, an aliphatic diisocyanate compound, and an amine compound having two or more amino groups in one molecule can solve the above-mentioned problems. At the same time, it was found that the above-mentioned polyurea polymer can be manufactured using secondary or tertiary alcohols as solvents, thus completing the present invention.

[0015] That is, the present invention provides:

[0016] 1. A polyurea polymer, which is the product of the reaction described in (a), (b) and (c) below:

[0017] (a) An amino-containing organopolysiloxane represented by the following general formula (1) with an amine equivalent of more than 1500 g / mol and less than 7500 g / mol.

[0018] [Chemistry 1]

[0019]

[0020] (In the above formula, R) 1 Independently, R is a monovalent hydrocarbon group with 1 to 20 carbon atoms having a primary or secondary amino group. 2 Each siloxane unit is a monovalent hydrocarbon group with 1 to 20 carbon atoms, and each group is independent of the others. n represents the value that satisfies the above-mentioned amine equivalent. Furthermore, the bonding order of the siloxane units shown in parentheses is arbitrary.

[0021] (b) Aliphatic diisocyanate compounds having two isocyanate groups in one molecule,

[0022] (c) An amine compound having two or more amino groups in one molecule, excluding component (a);

[0023] 2. The polyurea polymer according to 1, wherein component (c) is represented by the following formula (4);

[0024] H2N-R-NH2 (4)

[0025] (In the above formula, R is a divalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted.)

[0026] 3. A method for manufacturing a polyurea polymer, which is a method for manufacturing a polyurea polymer according to 1 or 2, comprising a step of reacting the components (a) to (c) in an alcohol having one secondary or tertiary hydroxyl group in one molecule to obtain a polyurea polymer.

[0027] 4. A polyurea composition comprising: (A) a polyurea polymer according to 1 or 2, and (B) an alcohol having one secondary or tertiary hydroxyl group in one molecule;

[0028] 5. The polyurea composition according to 4, wherein the polyurea polymer of component (A) is a solution dissolved in the alcohol of component (B);

[0029] 6. A method for manufacturing a polyurea composition, comprising the steps of reacting components (a) to (c) in an alcohol of component (B) to synthesize a polyurea polymer of component (A), and obtaining a polyurea composition in the form of a solution of the polyurea polymer of component (A) dissolved in an alcohol of component (B).

[0030] The effects of the invention

[0031] The polyurea polymer of the present invention is more soluble in solvents with low boiling points and high volatility compared to existing polyurea polymers. Furthermore, the polyurea polymer of the present invention has a low strain rate, making it suitable for use as a sealing material. Detailed Implementation

[0032] The present invention will now be described in detail.

[0033] [1] Polyurea polymers

[0034] The polyurea polymer of the present invention is obtained by reacting the components (a) to (c) below.

[0035] (a) An amino-containing organopolysiloxane represented by the following general formula (1) with an amine equivalent of more than 1500 g / mol and less than 7500 g / mol.

[0036] (b) Aliphatic diisocyanate compounds having two isocyanate groups in one molecule,

[0037] (c) Amine compounds having two or more amino groups in one molecule.

[0038] [(a) Ingredient]

[0039] The component (a) used in this invention is an amino-containing organopolysiloxane represented by the following general formula (1) with an amine equivalent of more than 1500 g / mol and less than 7500 g / mol, which acts as the main agent of the polyurea polymer of this invention.

[0040] [Chemistry 2]

[0041]

[0042] In the above formula (1), R 1 They are monovalent hydrocarbon groups with 1 to 20 carbon atoms and either a primary or secondary amino group, which are independent of each other.

[0043] As R 1 The group has a primary or secondary amino group and a monovalent hydrocarbon group with 1 to 20 carbon atoms, for example, the group represented by the following formula (2).

[0044] -R 3 NHR 4 (2)

[0045] In equation (2) above, R 3 It is a divalent hydrocarbon group with 1 to 20 carbon atoms, and can be straight-chain, branched, or cyclic. Examples include alkylene groups with 1 to 20 carbon atoms, preferably 1 to 10; cycloalkylene groups with 3 to 20 carbon atoms, preferably 3 to 10; alkenyl groups with 2 to 20 carbon atoms, preferably 2 to 10; aryl groups with 6 to 20 carbon atoms, preferably 6 to 10; and arylalkylene groups with 7 to 20 carbon atoms, preferably 7 to 10.

