Polyurea polymer, polyurea composition, and methods for producing same

Abstract

Provided is a polyurea polymer that is a product of a reaction between: (a) an amino group-containing organopolysiloxane which is represented by general formula (1) and has an amine equivalent weight of 235-1500 g / mol (in the formula, R1 moieties are each independently a monovalent hydrocarbon group which has a primary or secondary amino group and has 1-20 carbon atoms, R2 moieties are each independently a monovalent hydrocarbon group having 1-20 carbon atoms, and n is a value that satisfies the amine equivalent weight); (b) an aliphatic diisocyanate compound having two isocyanate groups per molecule; and (c) an amine compound having two or more amino groups per molecule (excluding component (a)). Also provided is a polyurea composition containing this polymer and an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule.

Description

Polyurea polymer, polyurea composition, and methods for producing the same

[0001] The present invention relates to a polyurea polymer, a polyurea composition, and a method for producing the same.

[0002] Polyurea resins have tensile strength, flex resistance, abrasion resistance, and oil resistance, and can be made thermoplastic or thermosetting depending on the composition, so they can be processed into various shapes. Polyamines, isocyanates, chain extenders, etc. are used as raw materials for polyurea resins, and in recent years, copolymerization of reactive siloxanes, such as amino group-containing siloxanes, as polyamines has been proposed (Patent Document 1). Patent Document 1 also proposes siloxane-modified polyurea fibers and a method for producing the same.

[0003] However, when a diamine is used as the chain extender described in Patent Document 1 and the reaction is carried out without a solvent, the polymer solidifies and becomes unable to be stirred, resulting in a non-uniform polymer. Therefore, although the solvent described in Patent Document 1 can be added to carry out polymerization, the solvents that can maintain a molten state during polymerization have been highly polar solvents such as DMF and DMAc. Furthermore, as described in Patent Document 1, alcohol-based solvents (monoalcohols) are used as end-capping reaction agents for isocyanates, and therefore, high-boiling-point solvents such as DMF and DMAc have not been used as solvents.

[0004] However, because highly polar solvents have high boiling points, poor volatility, and are difficult to use, alternative solvents are strongly desired. Although it is possible to replace a low-boiling solvent after synthesis using DMF or DMAc solvents, this is time-consuming and uneconomical, so it is necessary to be able to synthesize using a low-boiling solvent from the synthesis stage.

[0005] On the other hand, Patent Document 2 proposes a method using a chlorinated solvent as a reaction solvent, but chlorinated solvents are difficult to use because various regulations are imposed on their use, disposal, etc.

[0006] International Publication No. 2016 / 158967 Japanese Patent Application Laid-Open No. 63-3029

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyurea polymer that is soluble in a solvent that has a low boiling point and is easily volatile, and that has excellent strength, a polyurea composition containing the same, and methods for producing the same.

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a polyurea polymer obtained from an organopolysiloxane having a predetermined 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, and have also found that the above-mentioned polyurea polymer can be produced using a secondary alcohol or a tertiary alcohol as a solvent, thereby completing the present invention.

[0009] That is, the present invention provides: 1. (a) an amino group-containing organopolysiloxane represented by the following general formula (1) and having an amine equivalent of 235 to 1,500 g / mol; (In the above formula, R 1 are each independently a monovalent hydrocarbon group having a primary or secondary amino group and having 1 to 20 carbon atoms; R 2are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. n is a value that satisfies the above-mentioned amine equivalent. The bonding order of each siloxane unit shown in parentheses is arbitrary.) (b) a polyurea polymer that is a reaction product of an aliphatic diisocyanate compound having two isocyanate groups per molecule, and (c) an amine compound having two or more amino groups per molecule (excluding component (a)). 2. A polyurea polymer according to 1, wherein component (c) is represented by the following formula (4): H2N-R-NH2 (4) (In the above formula, R is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.) 3. The present invention provides: 1. a method for producing a polyurea polymer according to 1 or 2, comprising the step of reacting the components (a) to (c) in an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule to obtain a polyurea polymer; 3. a polyurea composition comprising (A) the polyurea polymer according to 1 or 2, and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule; 5. the polyurea composition according to 4, in which the polyurea polymer of component (A) is dissolved in the alcohol of component (B) as a solution; and 6. a method for producing a polyurea composition according to 5, comprising the steps of reacting the components (a) to (c) in the alcohol of component (B) to synthesize the polyurea polymer of component (A), and obtaining a polyurea composition as a solution of the polyurea polymer of component (A) dissolved in the alcohol of component (B).

