Siloxane-modified polyurethane composition

Abstract

Provided is a siloxane-modified polyurethane composition that contains: (A) a hydroxyl group-containing organosilicon compound represented by formula (1) (1): (R1 3SiO1 / 2)k(R1 2SiO2 / 2)p(R1SiO3 / 2)q(SiO4 / 2)r [wherein: R1 is a monovalent hydrocarbon group, etc., provided that at least one of all R1 groups is a group represented by formula (2); and k>0, p≥0, q≥0 and r≥0, provided that k+p+q≥2] (R2 is a hydrogen atom, etc., and R3 is a hydrogen atom or a methyl group; s is an integer of 0-4, t is an integer of 2-4 and u is a numerical value of 1-3; and the broken line represents a bond); (B) an isocyanate compound having two or more isocyanate groups per molecule; and (C) an organic compound having two or more functional groups capable of reacting with isocyanate groups per molecule.

Description

Technical Field

[0001] The present invention relates to a siloxane-modified polyurethane composition, and more specifically, to a siloxane-modified polyurethane composition having a novel structure and a cured product thereof.

Background Art

[0002] Polyurethane resins are excellent in tensile strength, flexural 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. As raw materials for polyurethane resins, polyols, isocyanates, chain extenders, etc. are used. In order to impart flexibility and slipperiness to this polyurethane resin, copolymerization of a hydroxyl group-containing siloxane as a polyol has been proposed (Patent Documents 1 to 8).

[0003] The hydroxyl group-containing polysiloxanes described in these patent documents are industrially produced by a hydrosilylation reaction of hydrogen polysiloxane with a hydroxyl group-containing olefin compound such as allyl glycol or polyoxyalkylene monoallyl ether. However, for example, allyl glycol has low compatibility with hydrogen polysiloxane, so when reacting without a solvent, it is necessary to use a large excess of allyl glycol with respect to the hydrosilyl group.

[0004] To solve this, when an alcohol solvent such as ethanol or 2-propanol is used during the hydrosilylation reaction, the reactivity increases, but by-products are likely to be generated due to the dehydrogenation reaction between the hydroxyl group in the solvent and the hydrosilyl group of hydrogen polysiloxane. This by-product causes a decrease in the strength of the siloxane-modified polyurethane resin.

[0005] In addition, although not industrially produced, hydroxyl group-containing polysiloxanes corresponding to a structure in which allyl alcohol is added to hydrogen polysiloxane have also been reported in the above patent documents. Furthermore, Patent Document 9 also proposes a polysiloxane having a phenolic hydroxyl group and a hydroxyalkylphenyl group. However, since the phenolic hydroxyl group has low reactivity with an isocyanate group, it is not suitable for urethane resin synthesis. In addition, it is difficult to industrially produce a polysiloxane having a hydroxyalkylphenyl group.

[0006] On the other hand, the polyurethane resin has problems such as low heat resistance, and the siloxane-modified polyurethane resin has problems such as a decrease in strength as described above. From the above, a siloxane-modified polyurethane resin excellent in heat resistance and strength is desired.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a siloxane-modified polyurethane composition that is easy to synthesize, gives a cured product having high resin physical property values such as tensile strength, and excellent heat resistance.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by blending a siloxane compound having a specific structure into a polyurethane composition, and have thus completed the present invention.

[0010] That is, the present invention is 1. (A) A hydroxyl group-containing organosilicon compound represented by the following general formula (1) (R 1 3SiO 1 / 2 ) k (R 1 2SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1) [In formula (1), R 1 is, independently of each other, a group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms and a group represented by the following formula (2), provided that at least one of all R 1 groups is a group represented by the following formula (2). k, p, q, and r are, respectively, a number where k > 0, a number where p ≧ 0, a number where q ≧ 0, and a number where r ≧ 0, provided that k + p + q is a number where k + p + q ≧ 2. Also, the bonding order of each siloxane unit shown in parentheses is arbitrary.