[0046] As R 3 Specific examples of divalent hydrocarbon groups include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecylene, tetradecylene, hexadecylene, octadecylene, nonadecanylene, eicosylene, etc.; cyclopentylene, cyclohexylene, etc.; vinylene, propenylene, etc.; phenylene, methylphenylene, naphthylene, etc.; benzylene, phenylethylene, etc., etc.

[0047] Of these, R 3 Preferably, it is an alkylene group having 1 to 10 carbon atoms, more preferably methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, more preferably methylene, ethylene, trimethylene, or propylene, and particularly preferably ethylene or trimethylene.

[0048] R 4It is a monovalent hydrocarbon group with 1 to 20 carbon atoms or hydrogen atoms. As a monovalent hydrocarbon group with 1 to 20 carbon atoms, it can be straight-chain, branched, or cyclic. Examples include alkyl groups with 1 to 20 carbon atoms, preferably 1 to 10; cycloalkyl groups with 3 to 20 carbon atoms, preferably 3 to 10; alkenyl groups with 2 to 20 carbon atoms, preferably 2 to 10; aryl groups with 6 to 20 carbon atoms, preferably 6 to 10; and aralkyl groups with 7 to 20 carbon atoms, preferably 7 to 10.

[0049] As R 4 Specific examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl.

[0050] Of these, R 4 Preferably, it is an alkyl group with 1 to 6 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, or propyl, and even more preferably a hydrogen atom or a methyl group.

[0051] Specific examples of groups represented by the above formula (2) include aminomethyl, 2-aminoethyl-1-yl, 2-aminopropyl-1-yl, 3-aminopropyl-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, N-methylaminomethyl, N-methyl-2-aminoethyl-1-yl, N-methyl-2-aminopropyl-1-yl, N-methyl-3-aminopropyl-1-yl, N-methyl-2-aminobut-1-yl, N-methyl-3-aminobut-1-yl, N-methyl-4-aminobut-1-yl, N-ethylaminomethyl, N- Ethyl-2-aminoethyl-1-yl, N-ethyl-2-aminopropyl-1-yl, N-ethyl-3-aminopropyl-1-yl, N-ethyl-2-aminobut-1-yl, N-ethyl-3-aminobut-1-yl, N-ethyl-4-aminobut-1-yl, N-butylaminomethyl, N-butyl-2-aminoethyl-1-yl, N-butyl-2-aminopropyl-1-yl, N-butyl-3-aminopropyl-1-yl, N-butyl-2-aminobut-1-yl, N-butyl-3-aminobut-1-yl, N-butyl-4-aminobut-1-yl, 8-aminooctyl-1-yl, etc.

[0052] Among these, aminomethyl, 2-aminoethyl-1-yl, 3-aminopropyl-1-yl, and 8-aminooctyl-1-yl are preferred, with 3-aminopropyl-1-yl being more preferred.

[0053] In the above equation (1), R 2 Each group is a monovalent hydrocarbon group with 1 to 20 carbon atoms, independent of the others. As R 2Specific examples of monovalent hydrocarbon groups can be listed, such as those related to R. 4 The same group as the group illustrated in the example, wherein R 2 Preferably, it is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a vinyl group; more preferably, it is methyl, ethyl, propyl, butyl, phenyl, or vinyl; and even more preferably, it is methyl or phenyl.

[0054] (a) The amine equivalent of component (a) is 1500–7500 g / mol. Preferably, it is greater than 1500 g / mol but less than 7500 g / mol, more preferably 1600–7500 g / mol, further preferably 1700–7000 g / mol, even more preferably 1900–6500 g / mol, and particularly preferably 2000–5500 g / mol. This amine equivalent represents the mass of component (a) relative to one mole of the amino group in component (a). If the amine equivalent is less than 1500 g / mol, a balance between hardness and strain rate is not achieved in the resulting polymer; if it exceeds 7500 g / mol, it is difficult to improve the strength. It should be noted that the above amine equivalent is a value determined using the neutralization titration method described later.