[0010] The polyurea polymer of the present invention is more soluble in solvents that have a low boiling point and are easily volatile than conventional polymers, and also has excellent strength.

[0011] The present invention is described in detail below. [1] Polyurea Polymer The polyurea polymer of the present invention is obtained by reacting the following components (a) to (c): (a) an amino group-containing organopolysiloxane represented by the following general formula (1) and having an amine equivalent of 235 to 1,500 g / mol; (b) an aliphatic diisocyanate compound having two isocyanate groups per molecule; and (c) an amine compound having two or more amino groups per molecule.

[0012] [Component (a)] The component (a) used in the present invention is an amino group-containing organopolysiloxane represented by the following general formula (1) having an amine equivalent of 235 to 1,500 g / mol, and acts as the base component of the polyurea polymer of the present invention.

[0013] In the above formula (1), R 1 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms and a primary or secondary amino group. 1 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and a primary or secondary amino group of the formula (2) include groups represented by the following formula (2): 3 NHR 4 (2)

[0014] In the above formula (2), R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic, and examples thereof include an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms; an alkenylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms; an arylene group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms; and an aralkylene group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. 3 Specific examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and eicosadecylene; cycloalkylene groups such as cyclopentylene and cyclohexylene; alkenylene groups such as vinylene and propenylene; arylene groups such as phenylene, methylphenylene, and naphthylene; and aralkylene groups such as benzylene and phenethylene. Among these, R 3is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, or decamethylene group, still more preferably a methylene, ethylene, trimethylene, or propylene group, and particularly preferably an ethylene or trimethylene group.

[0015] R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms; an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms; and an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. R 4 Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. 4 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl, ethyl or propyl group, and even more preferably a hydrogen atom or a methyl group.

[0016] Specific examples of the group represented by the above formula (2) include aminomethyl, 2-aminoeth-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, N-methylaminomethyl, N-methyl-2-aminoeth-1-yl, N-methyl-2-aminoprop-1-yl, N-methyl-3-aminoprop-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-aminobut-1-yl, Examples of aminoeth-1-yl include N-ethyl-2-aminoprop-1-yl, N-ethyl-3-aminoprop-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-aminoeth-1-yl, N-butyl-2-aminoprop-1-yl, N-butyl-3-aminoprop-1-yl, N-butyl-2-aminobut-1-yl, N-butyl-3-aminobut-1-yl, N-butyl-4-aminobut-1-yl, and 8-aminooct-1-yl groups. Among these, aminomethyl, 2-aminoeth-1-yl, 3-aminoprop-1-yl, and 8-aminooct-1-yl groups are preferred, and 3-aminoprop-1-yl group is more preferred.

[0017] In the above formula (1), R 2 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 Specific examples of the monovalent hydrocarbon group include R 4 Among them, R 2 is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a vinyl group, more preferably a methyl, ethyl, propyl, butyl, phenyl, or vinyl group, and even more preferably a methyl group or a phenyl group.

[0018] The amine equivalent of component (a) is 235 to 1,500 g / mol. It is preferably 300 to 1,500 g / mol, more preferably 400 to 1,500 g / mol, and even more preferably 400 to 1,000 g / mol. This amine equivalent represents the mass of component (a) per mole of amino groups in component (a). If the amine equivalent is less than 235 g / mol, the cured product will be too hard, while if it exceeds 1,500 g / mol, it will be difficult to increase the strength of the cured product. The above amine equivalent is a value measured by the neutralization titration method described below.