Chemical formula

Chemical formula

Advantages of the Invention

[0011] The siloxane-modified polyurethane composition of the present invention is easy to synthesize, and can provide a cured product having higher resin physical property values such as tensile strength than conventional ones and excellent heat resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] The present invention will be described in detail below. The siloxane-modified polyurethane composition of the present invention contains the following components (A) to (C). (A) A hydroxyl group-containing organosilicon compound represented by the following formula (1) (B) An isocyanate compound having two or more isocyanate groups in one molecule (C) An organic compound having two or more functional groups capable of reacting with isocyanate groups in one molecule

[0013] 〔Component (A)〕 (A) Component is a hydroxyl group-containing organosilicon compound represented by the following formula (1). (R 1 3SiO 1 / 2 ) k (R 1 2SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1)

[0014] In the above formula (1), R 1 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms and a group selected from the groups represented by the following formula (2). However, at least one of all the R 1 groups is an organic group represented by the following formula (2), and preferably 2 to 5 of all the R 1 groups are organic groups represented by the following formula (2).

[0015]

Chemical formula

[0016] R 1Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include linear, branched, and cyclic groups, such as an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms; a cycloalkyl group having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms; an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. R 1 Specific examples of the monovalent hydrocarbon group of 1 include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, R 1 is preferably a methyl group, an ethyl group, or a phenyl group.

[0017] In formula (2), R 2 is, independently of each other, a hydrogen atom or a group selected from a monovalent hydrocarbon group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. R 2 Examples of the monovalent hydrocarbon group having 1 to 5 carbon atoms of 2 include linear or branched groups. Specifically, examples thereof include the same linear or branched groups having 1 to 5 carbon atoms as those exemplified for R 1 , but among them, a methyl group, an isopropyl group, and a t-butyl group are preferable. R 2 Examples of the alkoxy group having 1 to 5 carbon atoms of 2 preferably have 1 to 3 carbon atoms, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and n-pentyloxy groups. Among them, a methoxy group and an ethoxy group are preferable. R 3 is a hydrogen atom or a methyl group.

[0018] In formula (2), s is an integer of 0 to 4, preferably an integer of 0 to 2. t is an integer from 2 to 4, preferably 2 or 3. u is a number from 1 to 3. However, the repeating unit in parentheses with u may be a chemically single repeating unit, a combination of different repeating units, or a combination where the average value is a number from 1 to 3. When u is 0, the hydroxyl group is phenolic, for example, and the reactivity with respect to the isocyanate group decreases. Therefore, u is 1 or more. When it is a combination of different repeating units, the case where u is 0 is not included. Also, when u exceeds 3, the heat resistance decreases, so the case where u is 4 or more is not included, and u is a number from 1 to 3. It is particularly preferable that the repeating unit in parentheses with u is a chemically single repeating unit.

[0019] Examples of the group represented by formula (2) include, but are not limited to, those represented by the following formulae.

[0020]

Chemical formula

[0021] Among these, those represented by the following formulae (3) to (5) are preferable.

Chemical formula

[0022] Specific examples of the group represented by the above formulae (3) to (5) include, but are not limited to, the groups represented by the following formulae. Among these, the groups represented by formulae (3a), (4a) to (4e), and (5a) are preferable.

[0023]

Chemical formula

[0024] In formula (1), k, p, q, and r are numbers where k > 0, p ≥ 0, q ≥ 0, and r ≥ 0. However, k + p + q is a number such that k + p + q ≥ 2. k is preferably a number from 2 to 5, more preferably a number from 2 to 4. p is preferably a number from 2 to 100, more preferably a number from 5 to 80. q is preferably a number from 0 to 3, more preferably a number from 0 to 2, and even more preferably 1 or 2. r is preferably a number from 0 to 3, more preferably 0 or 1, and even more preferably 0. k + p + q is preferably a number such that k + p + q ≥ 5, more preferably a number such that k + p + q ≥ 8. Note that the bonding order of each siloxane unit shown in the parentheses above is not particularly limited, and it may be randomly bonded or form a block structure.

[0025] As the hydroxyl group-containing organosilicon compound used in the present invention, in the above formula (1), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and 2 to 5 of all R 1 groups are preferably groups represented by the above formula (2), k is a number from 2 to 4, p is a number from 5 to 80, q is a number from 0 to 2, r is 0, and all R 1 2 or 3 of the groups are more preferably groups represented by the above formula (2). Also, the group represented by the above formula (2) may be present at either one of the molecular chain ends (one end or both ends) or in the middle of the molecular chain, or may be present at both of these, but it is preferably present at least at the molecular chain ends (one end or both ends), and more preferably present at both ends of the molecular chain.

