Polyurethane polymer, polyurethane composition, and methods for producing these

Abstract

The present invention provides a polyurethane polymer which is a reaction product of (a) a hydroxy group-containing organopolysiloxane which is represented by formula (1) and has a hydroxyl value of 5-250 mgKOH / g (in the formula, R1 is a monovalent hydrocarbon group that has a hydroxy group and may contain an oxygen atom in the chain (excluding the cases where an oxygen atom is directly bonded to a hydroxy group), R2 is a monovalent hydrocarbon group, n is a value that satisfies the hydroxyl value, and the bonding order of the siloxane units shown in the parentheses is arbitrary), (b) an aliphatic diisocyanate compound which has two isocyanate groups per molecule, and (c) an amine compound which has two or more amino groups per molecule. This polyurethane polymer contains 70-98 parts by mass of the component (a) in a total of 100 parts by mass of the components (a)-(c).

Description

Polyurethane polymer, polyurethane composition, and methods for producing the same

[0001] The present invention relates to polyurethane polymers, polyurethane compositions, and methods for producing the same.

[0002] Polyurethane 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 a variety of shapes. Polyols, isocyanates, chain extenders, etc. are used as raw materials for polyurethane resins, but in recent years, copolymerization of reactive siloxanes, such as hydroxyl-containing siloxanes, as polyols has been proposed (Patent Document 1). Patent Document 1 also proposes siloxane-modified polyurethane fibers and a method for producing the same.

[0003] However, when a diamine is used as the polyamine described in Patent Document 1 and the reaction is carried out without a solvent, the polymer solidifies and becomes inhomogeneous, making it impossible to stir. Therefore, although the solvent described in Patent Document 1 can be added for polymerization, the solvents that can maintain a molten state during polymerization are 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 are not used as solvents. For this reason, high-boiling-point solvents such as DMF and DMAc have been used.

[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 polyurethane polymer that is soluble in a solvent that has a low boiling point and is easily volatile, and that has a low distortion factor, a polyurethane 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 polyurethane polymer obtained from a specific organopolysiloxane containing a hydroxy group, 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 polyurethane polymer can be produced using a secondary alcohol or a tertiary alcohol as a solvent, which led to the completion of the present invention.

[0009] That is, the present invention provides: 1. (a) a hydroxyl group-containing organopolysiloxane represented by the following formula (1) and having a hydroxyl value of 5 to 250 mgKOH / g; (In the above formula, R 1 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which has a hydroxy group and may contain an oxygen atom in the chain (except when the oxygen atom is directly bonded to the hydroxy group); R 2are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. n is a value satisfying the above-mentioned hydroxyl value. The bonding order of each siloxane unit shown in parentheses is arbitrary.) A polyurethane 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, and contains 70 to 98 parts by mass of component (a) per 100 parts by mass of the total amount of components (a) to (c). 2. A method for producing a polyurethane polymer according to 1, comprising the step of reacting components (a) to (c) in an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule to obtain a polyurethane polymer. 3. A polyurethane composition comprising (A) the polyurethane polymer according to 1, and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule. 4. The polyurethane composition according to 3, wherein the polyurethane polymer of component (A) is a solution dissolved in the alcohol of component (B); 5. The method for producing the polyurethane composition according to 4, comprising the steps of reacting components (a) to (c) in the alcohol of component (B) to synthesize the polyurethane polymer of component (A), and obtaining the polyurethane composition as a solution of the polyurethane polymer of component (A) dissolved in the alcohol of component (B).

[0010] The polyurethane polymer of the present invention is more soluble in solvents with low boiling points and high volatility than conventional polymers. Furthermore, the polyurethane polymer of the present invention has a low distortion factor, making it suitable for use as a sealing material.

[0011] The present invention is described in detail below. [1] Polyurethane Polymer The polyurethane polymer of the present invention is obtained by reacting the following components (a) to (c): (a) a hydroxyl group-containing organopolysiloxane represented by the following general formula (1) and having a hydroxyl value of 5 to 250 mgKOH / g; (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 a hydroxyl group-containing organopolysiloxane represented by the following formula (1) and having a hydroxyl value of 5 to 250 mgKOH / g, and acts as the base component of the polyurethane polymer of the present invention.