[0019] n is a value that satisfies the above range of amine equivalent. 1 and R 2 For example, R 2 are all methyl groups, n is preferably a number from 3 to 24, more preferably a number from 4 to 19. In formula (1), the bonding order of the siloxane units shown in parentheses is arbitrary.

[0020] Specific examples of organopolysiloxanes represented by formula (1) include, but are not limited to, the following. In the following formula, Me represents a methyl group, and Ph represents a phenyl group. Among these, those represented by formulas (1-1) to (1-3) are preferred, and those represented by formula (1-1) are more preferred.

[0021]

[0022] In the above formula, n 1 ~n 6 are each a number equal to or greater than 1, and n 1 = n, n 2 +n 3 = n, n 4 +n 5 +n 6 = n. The arrangement of the repeating units may be block or random, and is arbitrary. The component (a) may be used alone or in combination of two or more types.

[0023] These organopolysiloxanes can be produced by conventional methods, for example, by reacting an amino group-containing disiloxane with a cyclic siloxane having an optional substituent under acidic or alkaline conditions. Alternatively, commercially available products may be used.

[0024] [Component (b)] The component (b) used in the present invention is an aliphatic diisocyanate compound having two isocyanate groups per molecule, and is a component that reacts with the component (a) to form the polyurea polymer of the present invention. Component (b) is not particularly limited as long as it has two isocyanate groups per molecule, and examples include those represented by the following formula (3): OCN-Q-NCO (3) (In formula (3), Q is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.)

[0025] The divalent hydrocarbon group having 1 to 20 carbon atoms represented by Q may be linear, branched, or cyclic. 3 Among them, Q is preferably an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms. It may also be a group that combines these groups. Note that these groups may have at least a portion of their hydrogen atoms substituted with other substituents, and examples of such other substituents include alkyl groups having 1 to 3 carbon atoms, such as a methyl group or an ethyl group.

[0026] Specific examples of the isocyanate compound represented by formula (3) include diisocyanate compounds such as 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(2-isocyanato-2-propyl)benzene. Among these, 1,6-hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(2-isocyanato-2-propyl)benzene are preferred, and 4,4'-dicyclohexylmethane diisocyanate and 1,3-bis(2-isocyanato-2-propyl)benzene are more preferred. Note that the component (b) may be used alone or in combination of two or more.

[0027] The amount of component (b) to be added is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 parts by mass, per 100 parts by mass of component (a).

[0028] [Component (c)] The component (c) used in the present invention is an amine compound having two or more amino groups per molecule, and acts as a chain extender or crosslinker for the polyurea polymer of the present invention. The number of amino groups in the amine compound of component (c) is two or more per molecule, preferably 2 to 4, more preferably 2 to 3, and even more preferably 2. The component (c) is not particularly limited as long as it is a compound other than component (a) and has two or more functional groups per molecule, but examples include those represented by the following formula (4): H2N-R-NH2 (4)

[0029] In formula (4), R is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic; 3 Examples of the substituent include the same groups as those exemplified in 1. Furthermore, a group that is a combination of these groups may also be used. Note that at least a portion of the hydrogen atoms of these groups may be substituted with other substituents, and examples of the other substituents include alkyl groups having 1 to 3 carbon atoms such as a methyl group or an ethyl group; halogen atoms such as a chlorine atom or a bromine atom; and groups containing heteroatoms such as an oxygen atom or a sulfur atom.