[0026] As the hydroxyl group-containing organosilicon compound used in the present invention, those represented by the following formula are particularly preferred.

Chemical formula

[0027] The weight-average molecular weight of the hydroxyl group-containing organosilicon compound used in the present invention is preferably from 400 to 15,000, more preferably from 600 to 10,000, still more preferably from 600 to 8,000, and particularly preferably from 600 to 5,000. Note that this weight-average molecular weight is the polystyrene conversion value measured by gel permeation chromatography (GPC) based on the following conditions.) 〔Measurement conditions〕 Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N (6.0 mm I.D. × 15 cm × 1) TSKgel SuperH2500 (6.0 mm I.D. × 15 cm × 1) (All are manufactured by Tosoh Corporation.) Column temperature: 40 °C Sample injection volume: 50 μL (THF solution with a concentration of 0.3 mass%)

[0028] The kinematic viscosity of the hydroxyl group-containing organosilicon compound used in the present invention is preferably from 40 to 10,000 mm 2 / s, more preferably from 50 to 5,000 mm 2 / s. Note that the method for measuring the kinematic viscosity is as described below.)

[0029] The hydroxyl group-containing organosilicon compound used in the present invention can be obtained, for example, by hydrosilylating an organohydrogenpolysiloxane represented by the following general formula (6) and a compound having a hydroxyl group and an aliphatic unsaturated group (allyl group or methallyl group) represented by the following general formula (7).

[0030] As the organohydrogenpolysiloxane, those represented by the following formula (6) are used. (R 4 3SiO 1 / 2 ) k (R 4 2SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (SiO 4 / 2 ) r (6)

[0031] In formula (6), R 4 is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. However, at least one of all the R 4 groups is a hydrogen atom, and it is preferable that 2 to 5 of all the R 4 groups are hydrogen atoms. Examples of the monovalent hydrocarbon group of R 4 include the same groups as those exemplified for R 1 , and among them, preferably a methyl group, an ethyl group, and a phenyl group. k, p, q, and r are the same as described above. Note that the bonding order of each siloxane unit shown in the above parentheses is not particularly limited, and they may be randomly bonded or form a block structure.

[0032] As the organohydrogenpolysiloxane, in the above formula (6), those in which k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and 2 to 5 of all the R 4 groups are hydrogen atoms are preferable, and those in which k is a number from 2 to 4, p is a number from 5 to 80, q is a number from 0 to 2, r is 0, and 2 or 3 of all the R 4 groups are hydrogen atoms are more preferable. Further, the hydrogen atom may be present at either one of the molecular chain ends (one end or both ends) or in the middle of the molecular chain, or may be present at both of these, but it is preferably present at least at the molecular chain ends (one end or both ends), and more preferably present at both ends of the molecular chain.

[0033] Specific examples of the organohydrogenpolysiloxane represented by the formula (6) include, for example, 1,1,3,3 - tetramethyldisiloxane, dimethylpolysiloxane blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, methylhydrogenpolysiloxane blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, methylhydrogen siloxane·dimethylsiloxane copolymer blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, methylhydrogen siloxane·diphenylsiloxane copolymer blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, methylhydrogen siloxane·dimethylsiloxane·diphenylsiloxane copolymer blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, (CH3)3SiO 1 / 2 units and (CH3)2HSiO 1 / 2 units and (CH3)2SiO units and CH3SiO 3 / 2 copolymer composed of units, (CH3)2HSiO 1 / 2 units and (CH3)2SiO units and CH3SiO 3 / 2 copolymer composed of units, (CH3)2HSiO 1 / 2 units and (C6H5)2SiO units and (CH3)2SiO units and CH3SiO 3 / 2 copolymer composed of units, (CH3)(C6H5)HSiO 1 / 2 units and (CH3)2SiO units and CH3SiO 3 / 2 copolymer composed of units, (CH3)2HSiO 1 / 2 units and (CH3)2SiO units and C6H5SiO 3 / 2 copolymers and the like composed of units. These may be used alone or in combination of two or more. Among these, dimethylpolysiloxane blocked at both ends of the molecular chain with dimethylhydrogen siloxy groups, (CH3)2HSiO 1 / 2 units and (CH3)2SiO units and CH3SiO3 / 2 A copolymer consisting of units is preferred.