[0013]

[0014] In the above formula (1), R 1 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which has a hydroxy group and may contain an oxygen atom in the chain (except when the oxygen atom is directly bonded to the hydroxy group; the same applies hereinafter). 1 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group of the formula (1) and optionally containing an oxygen atom in the chain include groups represented by the following formula (2): 3 OH (2)

[0015] In the above formula (2), R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an oxygen atom in the chain (except when the oxygen atom is directly bonded to an —OH group; the same applies hereinafter), and may be linear, branched, or cyclic. Examples include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 11 carbon atoms; cycloalkylene groups having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms; alkenylene groups having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms; arylene groups having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms; and aralkylene groups having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. 3Specific examples of the divalent hydrocarbon group which may contain an oxygen atom in the chain include alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, 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; aralkylene groups such as benzylene and phenethylene; and -CHCHCH-O-CHCH-. Among these, R 3 is preferably an alkylene group having 1 to 11 carbon atoms which may contain an oxygen atom in the chain, more preferably ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, -CHCHCH-O-CHCH-, still more preferably ethylene, trimethylene, propylene, octamethylene, undecamethylene, -CHCHCH-O-CHCH-, and particularly preferably trimethylene, octamethylene, undecamethylene, -CHCHCH-O-CHCH-.

[0016] Specific examples of the group represented by the above formula (2) include, -CH2CH2-OH, -CH2CH2CH2-OH, -CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-OH, -CH2CH2CH2-O-CH2CH2-OH, and the like. Among these, —CH2CH2CH2—OH, —CH2CH2CH2CH2—OH, —CH2CH2CH2CH2CH2—OH, —CH2CH2CH2CH2CH2CH2CH2CH2—OH, —CH2CH2CH2—O—CH2CH2—OH is preferred, and —CH2CH2CH2—O—CH2CH2—OH is more preferred.

[0017] In the above formula (1), R 2 are each independently 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 2 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. 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 hydroxyl value of component (a) is 5 to 250 mgKOH / g, preferably 10 to 200 mgKOH / g, and more preferably 15 to 150 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it is difficult to increase the strength, and if it exceeds 250 mgKOH / g, it is difficult to achieve a balance between the hardness and distortion rate of the resulting polymer. The hydroxyl value is a value measured by the method described below.

[0019] n is a value that satisfies the above-mentioned range of the hydroxyl value. 1 and R 2 For example, R 2 are all methyl groups, n is a number from 4 to 300, preferably from 5 to 149, and more preferably from 7 to 98. 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 (1-7) to (1-12) are preferred, and those represented by formulas (1-7) to (1-9) 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 a hydrosilylation reaction between a polyorganosiloxane having hydrosilyl groups at both ends and a compound having an allyl group and a hydroxyl group, such as allyl alcohol. Alternatively, commercially available products may be used.

[0024] In the polyurethane polymer of the present invention, the content of component (a) is 70 to 98 parts by mass, preferably 70 to 95 parts by mass, and more preferably 75 to 90 parts by mass, per 100 parts by mass of the total amount of components (a) to (c). Note that in the present invention, the content of component (a) in the polyurethane polymer is the same as the blending ratio when producing the polyurethane polymer.

[0025] [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 polyurethane 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.)

[0026] The divalent hydrocarbon group having 1 to 20 carbon atoms for Q 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.

[0027] Specific examples of the divalent hydrocarbon group for Q 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. Of these, Q is preferably an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 3 to 20 carbon atoms. Furthermore, Q may be a group formed by combining these groups. At least a portion of the hydrogen atoms in these groups may be substituted with other substituents, such as alkyl groups having 1 to 3 carbon atoms, such as methyl and ethyl groups.

[0028] 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 1,4-bis(isocyanatomethyl)cyclohexane. Among these, 1,6-hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-bis(isocyanatomethyl)cyclohexane are preferred, and isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and 1,4-bis(isocyanatomethyl)cyclohexane are more preferred. Note that the component (b) may be used alone or in combination of two or more.

[0029] The amount of component (b) to be added is not particularly limited, but is preferably 5 to 50 parts by mass, more preferably 8 to 25 parts by mass, and even more preferably 9 to 20 parts by mass, per 100 parts by mass of component (a).

[0030] [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 polyurethane 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 has two or more functional groups per molecule, but examples include those represented by the following formula (4): H2N-R-NH2 (4)

[0031] 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, and examples thereof include the same groups as those exemplified for Q. It may also be a group formed by combining these groups. Note that at least a portion of the hydrogen atoms in these groups may be substituted with other substituents, and examples of such other substituents include alkyl groups having 1 to 3 carbon atoms, such as methyl groups and ethyl groups; halogen atoms, such as chlorine atoms and bromine atoms; and groups containing heteroatoms, such as oxygen atoms and sulfur atoms.