[0055] n is a value that satisfies the above-mentioned range of amine equivalents. The specific range of n is based on the above R... 1 and R 2 It is determined by the type of substituents. For example, in R 2 When all methyl groups are used, n is preferably a number from 37 to 199, more preferably from 42 to 186, and even more preferably from 48 to 172. It should be noted that in formula (1), the bonding order of the siloxane units shown in parentheses is arbitrary.

[0056] As specific examples of organopolysiloxanes represented by formula (1), the following organopolysiloxanes can be listed, but are not limited to these. It should be noted that in the following formulas, Me represents methyl and Ph represents phenyl. Among these, organopolysiloxanes represented by formulas (1-1) to (1-3) are preferred, and organopolysiloxanes represented by formulas (1-1) and (1-3) are more preferred.

[0057] [Chemistry 3]

[0058]

[0059] In the above formula, n 1 ~n 6 Each of the numbers is 1 or higher, n 1 =n, n 2 +n 3 =n, n 4 +n 5 +n 6=n. It should be noted that the arrangement of each repeating unit can be a block or random, and is arbitrary. In addition, (a) can use one type of component alone, or two or more types can be used together.

[0060] These organopolysiloxanes can be manufactured using conventionally known methods, for example, by reacting an amino-containing disiloxane with a cyclic siloxane having any substituents under acidic or alkaline conditions. Alternatively, commercially available products can be used.

[0061] [(b) Components]

[0062] The component (b) used in this invention is an aliphatic diisocyanate compound having two isocyanate groups in one molecule, which is a component that reacts with the component (a) above to form the polyurea polymer of this invention.

[0063] As for component (b), there are no particular restrictions as long as it has two isocyanate groups in one molecule, for example, compounds represented by the following formula (3) can be listed.

[0064] OCN-Q-NCO (3)

[0065] (In formula (3), Q is a divalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted.)

[0066] As a divalent hydrocarbon group with 1 to 20 carbon atoms in Q, it can be straight-chain, branched, or cyclic. Examples of its similarity to R can be listed. 3 The same group as the one illustrated herein, wherein Q is preferably an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms. Alternatively, it may be a group formed by combining these groups. Furthermore, at least a portion of the hydrogen atoms in these groups may be replaced by other substituents, such as alkyl groups having 1 to 3 carbon atoms, including methyl and ethyl groups.

[0067] Specific examples of isocyanate compounds represented by formula (3) include, for example, 1,6-hexamethylene diisocyanate, dodecamethyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, tetramethylphenyldimethyl diisocyanate (TMXDI), hydrogenated phenyldimethyl diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.

[0068] Among these, 1,6-hexamethylene diisocyanate, hydrogenated phenylenedimethylene diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate are preferred, and isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate are more preferred.

[0069] Furthermore, (b) ingredient can be used alone or in combination of two or more ingredients.

[0070] There is no particular limitation on the amount of component (b) to be mixed, but 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to 100 parts by mass of component (a).

[0071] [(c) Components]

[0072] The component (c) used in this invention is an amine compound having two or more amino groups in one molecule, which acts as a chain extender or crosslinking agent for the polyurea polymer of this invention.

[0073] (c) The amine compound of component (c) has two or more amino groups in one molecule, preferably two to four, more preferably two to three, and even more preferably two.

[0074] As a component (c), a compound other than component (a) is not particularly limited as long as it has more than two of the functional groups in one molecule. For example, compounds represented by the following formula (4) can be listed.

[0075] H2N-R-NH2 (4)

[0076] In formula (4), R is a divalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, and can be straight-chain, branched, or cyclic. Examples of compounds with R can be listed. 3 The same group as the one illustrated. Alternatively, it can be a group formed by combining these groups. Furthermore, at least some of the hydrogen atoms in these groups can be replaced by other substituents, such as alkyl groups with 1 to 3 carbon atoms (e.g., methyl, ethyl); halogen atoms (e.g., chlorine, bromine); and groups containing heteroatoms such as oxygen and sulfur atoms.