[0034] On the other hand, as the compound having a hydroxyl group and an aliphatic unsaturated group, those represented by the following formula (7) are used.

[0035]

Chemical formula

[0036] Examples of those represented by formula (7) Compound include, but are not limited to, those represented by the following formula. These may be used alone or in combination of two or more.

[0037]

Chemical formula

[0038] Among these, those represented by the following formulas (8) to (10) are preferred.

Chemical formula

[0039] Examples of those represented by the above formulas (8) to (10) Compound include, but are not limited to, the groups represented by the following formula. Among these, those represented by formula (8a), (9a) to (9e), and (10a) are preferred.

[0040]

Chemical formula

[0041] The compound having a hydroxyl group and an aliphatic unsaturated group represented by formula (7) can be obtained, for example, by the following method. When using a phenolic compound having an allyl group in the molecule, such as ortho-allylphenol or eugenol (2-methoxy-4-allylphenol), which is easily available as a commercial product, a predetermined amount of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or a mixture thereof can be added to the phenolic hydroxyl group by a known method through an addition reaction.

[0042] Also, for example, when using a phenolic compound such as phenol, 2,6-dimethylphenol, 2,4-di-t-butylphenol, or 2,6-di-t-butylphenol as a starting material, first, an allyl halide compound such as allyl bromide, allyl chloride, or methallyl chloride is reacted with these phenolic compounds under basic conditions by a known method to obtain an allyl (or methallyl) phenyl ether. Next, a thermal rearrangement reaction of the allyl group is carried out to obtain an allylated (or methallylated) phenol, and a predetermined amount of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or a mixture thereof can be added to this by an addition reaction in the same manner as described above. Since the thermal rearrangement reaction of the allyl group occurs at the ortho or para position, in order to obtain a high-purity product, it is more preferable to use a compound in which only one of the ortho and para positions is vacant, such as 2,6-dimethylphenol, 2,4-di-t-butylphenol, or 2,6-di-t-butylphenol.

[0043] In the reaction between an organohydrogenpolysiloxane and a compound having a hydroxyl group and an aliphatic unsaturated group, the amount of the compound having a hydroxyl group and an aliphatic unsaturated group used in the reaction is preferably in an amount ratio such that the number of moles of the aliphatic unsaturated group (allyl group or methallyl group) in the compound having a hydroxyl group and an aliphatic unsaturated group is in excess with respect to the number of moles of the hydrosilyl group in the organohydrogenpolysiloxane. For example, with respect to 1 mole of the hydrosilyl group, the molar ratio of the aliphatic unsaturated group is preferably 1 to 5 moles, more preferably 1 to 2 moles, and even more preferably 1 to 1.5 moles. If it is less than 1 mole, the amount of the aliphatic unsaturated group may be insufficient, and dehydrogenation may easily occur. On the other hand, if it exceeds 5 moles, a large amount of unreacted product of the compound having a hydroxyl group and an aliphatic unsaturated group remains in the reaction system, which may be uneconomical.

[0044] The hydrosilylation reaction between the organohydrogenpolysiloxane of the formula (6) and the compound having a hydroxyl group and an aliphatic unsaturated group of the formula (7) is preferably carried out in the presence of a catalyst. The catalyst is not particularly limited, and a conventionally known addition reaction catalyst can be used. Specific examples of the catalyst include, for example, simple substances of platinum group metals such as platinum (including platinum black), palladium, rhodium, ruthenium, and metal catalysts having these platinum group metals, gold, nickel, cobalt, etc. Among these, a platinum group metal catalyst having platinum, palladium or rhodium is particularly preferred. Specific examples of the catalyst having platinum, palladium or rhodium include, for example, PtCl4, H2PtCl6·6H2O, Pt-ether complex, Pt-olefin complex, PdCl2(PPh3)2, PdCl2(PhCN)2, RhCl2(PPh3)3 (in the above formula, Ph is a phenyl group), platinum chloride, chloroplatinic acid or a complex of chloroplatinic acid salt and a vinyl group-containing siloxane. These catalysts may be used alone or as a mixture of two or more. Among these, a metal catalyst having platinum is even more preferred, and a Karstedt catalyst (a complex of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the sodium bicarbonate neutralized product of chloroplatinic acid) is particularly preferred. In addition, these catalysts can be diluted with solvents such as alcohols, aromatics, hydrocarbons, ketones, etc. and used as necessary.