[0032] 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. Furthermore, cyclic diamines such as piperazine; and triamines such as diethylenetriamine, bis(hexamethylene)triamine, and trisaminoethylamine can also be used.Among these, isophoronediamine, 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'-methylenedianiline, and 4,4'-diaminodicyclohexylmethane are preferred. These may be used alone or in combination of two or more.

[0033] The amount of component (c) to be added is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of component (a).

[0034] The amounts of components (a), (b), and (c) blended together are preferably such that {the number of all isocyanate groups in component (b)} / {the total number of hydroxyl groups and 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.

[0035] The polyurethane polymer of the present invention may contain other components, such as polyols (diols), within the range that does not impair the effects of the present invention.

[0036] 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.

[0037] [2] Method for Producing Polyurethane Polymer The method for producing (synthesizing) the polyurethane polymer of the present invention is not particularly limited, and any method conventionally used for producing polyurethane resins can be used, such as a prepolymer method.

[0038] 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), component (a) may be added to component (b), or component (a) may be added to component (b), or components (a) and (b) may be added simultaneously and reacted. Furthermore, these reactions are preferably carried out in the presence of a catalyst.

[0039] 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 acetate and dibutyltin dilaurate.

[0040] The reaction is preferably carried out without a solvent. When component (c) is added after the reaction of component (a) with component (b), the solvent may be added simultaneously with component (c), before component (c) is added, or after component (c) is added and the reaction is completed. The components may be added dropwise or all at once.

[0041] The reaction temperature is not particularly limited, and the reaction between component (a) and component (b) is preferably carried out at 10 to 150°C, more preferably 20 to 120°C, and even more preferably 50 to 100°C. The reaction time is also not particularly limited, and is preferably 2 to 10 hours, and more preferably 3 to 8 hours. The reaction after addition of component (c) is preferably carried out at 10 to 150°C, more preferably 20 to 100°C, and even more preferably 20 to 50°C. The reaction time is also not particularly limited, and is preferably 10 minutes to 20 hours, and more preferably 3 to 15 hours.

[0042] 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.

[0043] 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.

[0044] After completion of the reaction, the polyurethane 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 preferably 1 to 30 hours, more preferably 5 to 20 hours. The drying step is preferably carried out in an inert gas atmosphere such as nitrogen or under reduced pressure of 700 Pa or less, since this prevents deterioration of the product.

[0045] The weight-average molecular weight of the polyurethane polymer of the present invention is not particularly limited, but is preferably 5,000 to 500,000, more preferably 10,000 to 300,000, and even more preferably 10,000 to 200,000. The weight-average molecular weight is a value calculated as a standard polymethyl methacrylate by gel permeation chromatography (GPC).

[0046] The polyurethane polymer of the present invention preferably has a Shore A hardness of 85 or less, more preferably 80 or less, and even more preferably 75 or less, measured under the following conditions. The strain at 100°C, measured under the following conditions, is preferably 55% or less, more preferably 50% or less, and even more preferably 45% or less. Because the polyurethane polymer of the present invention has the above Shore A hardness and strain, it is particularly suitable for use as a sealing material. [Hardness Measurement Method] The polyurethane 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 two days or more. Three of the obtained sheets are stacked and measured using a Shore A hardness tester. [Strain Rate Measurement Method] (1) The polyurethane polymer of the present invention is press-molded using a mold measuring 50 mm x 50 mm x 6 mm (thickness), cut into a 10 mm x 10 mm piece, and annealed at 100°C for 16 hours. (2) The polymer annealed in (1) is compressed to a thickness of 3.9 mm and heated at 100°C for 22 hours. (3) After the heat compression, the sample is cooled to room temperature and then released from compression. The thickness is measured and the strain rate is calculated using the following formula: Strain rate (%) = [1 - (recovered thickness - 3.9) / (initial thickness - 3.9)] x 100

[0047] [3] Polyurethane Composition The polyurethane composition of the present invention contains (A) the polyurethane polymer described above and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule.

[0048] [Component (A)] The component (A) is the polyurethane polymer described above, and its content in the composition is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.

[0049] [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 polyurethane 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 polyurethane polymer of the present invention described above.

[0050] 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, per 100 parts by mass of polyurethane polymer (A). If the amount is too small, the polyurethane polymer may not be compatible. 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.