[0077] Specific examples of amine compounds represented by formula (4) include, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3-butanediamine, 1,2-butanediamine, 1,5-pentanediamine, 1,4-pentanediamine, 1,3-pentanediamine, 1,2-pentanediamine, 2,5-pentanediamine, 2,4-pentanediamine, 2,3-pentanediamine, 1,6-hexanediamine, 1,5-hexanediamine, 1,4-hexanediamine, 1,3-hexanediamine, 1,2-hexanediamine, 2,6-hexanediamine, 2,5-hexanediamine, 2,4-hexanediamine, 2,3-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine. Diamines include diaminotoluene, diphenylmethane diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis(aminocyclohexane), diethylmethylphenylenediamine, 4,4'-methylenediphenylamine, 4,6-diethyl-2-methyl-1,3-phenylenediamine, 2-methyl-4,6-bis(methylthio)-1,3-phenylenediamine, 4-methyl-2,6-bis(methylthio)-1,3-phenylenediamine, bis(4-amino-2,3-dichlorophenyl)methane (TCDAM), trimethylenebis(4-aminobenzoate), isophorone diamine, and 4,4'-diaminodicyclohexylmethane.

[0078] In addition, cyclic diamines such as piperazine, and triamines such as diethylenetriamine, bis(hexamethylene)triamine, and tri(aminoethyl)amine can also be used.

[0079] Among these, isophorone diamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, piperazine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 4,4'-methylenebis(aminocyclohexane), 4,4'-methylenediphenylamine, and 4,4'-diaminodicyclohexylmethane are preferred.

[0080] These can be used individually, or in combination of two or more types.

[0081] There is no particular limitation on the amount of component (c) to be mixed. It is preferred to be 1 to 20 parts by mass relative to 100 parts by mass of component (a), more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass.

[0082] Furthermore, the mixing amount of components (a) to (c) is preferably such that the ratio of {the total number of isocyanates contained in component (b)} to {the total number of amino groups contained in components (a) and (c)} is 0.7 to 1.4, more preferably 0.8 to 1.2, even more preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.05.

[0083] Furthermore, other components may be incorporated into the polyurea polymer of the present invention without impairing the effects of the invention. Examples of such other components include polyols (diols), catalysts, etc.

[0084] Specific examples of polyols (diols) include polyether polyols, polyester polyols, polycarbonate polyols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 2,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, 2,6-hexanediol, 2,5-hexanediol, 2,4-hexanediol, 2,3-hexanediol, neopentanediol, methylpentanediol, etc. Examples of other examples include trifunctional alcohols such as glycerol and trimethylolpropane; quadrifunctional alcohols such as pentaerythritol and α-methylglucoside; hexafunctional alcohols such as sorbitol and sucrose; and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

[0085] Specific examples of catalysts include triethylamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, triethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-ethylmorpholine, 1,2-dimethylimidazolium, dimethylethanolamine, dimethylaminoethoxyethanol, and N,N,N'-trimethyl... Amine compounds such as methylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, and bis(2-dimethylaminoethyl) ether; tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-tert-butoxytitanium, and diisopropoxybisacetylacetone titanium complexes; organotitanium compounds such as tetra-2-ethylhexyloxytitanium and diisopropoxybis(ethyl acetoacetate)titanium; organozirconium compounds such as tetrabutoxyzirconium, tetrapropoxyzirconium, tetra(2,4-pentanedione)zirconium, and dibutoxybis(ethyl acetoacetate)zirconium; and organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate.

[0086] [2] Manufacturing method of polyurea polymer

[0087] There are no particular limitations on the manufacturing method (synthesis method) of the polyurea polymer of the present invention, and methods conventionally used in the manufacture of polyurea resins can be used, such as the prepolymer method, the one-shot method, etc.

[0088] In the prepolymer method, firstly, component (a) reacts with component (b), and then component (c) is added to react with it. When reacting component (a) with component (b), component (b) can be added to component (a) or component (a) can be added to component (b), but the method of adding component (b) to component (a) is preferred.

[0089] The above reaction can be carried out without a solvent, but a solvent is preferred. The solvent can be added to component (a) or component (b). Alternatively, components (a) and (b) can be added together, or components (a) and (b) can be added to the solvent. Furthermore, component (c) can be added simultaneously with component (c), before adding component (c), or after the reaction of component (c). When adding the above components, they can be added dropwise or all at once.

[0090] There are no particular limitations on the reaction temperature, but it is preferably 10–150°C, more preferably 15–100°C, and even more preferably 20–60°C. There are also no particular limitations on the reaction time, but it is preferably 10 minutes–20 hours, more preferably 10 minutes–15 hours, even more preferably 10 minutes–10 hours, and even more preferably 0.5–5 hours.