[0030] Specific examples of the amine compound represented by formula (4) include 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, and 2,3-pentanediamine. Amines, 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, 2,4 , 4-trimethylhexamethylenediamine, diaminotoluene, diphenylmethanediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis(aminocyclohexane), diethylmethylbenzenediamine, 4,4'-methylenedianiline, 4,6-diethyl-2-methyl-1,3-phenylenediamine, 2-methyl-4,6-bis(methylthio)-1,3-benzenediamine, 4-methyl-2,6-bis(methylthio)-1,3-benzenediamine, bis(4-amino-2,3-dichlorophenyl)methane (TCDAM), trimethylenebis(4-aminobenzoate), isophoronediamine, 4,4'-diaminodicyclohexylmethane and other diamines. In addition, cyclic diamines such as piperazine, and triamines such as diethylenetriamine, bis(hexamethylene)triamine, and trisaminoethylamine can also be used. Among these, isophoronediamine is preferred. These may be used alone or in combination of two or more.

[0031] The amount of component (c) blended is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 15 parts by mass, per 100 parts by mass of component (a).

[0032] The amounts of components (a), (b), and (c) blended together are preferably such that {total number of isocyanates in component (b)} / {total number of amino groups in components (a) and (c)}=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.

[0033] In the synthesis of the polyurea polymer of the present invention, other components may be blended within the range that does not impair the effects of the present invention. Examples of other components include polyols (diols), catalysts, etc.

[0034] 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, neopentyl glycol, and methylpentanediol. Other examples include trifunctional alcohols such as glycerin and trimethylolpropane; tetrafunctional alcohols such as pentaerythritol and α-methylglycoside; hexafunctional alcohols such as sorbitol and sucrose; and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

[0035] Specific examples of the catalyst 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-dimethylimidazole, dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxy amine compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetra t-butoxytitanium, titanium diisopropoxybisacetylacetone complex; organic titanium compounds such as titanium tetra-2-ethylhexoxide and titanium diisopropoxybis(ethylacetoacetate); organic zirconium compounds such as zirconium tetrabutoxide, zirconium tetrapropoxide, tetrakis(2,4-pentanedionato)zirconium and zirconium dibutoxybis(ethylacetoacetate); and organic tin compounds such as dibutyltin diacetate and dibutyltin dilaurate.

[0036] [2] Method for Producing Polyurea Polymer The method for producing (synthesizing) the polyurea polymer of the present invention is not particularly limited, and any method conventionally used for producing polyurea resins can be used, such as a prepolymer method or a one-shot method.

[0037] In the prepolymer method, component (a) and component (b) are first reacted, and then component (c) is added and reacted. When reacting component (a) and component (b), component (b) may be added to component (a) or component (a) to component (b), but a method of adding component (b) to component (a) is preferred. The reaction can be carried out without a solvent, but it is preferable to use a solvent. The solvent may be added to component (a) or component (b). Alternatively, the solvent may be added after mixing components (a) and (b), or components (a) and (b) may be added to the solvent. Furthermore, when component (c) is added after reacting components (a) and (b), it may be added simultaneously with component (c), before adding component (c), or after adding component (c) and reacting. The components may be added dropwise or all at once.

[0038] The reaction temperature is not particularly limited and is preferably 10 to 150° C., more preferably 15 to 100° C., and even more preferably 20 to 60° C. The reaction time is also not particularly limited and is preferably 10 minutes to 20 hours, more preferably 10 minutes to 15 hours, and even more preferably 0.5 hours to 15 hours.

[0039] On the other hand, the one-shot method is a method in which components (a), (b), and (c) are reacted simultaneously. The reaction temperature is not particularly limited, but is preferably 10 to 150°C, more preferably 15 to 100°C, and even more preferably 20 to 60°C. The reaction time is also not particularly limited, but is preferably 10 minutes to 10 hours, and more preferably 0.5 to 5 hours.

[0040] In the present invention, it is preferable to use a prepolymer method, more preferably to react components (a) to (c) in a solvent using the prepolymer method, and even more preferably to mix component (a) with a solvent, add component (b) to react, and then add component (c) to further react. Note that other components can be added to components (a) to (c) at any timing.