[0051] [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).

[0052] Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0053] Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

[0054] Specific examples of the light stabilizer include hindered amine light stabilizers.

[0055] 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.

[0056] [4] Method for Producing Polyurethane Composition The method for producing the polyurethane composition of the present invention is not particularly limited, and the polyurethane composition can be obtained by mixing the above-described components (A), (B), and other components according to a conventional method. The other components can be added to components (A) and (B) at any time. Furthermore, in the present invention, the above-described components (a) to (c) are reacted in the alcohol of component (B) to synthesize the polyurethane polymer of component (A), and the solution after the reaction in which the polyurethane polymer of component (A) is dissolved in the alcohol of component (B) can be directly obtained as the polyurethane composition of the present invention.

[0057] The polyurethane 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 for the polyurethane composition of the present invention is not particularly limited, and conventionally known methods can be used. For example, the polyurethane composition can be cut into pellets using a twin-screw extruder and then processed into a molded product using various commonly used molding machines, such as an extrusion molding machine, an injection molding machine, a calendar molding machine, or a press molding machine. Another example is a method in which the polyurethane composition is cut into pellets or filaments using a twin-screw extruder and then processed into a molded product using a 3D printer.

[0058] The polyurethane composition of the present invention, in a liquid state in which the polyurethane 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, can also be suitably used as a primer coating agent or a 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, shoes, ski boots, adhesive, sealing material, wood binder, robot parts, wearable parts, protectant for electronic parts, cosmetics, furniture parts, sporting goods, leisure goods, medical supplies, nursing care goods, skin-contacting parts, thermoplastic elastomer, thermosetting elastomer, etc., and also includes uses in which two or more of these uses are combined arbitrarily.

[0059] 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.

[0060] The compounds used are as follows: Component (a) is a compound represented by formula (1): 1 =-CH2CH2CH2OCH2CH2OH, R 2 =-CH3, and n is a value that corresponds to each hydroxyl value.

[0061] The hydroxyl value was measured using the following method. [Method for Measuring Hydroxyl Value] An acetylation reagent was prepared by diluting 25 g of acetic anhydride with 100 mL of pyridine. A sample was weighed into a recovery flask, and 5 mL of the acetylation reagent was added (sample). Another recovery flask was prepared by adding 5 mL of the acetylation reagent (blank). Each recovery flask was heated at 100°C for 1 hour, after which 1 mL of purified water was added, and the mixture was further heated at 100°C for 10 minutes. 5 mL of ethanol was then added to each flask, and 1-2 drops of phenolphthalein were added. The mixture was titrated with 0.5 N KOH ethanol solution, and the hydroxyl value was calculated from the titer of the sample and blank.

[0062] Component (A) Component (a) (a-1) Hydroxyl value 21 mg KOH / g (a-2) Hydroxyl value 23 mg KOH / g (a-3) Hydroxyl value 36 mg KOH / g (a-4) Hydroxyl value 58 mg KOH / g (a-5) Hydroxyl value 118 mg KOH / g

[0063] Component (b) H-MDI 4,4'-dicyclohexylmethane diisocyanate (mixture of isomers) HDI 1,6-hexamethylene diisocyanate 1,4-H6XDI 1,4-bis(isocyanatomethyl)cyclohexane

[0064] Component (c) IPDA: isophoronediamine (cis-, trans-mixture) HMDA: 1,6-hexanediamine

[0065] (B) Component IPA Isopropyl alcohol

[0066] Other ingredients: Zr(acac)4 tetrakis(2,4-pentanedionato)zirconium(IV)

[0067] [1] Production of polyurethane polymer and evaluation of physical properties [Example 1-1] 80 parts by mass of (a-1), 13.78 parts by mass of H-MDI, and 0.005 parts by mass of Zr(acac) were reacted at 100°C for 5 hours. The temperature was then lowered to 20°C, and 233.33 parts by mass of IPA was mixed, followed by the addition of 6.22 parts by mass of IPDA at 20°C, and the reaction was continued for 12 hours. The reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours. It was then dried for 5 hours at 1 mmHg in a vacuum dryer at 120°C to obtain a block.