[0091] On the other hand, the one-step method is a method that allows components (a), (b), and (c) to react simultaneously.

[0092] There are no particular limitations on the reaction temperature, but it is preferably 10–150°C, more preferably 15–100°C, and even more preferably 20–60°C. There are also no particular limitations on the reaction time, but it is preferably 10 minutes to 10 hours, and more preferably 0.5 to 5 hours.

[0093] In this invention, a prepolymer method is preferably used, more preferably, to react components (a) to (c) in a solvent. A further preferred method is to mix component (a) and the solvent, add component (b) to react, and then add component (c) to react. Furthermore, other components can be added to components (a) to (c) at any time.

[0094] There are no particular limitations on the solvents that can be used in the above reactions, but alcohols having one secondary or tertiary hydroxyl group per molecule are preferred. As long as the alcohol has one secondary or tertiary hydroxyl group per molecule, there are no particular limitations; examples include isopropanol, 2-butanol, 2-methyl-2-propanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclohexanol, 1-methoxy-2-propanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-ethoxy-2-propanol, etc.

[0095] Among these, isopropanol, 2-methyl-2-butanol, 2-butanol, and 1-methoxy-2-propanol are preferred.

[0096] In addition, the boiling point of the solvent is preferably below 200°C, more preferably 50–180°C, even more preferably 60–150°C, and particularly preferably 70–120°C.

[0097] When using a solvent, the amount added relative to the total of components (a) to (c) and other components of 100 parts by mass is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more. Furthermore, there is no particular limitation on the upper limit, but it is preferably 300 parts by mass or less, more preferably 250 parts by mass or less.

[0098] After the above reaction is completed, the polyurea polymer of the present invention can be obtained by drying at 20 to 200°C, more preferably at 20 to 150°C, preferably for 1 to 30 hours, more preferably for 5 to 20 hours.

[0099] Furthermore, if the above-mentioned drying process is carried out in an atmosphere of inactive gas such as nitrogen, or under reduced pressure of 700 Pa or less, the deterioration of the product is suppressed, and therefore it is preferred.

[0100] The weight-average molecular weight of the polyurea polymer of the present invention is not particularly limited, but is preferably 4,000 to 800,000, more preferably 50,000 to 800,000, and even more preferably 50,000 to 600,000. It should be noted that the above weight-average molecular weight is a converted value of standard polymethyl methacrylate obtained by gel permeation chromatography (GPC).

[0101] In the polyurea polymer of the present invention, the hardness measured under the following conditions is expressed as Shore A, preferably 85 or less, more preferably 80 or less, and even more preferably 75 or less.

[0102] Furthermore, the strain rate at 100°C obtained under the following conditions is preferably 55% or less, more preferably 50% or less, and even more preferably 45% or less.

[0103] The polyurea polymer of the present invention is particularly suitable for use as a sealing material because it has the aforementioned Shore A hardness and strain rate.

[0104] [Methods for measuring hardness]

[0105] The polyurea polymer of the present invention was pressed at a specified temperature and melt-molded to produce a 2 mm thick sheet, which was then left at 25°C for more than 2 days. Three sheets of the resulting material were overlapped and their hardness was measured using a Shore A hardness tester.

[0106] [Methods for determining strain rate]

[0107] (1) The polyurea polymer of the present invention is molded using a mold with a thickness of 50mm×50mm×6mm, cut into 10mm×10mm pieces, and annealed at 100°C for 16 hours.

[0108] (2) Compress the annealed polymer in (1) to a thickness of 3.9 mm and heat it at 100°C for 22 hours.

[0109] (3) After heating and compression, cool to room temperature, release the compression, measure the thickness, and calculate the strain rate using the following formula.

[0110] Strain rate (%) = [1 - (thickness after recovery - 3.9) / (initial thickness - 3.9)] × 100

[0111] [3] Polyurea composition

[0112] The polyurea composition of the present invention comprises (A) the above-described polyurea polymer and (B) an alcohol having one secondary or tertiary hydroxyl group in one molecule.

[0113] [(A)Component]

[0114] (A) The component is the polyurea polymer described above, and its mixing amount is preferably 10 to 50% by mass in the composition, more preferably 20 to 40% by mass.