[0041] The solvent that can be used in the above reaction is not particularly limited, but an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule is preferred. Such alcohols are not particularly limited as long as they have one secondary hydroxyl group or one tertiary hydroxyl group per molecule, and examples thereof include isopropyl alcohol, 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, and 1-ethoxy-2-propanol. Among these, isopropyl alcohol, 2-methyl-2-butanol, 2-butanol, and 1-methoxy-2-propanol are preferred. The boiling point of the solvent is preferably 200°C or less, more preferably 50 to 180°C, even more preferably 60 to 150°C, and particularly preferably 70 to 120°C.

[0042] When a solvent is used, the amount added 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 total of components (a) to (c) and other components. There is no particular upper limit, but the amount is preferably 300 parts by mass or less, more preferably 250 parts by mass or less.

[0043] After completion of the reaction, the polyurea polymer of the present invention can be obtained by drying the reaction mixture preferably at 20 to 200° C., more preferably at 20 to 150° C., for 1 to 30 hours, more preferably 5 to 20 hours. The drying step is preferably carried out under an inert gas atmosphere such as nitrogen or under reduced pressure of 700 Pa or less, since this prevents deterioration of the product.

[0044] The weight-average molecular weight of the polyurea polymer of the present invention is not particularly limited, but is preferably 4,000 to 500,000, more preferably 10,000 to 300,000, even more preferably 10,000 to 100,000, and still more preferably 15,000 to 50,000. The weight-average molecular weight is a value calculated as a standard polymethyl methacrylate by gel permeation chromatography (GPC).

[0045] The polyurea polymer of the present invention preferably has a Shore A hardness of 50 or more, more preferably 60 or more, measured under the following conditions. The tensile strength is preferably 10 MPa or more, more preferably 12 MPa or more. [Method for Measuring Hardness] The polyurea polymer of the present invention is pressed at a predetermined temperature to prepare a 2 mm thick sheet by melt molding, and then left at 25°C for 2 days or more. Three of the obtained sheets are stacked and measured using a Shore A hardness tester. [Measurement of Tensile Strength] The polyurea polymer of the present invention is press-molded at 235°C for 10 minutes with a molding pressure of 10 MPa to form a cured sheet of 1 mm thickness. A dumbbell No. 6 according to JIS K7312:1996 is punched out from this sheet, and the tensile strength is measured at a speed of 100 mm / min.

[0046] [3] Polyurea Composition The polyurea composition of the present invention contains (A) the polyurea polymer described above and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule.

[0047] [Component (A)] The component (A) is the polyurea polymer described above, and its content in the composition is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.

[0048] [Component (B)] The component (B) used in the present invention is an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule, and is used as a dilution solvent for the polyurea composition of the present invention. The component (B) is not particularly limited as long as it has one secondary hydroxyl group or one tertiary hydroxyl group per molecule, and examples thereof include the same solvents as those used in the production of the polyurea polymer of the present invention described above.

[0049] The amount of component (B) 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 is too small, the polyurea polymer may not be compatible. There is no particular upper limit, but it is preferably 300 parts by mass or less, more preferably 250 parts by mass or less.

[0050] [Other Components] In addition to components (A) and (B), other components may be blended into the composition of the present invention to the extent that the effects of the present invention are not impaired. Examples of other components include antioxidants, ultraviolet absorbers, light stabilizers, and solvents other than component (B).

[0051] Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0052] Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

[0053] Specific examples of the light stabilizer include hindered amine light stabilizers.

[0054] Specific examples of the solvent include those other than component (B), such as toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, and butyl acetate.

[0055] [4] Method for Producing Polyurea Composition The method for producing the polyurea composition of the present invention is not particularly limited, and the polyurea composition can be obtained by mixing the above-mentioned components (A) and (B) and, if necessary, other components according to a conventional method. The other components can be added to the components (A) and (B) at any time. Furthermore, in the present invention, the above-mentioned components (a) to (c) are reacted in the alcohol of the component (B) to synthesize the polyurea polymer of the component (A), and the solution after the reaction in which the polyurea polymer of the component (A) is dissolved in the alcohol of the component (B) can be directly obtained as the polyurea composition of the present invention.