[0068] [Measurement of Weight-Average Molecular Weight] The weight-average molecular weight of the obtained polyurethane 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: differential 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)

[0069] [Measurement of Tensile Strength and Elongation at Break] The resulting block was press-molded at 230°C for 10 minutes under a molding pressure of 10 MPa to obtain a 1 mm thick cured sheet. From this sheet, a No. 6 dumbbell shape according to JIS K7312:1996 was punched, and tensile strength and elongation at break were measured at a speed of 100 mm / min. [Measurement of Hardness] The resulting block was pressed at the temperature listed in Table 2 to produce a 2 mm thick sheet by melt molding, and then left at 25°C for at least 2 days. Three resulting sheets were stacked and measured using a Shore A hardness tester. [Measurement of Strain Rate] The resulting block was press-molded using a 50 mm x 50 mm x 6 mm (thickness) mold, cut into a 10 mm x 10 mm piece, and annealed at 100°C for 16 hours. This was compressed to a thickness of 3.9 mm, heated at 100°C for 22 hours, cooled to room temperature, and the thickness was measured upon release from compression, and the strain rate was calculated. The distortion rate was calculated using the following formula: Distortion rate (%) = [1 - (recovered thickness - 3.9) / (initial thickness - 3.9)] x 100 The compounding compositions are shown in Table 1, and the evaluation results are shown in Table 2.

[0070] [Examples 1-2 to 1-6] The same operation as in Example 1-1 was carried out to obtain lumps of Examples 1-2 to 1-6. 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.

[0071] [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.

[0072]

[0073]

[0074] As shown in Table 2, the polyurethane polymers of Examples 1-1 to 1-6 have a distortion rate at 100° C. of 50% or less.

[0075] [2] Production of Polyurethane Composition [Example 2-1] 80 parts by mass of (a-1), 13.78 parts by mass of H-MDI, and 0.005 parts by mass of Zr(acac) were reacted for 5 hours at 100° C. Thereafter, the temperature was lowered to 20° C., and 233.33 parts by mass of IPA was mixed, followed by the addition of 6.22 parts by mass of IPDA at 20° C. The mixture was reacted for 12 hours to synthesize a polyurethane polymer. After completion of the reaction, a polyurethane composition was obtained as a solution in which the polyurethane polymer was dissolved in IPA.

[0076] [Examples 2-2 to 2-6] The same procedure as in Example 2-1 was carried out to obtain polyurethane compositions of Examples 2-2 to 2-6 as solutions in which polyurethane polymers were dissolved in IPA. The blending compositions were the same as in Examples 1-2 to 1-6, respectively. The amount of IPA used was the same as in Example 2-1.

[0077] [Comparative Examples 2-1 and 2-2] The same procedure as in Example 2-1 was carried out to obtain polyurethane compositions of Comparative Examples 2-1 and 2-2, each of which was a solution of a polyurethane polymer dissolved in IPA. The blending compositions 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.

[0078] Example 2-7: 80 parts by mass of (a-1), 13.78 parts by mass of H-MDI, and 0.005 parts by mass of Zr(acac) were reacted at 100°C for 5 hours. The temperature was then lowered to 20°C, and 233.33 parts by mass of IPA was added. Then, 6.22 parts by mass of IPDA was added at 20°C, and the reaction was continued for 12 hours. The reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours. It was then dried at 120°C in a vacuum dryer at 1 mmHg for 5 hours to obtain lumps. When 70 parts by mass of IPA was added to 30 parts by mass of the obtained lumps, they dissolved again, yielding a polyurethane composition.

Claims

(a) a hydroxyl group-containing organopolysiloxane represented by the following formula (1) having a hydroxyl value of 5 to 250 mgKOH / g; (In the above formula, R 1 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which has a hydroxy group and may contain an oxygen atom in the chain (except when the oxygen atom is directly bonded to the hydroxy group); R 2 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. n is a value that satisfies the above hydroxyl value. The bonding order of each siloxane unit shown in parentheses is arbitrary. (b) an aliphatic diisocyanate compound having two isocyanate groups in one molecule; (c) an amine compound having two or more amino groups in one molecule; and a polyurethane polymer containing 70 to 98 parts by mass of component (a) relative to 100 parts by mass in total of components (a) to (c).

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

4. The polyurethane composition according to claim 3, wherein the polyurethane polymer (A) is a solution dissolved in the alcohol (B).

5. A method for producing a polyurethane composition according to claim 4, comprising the steps of: reacting components (a) to (c) in the alcohol of component (B) to synthesize a polyurethane polymer of component (A); and obtaining a polyurethane composition as a solution in which the polyurethane polymer of component (A) is dissolved in the alcohol of component (B).

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