[0115] [(B) Component]

[0116] The component (B) used in this invention is an alcohol having one secondary or tertiary hydroxyl group in one molecule, and is used as a diluent in the polyurea composition of this invention.

[0117] As for component (B), there are no particular limitations as long as it has one secondary or tertiary hydroxyl group in one molecule, and solvents that are the same as those used in the manufacture of the polyurea polymer of the present invention described above can be listed.

[0118] The amount of component (B) in the mixture is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more, relative to 100 parts by mass of the polyurea polymer (A). If the amount in the mixture is too small, the polyurea polymer may not be compatible. Furthermore, there is no particular limit to the upper limit, but it is preferably 300 parts by mass or less, more preferably 250 parts by mass or less.

[0119] [Other ingredients]

[0120] In the composition of the present invention, other components besides components (A) and (B) may be mixed in without impairing the effects of the present invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, and solvents other than component (B).

[0121] Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants.

[0122] Specific examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoic acid ester-based ultraviolet absorbers.

[0123] Specific examples of light stabilizers include hindered amine light stabilizers.

[0124] Specific examples of solvents are compounds other than component (B), such as toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, butyl acetate, etc.

[0125] [4] Method for manufacturing polyurea compositions

[0126] There are no particular limitations on the method for manufacturing the polyurea composition of the present invention. It can be obtained by mixing the above-described components (A) and (B) with other components used as needed, according to conventional methods. Furthermore, other components can be added to components (A) and (B) at any time.

[0127] Furthermore, in this invention, the components (a) to (c) described above can be reacted in the alcohol of component (B) to synthesize the polyurea polymer of component (A), thereby obtaining a solution after the reaction of the polyurea polymer of component (A) dissolved in the alcohol of component (B) is completed, which can be directly used as the polyurea composition of this invention.

[0128] The polyurea compositions of the present invention, depending on their composition, form thermoplastic resins or elastomers, but thermosetting compositions can also be made by using alcohols with more than three functions.

[0129] There are no particular limitations on the molding method of the polyurea composition of the present invention. Existing known methods can be used, such as cutting it into granules using a twin-screw extruder and then processing it into a molded article using various commonly used molding machines, i.e., extrusion molding machines, injection molding machines, calendering machines, compression molding machines, etc.

[0130] Furthermore, the polyurea composition of the present invention, in a liquid state where the polyurea polymer (A) is dissolved in component (B), or in a liquid state such as a two-component or three-component mixture where the prepolymer and chain extender are separated, is also suitable as a primer or topcoat for various plastics such as polyester, nylon, polyvinyl chloride, ABS, OPP, and CPP. Moreover, it can be used as a coating, surface coating material, sealant, OA roller, shoe, ski boot, adhesive, sealing material, wood adhesive, thermoplastic elastomer, thermosetting elastomer, etc., for various fibers such as elastic fibers, various fiber woven fabrics, nonwoven fabrics, paper, natural leather, artificial leather, synthetic leather, and wood.

[0131] Example

[0132] The following examples and comparative examples illustrate the invention in more detail, but the invention is not limited to the examples described below.

[0133] The compounds used are described below.

[0134] (a) Components (a-1) to (a-4), (a-6), (a'-7), and (a'-8) of component (a) are in equation (1), R 1 =-CH2CH2CH2NH2, R 2 =-CH3, where n is a value corresponding to the amine equivalent.

[0135] (a-5) The component is an organopolysiloxane represented by the following formula.

[0136] [Chemistry 4]

[0137]

[0138] (The bonding of each siloxane unit can be block or random.)

[0139] The method for determining amine equivalent is as follows.

[0140] [Method for determining amine equivalent]

[0141] The determination was performed using an automatic titration apparatus COM1750 (manufactured by HIRANUMA Co., Ltd.), with a glass composite electrode GR-511B used, under the following conditions.

[0142] The sample was weighed into a beaker, and 25 mL each of toluene and IPA were added. After stirring, a neutralization titration was performed using 0.1 N hydrochloric acid.