[0045] The amount of the catalyst is not particularly limited as long as it is a catalytic amount. The catalytic amount is an amount sufficient to promote the addition reaction. For example, in terms of the main metal atom conversion amount of the metal catalyst with respect to 100 parts by mass of the hydrogen polysiloxane, it is preferably 0.02 part by mass or less, more preferably 0.00001 to 0.02 part by mass, still more preferably 0.0001 to 0.01 part by mass, and particularly preferably 0.0003 to 0.005 part by mass. The catalyst may be added in its entirety from the beginning of the reaction or added in several portions during the reaction. Even with a low catalyst amount, the reaction can proceed sufficiently. However, if the amount of the catalyst is too small, the reaction rate may become too slow, so the amount above the lower limit is preferred. Also, even if the amount of the catalyst is too large, the reaction rate will not be particularly improved and it may be uneconomical.

[0046] If the resulting hydroxy group-containing siloxane contains a large amount of the residual metal catalyst, it will cause coloring. Therefore, it is better that the amount of the residual metal catalyst is small. In the production method of the present invention, the amount of the metal catalyst contained in the resulting hydroxy group-containing siloxane can be, in terms of the conversion amount of the main metal atom, preferably 0.02 part by mass or less, more preferably 0.01 part by mass or less, still more preferably 0.005 part by mass or less with respect to 100 parts by mass of the siloxane. After completion of the addition reaction, the residual metal catalyst may be adsorbed and removed by activated carbon or the like.

[0047] Another feature of the hydrosilylation reaction between the organohydrogenpolysiloxane and the compound having a hydroxyl group and an aliphatic unsaturated group in the present invention is that it can be carried out without using a solvent, unlike the known method for synthesizing a hydroxyalkyl group-containing polysiloxane. However, a solvent may be used as necessary within a range not impairing the object of the present invention. Specific examples of the solvent include toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, dimethylformamide (DMF), acetonitrile, and the like. When using a solvent, it may or may not be distilled off after the addition reaction is completed.

[0048] The reaction temperature of hydrosilylation is preferably 20 to 200 °C, more preferably 40 to 180 °C, and even more preferably 60 to 150 °C. The reaction time is preferably within 20 hours, more preferably within 12 hours, and even more preferably within 8 hours.

[0049] [Component (B)] Component (B) is an isocyanate compound having two or more isocyanate groups in one molecule. As component (B), as long as it has two or more isocyanate groups in one molecule, it is not particularly limited. For example, those represented by the following formula (11) can be mentioned. OCN-Q-NCO (11) (In the above formula, Q is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted or unsubstituted.)

[0050] Examples of the divalent hydrocarbon group of Q include, preferably, a linear or branched alkylene group having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms; a cycloalkylene group having preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms; an alkylene group having an alicyclic structure having preferably 4 to 15 carbon atoms, more preferably 4 to 13 carbon atoms; an arylene group having preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms; an aralkylene group having preferably 7 to 15 carbon atoms, preferably 7 to 13 carbon atoms, and the like. Further, groups obtained by combining these are also included. Among these, Q is preferably a linear or branched alkylene group, an alkylene group having an alicyclic structure, or an aralkylene group, and more preferably a linear or branched alkylene group or an alkylene group having an alicyclic structure.

[0051] Specific examples of the alkylene group include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, tetradecamethylene groups, and the like. Specific examples of the cycloalkylene group include cyclopentylene, cyclohexylene groups, and the like. As the alkylene group having an alicyclic structure, an alkylene group having a saturated alicyclic structure is preferable, and specific examples thereof include methylenecyclohexylene, methylenebiscyclohexylene groups, and the like. Specific examples of the arylene group include phenylene, naphthylene groups, and the like. Specific examples of the aralkylene group include methylenephenylene, methylenebisphenylene groups, and the like.