[0056] The polyurea composition of the present invention forms a thermoplastic resin or elastomer depending on its composition, but can also be made into a thermosetting composition by using a tri- or higher functional alcohol. The molding method of the polyurea composition of the present invention is not particularly limited, and a conventionally known method can be used, for example, a method in which the polyurea composition is cut into pellets using a twin-screw extruder and then processed into a molded product using various commonly used molding machines, i.e., an extrusion molding machine, an injection molding machine, a calendar molding machine, a press molding machine, etc.

[0057] The polyurea composition of the present invention, in a liquid state in which the polyurea polymer (A) is dissolved in the component (B), or in a two-component, three-component, or other liquid state in which the prepolymer and the chain extender are separated, is also suitably used as a primer coating agent or top coating agent for various plastics such as polyester, nylon, polyvinyl chloride, ABS, OPP, CPP, etc. Furthermore, it can be used as a paint, surface coating material, sealant, office automation roll, shoe, ski boot, adhesive, sealing material, wood binder, thermoplastic elastomer, thermosetting elastomer, etc. for various fibers such as elastic fibers, various knitted and woven fibers, nonwoven fabric, paper, natural leather, artificial leather, synthetic leather, wood, etc.

[0058] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0059] The compounds used are as follows: Components (a-1) to (a-3), (a'-4), and (a'-5) of component (a) are compounds represented by the formula (1) where R 1 =-CH2CH2CH2NH2, R 2 = -CH3, where n is the value adjusted for each amine equivalent.

[0060] The amine equivalent was measured by the following method. [Method for measuring amine equivalent] Measurement was performed using an automatic titrator COM1750 (manufactured by HIRANUMA Corporation) and a glass composite electrode GR-511B under the following conditions: A sample was weighed into a beaker, and 25 mL each of toluene and IPA was added and stirred, followed by neutralization titration with 0.1 N hydrochloric acid.

[0061] Component (A) Component (a) (a-1) Amine equivalent: 430 g / mol (a-2) Amine equivalent: 770 g / mol (a-3) Amine equivalent: 1500 g / mol (a'-4) Amine equivalent: 2140 g / mol (a'-5) Amine equivalent: 5300 g / mol

[0062] Component (b) H-MDI 4,4'-dicyclohexylmethane diisocyanate (mixture of isomers) TMXDI 1,3-bis(2-isocyanato-2-propyl)benzene

[0063] Component (c) IPDA isophoronediamine (cis-, trans-mixture)

[0064] (B) Component IPA Isopropyl alcohol

[0065] [1] Production of Polyurea Polymer and Evaluation of Physical Properties [Example 1-1] 70 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and then 26.81 parts by mass of H-MDI was added at 20°C, and the mixture was allowed to react for 1 hour. Thereafter, 3.20 parts by mass of IPDA was added at 20°C, and the mixture was allowed to react for 12 hours. The reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours, and then dried for 5 hours at 1 mmHg in a vacuum dryer at 120°C to obtain a mass.

[0066] [Measurement of Weight-Average Molecular Weight] The weight-average molecular weight of the obtained polyurea polymer (lump) was determined by gel permeation chromatography (GPC) in terms of standard polymethyl methacrylate. [Measurement Conditions] Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: hexafluoro-2-propanol (HFIP) containing 5 mM sodium trifluoroacetate Flow rate: 0.2 mL / min Detector: refractive index detector (RI) Column: TSK Guard column Super H-L TSKgel Super HM-N (4.6 mm I.D. × 15 cm × 2) (both manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (0.5% by mass concentration developing solvent solution)

[0067] [Measurement of tensile strength and elongation at break] The obtained block was press-molded at 235°C for 10 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm. From this sheet, a No. 6 dumbbell shape according to JIS K7312:1996 was punched out, and the tensile strength and elongation at break were measured at a speed of 100 mm / min. [Measurement of hardness] The obtained block was pressed at the temperature shown in Table 2 to produce a sheet having a thickness of 2 mm by melt molding, and then left at 25°C for two days or more. Three obtained sheets were stacked and measured using a Shore A hardness tester. The formulations are shown in Table 1, and the evaluation results are shown in Table 2.