[0143] (a) Ingredients

[0144] ・(a) Ingredients

[0145] (a-1) Amine equivalent 2030 g / mol

[0146] (a-2) Amine equivalent 2140 g / mol

[0147] (a-3) Amine equivalent 2160 g / mol

[0148] (a-4) Amine equivalent 5440 g / mol

[0149] (a-5) Amine equivalent 2160 g / mol

[0150] (a-6) Amine equivalent 2070 g / mol

[0151] (a'-7) Amine equivalent 770 g / mol

[0152] (a'-8) amine equivalent 1480 g / mol

[0153] • (b) Components

[0154] H-MDI 4,4'-Dicyclohexylmethane diisocyanate (mixture of isomers)

[0155] IPDI (Isophorone Diisocyanate) (Mixed Isomeric Forms)

[0156] • (c) Ingredients

[0157] IPDA (Isophorone diamine) (a mixture of cis-isophorone diamine and trans-isophorone diamine)

[0158] MDA 4,4'-methylenediphenylamine

[0159] DDDA 1,12-dodecanediamine

[0160] DDA 1,10-decanediamine

[0161] TMHMDA (a mixture of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine)

[0162] ODA 1,8-Octandiamine

[0163] H-MDA 4,4'-Diaminodicyclohexylmethane (mixture of isomers)

[0164] PRZ Piperazine

[0165] HDA 1,6-hexanediamine

[0166] (B) Components

[0167] IPA isopropanol

[0168] [1] Manufacturing and physical property evaluation of polyurea polymers

[0169] [Example 1-1]

[0170] 85 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and 11.34 parts by mass of H-MDI were added at 20°C, and the reaction was carried out for 1 hour. Then, 8.65 parts by mass of IPDA were added at 20°C, and the reaction was carried out for 12 hours.

[0171] The reaction product was transferred to a polytetrafluoroethylene (PTFE) drum and dried at room temperature for 12 hours. Then, it was dried in a vacuum dryer at 120°C for 5 hours at 1 mmHg to obtain a block.

[0172] [Determination of weight-average molecular weight]

[0173] The weight-average molecular weight of the obtained polyurea polymer (bulk) was determined by gel permeation chromatography (GPC) using the equivalent value of standard polymethyl methacrylate.

[0174] [Measurement Conditions]

[0175] Device: HLC-8320GPC manufactured by Tosoh Corporation

[0176] Elution solvent: hexafluoro-2-propanol (HFIP) with 5 mM sodium trifluoroacetate added.

[0177] Flow rate: 0.2 mL / min

[0178] Detector: Differential Refractive Index Detector (RI)

[0179] Column: TSK Guardcolumn SuperH-L

[0180] TSKgel SuperHM-N (4.6mmI.D.×15cm×2)

[0181] (All manufactured by Tosoh Corporation)

[0182] Column temperature: 40℃

[0183] Sample injection volume: 50 μL (0.5% by mass elution solvent solution)

[0184] [Determination of tensile strength and elongation at break]

[0185] The obtained block was pressed at 210°C and a molding pressure of 10 MPa for 10 minutes to obtain a 1 mm thick cured sheet. The sheet was punched into a dumbbell shape (JIS K7312:1996) and the tensile strength and elongation at break were measured at a speed of 100 mm / min.

[0186] [Hardness Measurement]

[0187] The obtained block material was pressed at the temperature listed in Table 2, and then melt-molded into a 2 mm thick sheet, which was then left at 25°C for more than 2 days. Three sheets were then overlapped and their Shore A hardness was measured using a Shore A hardness tester.

[0188] [Determination of strain rate]

[0189] The obtained block was pressed into shape using a 50mm×50mm×6mm (thickness) mold, and cut into 10mm×10mm×6mm (thickness) pieces. It was then annealed at 100℃ for 16 hours. After being compressed to a thickness of 3.9mm, it was heated at 100℃ for 22 hours, cooled to room temperature, and the thickness upon release of compression was measured. The strain rate was calculated using the following formula.

[0190] Strain rate (%) = [1 - (thickness after recovery - 3.9) / (initial thickness - 3.9)] × 100

[0191] The formulation composition is recorded in Table 1, and the evaluation results are recorded in Table 2.

[0192] [Examples 1-2 to 1-14]

[0193] The same procedures as in Example 1-1 were performed to obtain the block materials of Examples 1-2 to 1-14. The physical properties of the obtained block materials were evaluated in the same manner as in Example 1-1.

[0194] The amount of IPA used was the same as in Example 1-1. The formulation composition is recorded in Table 1, and the evaluation results are recorded in Table 2.