[0068] [Examples 1-2, 1-3] The same operation as in Example 1-1 was carried out to obtain lumps of Examples 1-2 and 1-3. The physical properties of the obtained lumps were evaluated in the same manner as in Example 1-1. The amount of IPA used was the same as in Example 1-1. The blending compositions are shown in Table 1, and the evaluation results are shown in Table 2.

[0069] [Comparative Examples 1-1 and 1-2] The same operation as in Example 1 was carried out to obtain lumps of Comparative Examples 1-1 and 1-2. The amount of IPA used was the same as in Example 1-1. The blending compositions are shown in Table 1, and the evaluation results are shown in Table 2.

[0070]

[0071]

[0072] As shown in Table 2, the polyurea polymers of Examples 1-1 to 1-3 have a Shore A of 50 or more and a tensile strength of 10 MPa or more.

[0073] [2] Production of Polyurea Composition [Example 2-1] 70 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and then 26.81 parts by mass of H-MDI was added at 20° C. and the mixture was allowed to react for 1 hour. Thereafter, 3.20 parts by mass of IPDA was added at 20° C. and the mixture was allowed to react for 12 hours to synthesize a polyurea polymer. After completion of the reaction, a polyurea composition was obtained as a solution in which the polyurea polymer was dissolved in IPA.

[0074] [Examples 2-2 and 2-3] The same procedure as in Example 2-1 was carried out to obtain the polyurea compositions of Examples 2-2 to 2-3 as solutions in which a polyurea polymer was dissolved in IPA. The formulations were the same as in Examples 1-2 to 1-3, respectively. The amount of IPA used was the same as in Example 2-1.

[0075] [Comparative Examples 2-1 and 2-2] The same procedure as in Example 2-1 was carried out to obtain polyurea compositions of Comparative Examples 2-1 and 2-2, each of which was a solution of a polyurea polymer dissolved in IPA. The formulations were the same as in Comparative Examples 1-1 and 1-2, respectively. The amount of IPA used was the same as in Example 2-1.

[0076] Example 2-4 After mixing 70 parts by mass of (a-1) and 233.33 parts by mass of IPA, 26.81 parts by mass of H-MDI was added at 20°C and the mixture was allowed to react for 1 hour. Thereafter, 3.20 parts by mass of IPDA was added at 20°C and the mixture was allowed to react for 12 hours. The reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours, and then dried at 1 mmHg in a vacuum dryer at 120°C for 5 hours to obtain lumps. When 70 parts by mass of IPA was added to 30 parts by mass of the obtained lumps, the lumps dissolved again, and a polyurea composition was obtained.

Claims

1. (a) an amino group-containing organopolysiloxane represented by the following general formula (1) having an amine equivalent of 235 to 1,500 g / mol; (In the above formula, R 1 are each independently a monovalent hydrocarbon group having a primary or secondary amino group and having 1 to 20 carbon atoms; R 2 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. n is a value that satisfies the above amine equivalent. The bonding order of each siloxane unit shown in parentheses is arbitrary.) A polyurea polymer which is a reaction product of (b) an aliphatic diisocyanate compound having two isocyanate groups per molecule, and (c) an amine compound having two or more amino groups per molecule (excluding component (a)).

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

3. A method for producing a polyurea polymer according to claim 1 or 2, comprising the step of reacting the components (a) to (c) in an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule to obtain a polyurea polymer.

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

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

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