[0195] [Comparative Examples 1-1, 1-2]

[0196] The same operation as in Example 1 was performed to obtain block-shaped products of Comparative Examples 1-1 and 1-2.

[0197] The amount of IPA used was the same as in Example 1-1. The formulation composition is recorded in Table 1, and the evaluation results are recorded in Table 2.

[0198] [Table 1]

[0199]

[0200] [Table 2]

[0201]

[0202] As shown in Table 2, the polyurea polymers of Examples 1-1 to 1-14 have a Shore A of 75 or less and a strain rate of 50% or less at 100°C.

[0203] [2] Manufacturing of polyurea compositions

[0204] [Example 2-1]

[0205] 85 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and 11.34 parts by mass of H-MDI were added at 20°C, and the reaction was carried out for 1 hour. Then, 8.65 parts by mass of IPDA were added at 20°C, and the reaction was carried out for 12 hours to synthesize a polyurea polymer. After the reaction was completed, a polyurea composition was obtained in the form of a solution of polyurea polymer dissolved in IPA.

[0206] [Examples 2-2 to 2-14]

[0207] The same procedures as in Example 2-1 were performed to obtain the polyurea compositions of Examples 2-2 to 2-14, respectively, in the form of solutions of polyurea polymer dissolved in IPA. The formulations were the same as in Examples 1-2 to 1-14. In addition, the amount of IPA used was the same as in Example 2-1.

[0208] [Comparative Examples 2-1 and 2-2]

[0209] The same procedures as in Example 2-1 were performed to obtain the polyurea compositions of Comparative Examples 2-1 and 2-2, respectively, in the form of solutions of polyurea polymer dissolved in IPA. The formulations were the same as those of Comparative Examples 1-1 and 1-2, respectively. In addition, the amount of IPA used was the same as in Example 2-1.

[0210] [Example 2-15]

[0211] 85 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and 11.34 parts by mass of H-MDI were added at 20°C, and the reaction was carried out for 1 hour. Then, 8.65 parts by mass of IPDA were added at 20°C, and the reaction was carried out for 12 hours.

[0212] The reaction product was transferred to a polytetrafluoroethylene (PTFE) drum and dried at room temperature for 12 hours. Then, it was dried in a vacuum dryer at 120°C and 1 mmHg for 5 hours to obtain a block.

[0213] Adding 70 parts by weight of IPA to 30 parts by weight of the obtained blocky material resulted in dissolution again, yielding a polyurea composition.

Claims

1. A polyurea polymer, which is the product of the reaction described in (a), (b) and (c) below: (a) An amino-containing organopolysiloxane represented by the following general formula (1) with an amine equivalent of more than 1500 g / mol and less than 7500 g / mol. [Chemistry 1] In the above formula, R 1 Independently, R is a monovalent hydrocarbon group with 1 to 20 carbon atoms having a primary or secondary amino group. 2 Each siloxane unit is a monovalent hydrocarbon group with 1 to 20 carbon atoms, and n is the value that satisfies the above amine equivalent. Furthermore, the bonding order of the siloxane units shown in parentheses is arbitrary. (b) Aliphatic diisocyanate compounds having two isocyanate groups in one molecule, (c) Amine compounds having two or more amino groups in one molecule, wherein, Component (a) is not included.

2. The polyurea polymer according to claim 1, wherein, (c) The component is represented by the following formula (4), H2N-R-NH2 (4) In the above formula, R is a divalent hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted.

3. A method for manufacturing a polyurea polymer, comprising the method for manufacturing a polyurea polymer according to claim 1 or 2, wherein the components (a) to (c) are reacted in an alcohol having one secondary or tertiary hydroxyl group in one molecule to obtain the polyurea polymer.

4. A polyurea composition comprising: (A) the polyurea polymer according to claim 1 or 2, and (B) an alcohol having one secondary or tertiary hydroxyl group in one molecule.

5. The polyurea composition according to claim 4, wherein, (A) The polyurea polymer is a solution dissolved in the alcohol of (B).

6. A method for manufacturing a polyurea composition, which is a method for manufacturing a polyurea composition according to claim 5, comprising the steps of reacting the components (a) to (c) in an alcohol of the component (B) to synthesize a polyurea polymer of component (A), and obtaining a polyurea composition in the form of a solution of the polyurea polymer of component (A) dissolved in an alcohol of component (B).

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