[0052] In addition, some of the hydrogen atoms of these groups may be substituted with other substituents. Examples of the other substituents include alkyl groups having 1 to 3 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 3 carbon atoms such as methoxy group and ethoxy group; halogen atoms such as chlorine and bromine; carboxy group, and the like.

[0053] Specific examples of the isocyanate compound represented by the formula (11) include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and other diisocyanate compounds. Also, as the component (B), polymeric MDI, a reaction product of the diisocyanate compound and trimethylolpropane, an isocyanate compound such as a trimer of the isocyanate compound, etc. can also be used. (B) component may be used alone or in combination of two or more.

[0054] Among these, preferably 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate.

[0055] [(C) component] Component (C) is an organic compound having two or more functional groups capable of reacting with isocyanate groups in one molecule. Examples of the functional groups capable of reacting with isocyanate groups include a hydroxyl group, an amino group, a carboxy group, a mercapto group and the like. Component (C) is not particularly limited as long as it has two or more such functional groups in one molecule, but those having a hydroxyl group or an amino group are preferred.

[0056] Specific examples of Component (C) include, for example, polyols (diols) such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-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, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol (1,4-dihydroxymethylcyclohexane), 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, methylpentanediol and the like.

[0057] Furthermore, trifunctional alcohols such as glycerin and trimethylolpropane; tetrafunctional alcohols such as pentaerythritol and α-methylglycoside; hexafunctional alcohols such as sorbitol and sucrose; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; diamines such as ethylenediamine, diaminotoluene, diphenylmethanediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), diethylmethylbenzenediamine, 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, etc. are exemplified. These may be used alone or in combination of two or more. Among these, polyols (diols) and diamines are preferred, and 1,4-butanediol, 1,4-cyclohexanedimethanol (1,4-dihydroxymethylcyclohexane), and isophoronediamine are particularly preferred.

[0058] The blending amounts of components (A) to (C) are preferably such that {(the number of all isocyanate groups (pieces) contained in component (B))} / {(the number of all hydroxy groups and amino groups (pieces) contained in components (A) and (C))}=0.7 to 1.4, more preferably 0.8 to 1.2, still more preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.05.

[0059] 〔Other Components〕 In the composition of the present invention, other components can be blended within a range that does not interfere with the effects of components (A) to (C). Examples of other components include polyols, catalysts, antioxidants, ultraviolet absorbers, light stabilizers, solvents, etc.

[0060] Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, etc., other than the component (C). Specifically, polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polytetramethylene ether glycol, polytetramethylene glycol, polyhexamethylene glycol, etc., which are obtained by polymerizing or copolymerizing alkylene oxide or cyclic ether, can be mentioned.

[0061] Examples of the catalyst include amine compounds such as 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-hydroxyethyl)piperazine, bis(2-dimethylaminoethyl)ether; organic titanium compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, titanium diisopropoxybisacetylacetone complex; titanium tetra-2-ethylhexoxide, titanium diisopropoxybis(ethylacetoacetate); organic zirconium compounds such as zirconium tetrabutoxide, zirconium tetrapropoxide, tetrakis(2,4-pentanedionato)zirconium, zirconium dibutoxybis(ethylacetoacetate); organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, etc.

[0062] Examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc.

[0063] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and the like.

[0064] Examples of the light stabilizer include hindered amine-based light stabilizers and the like.

[0065] Examples of the solvent include toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, dimethylformamide (DMF), acetonitrile, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide (DMAc), ethyl acetate, butyl acetate, water, and the like.

[0066] Moreover, organopolysiloxanes containing amino groups at both ends of the molecular chain, such as dimethylpolysiloxane having amino groups at both ends of the molecular chain, can also be used.

[0067] The siloxane-modified polyurethane composition of the present invention can be obtained by mixing the above-described components according to a conventional method. Other components can be added to the components (A) to (C) at an arbitrary timing.

[0068] The method (synthesis method) for producing a resin from the siloxane-modified polyurethane composition of the present invention is not particularly limited, and a method conventionally used for producing a polyurethane resin can be used. Examples thereof include a prepolymer method and a one-shot method.

[0069] The prepolymer method first reacts component (A) and component (B). The reaction temperature is preferably 10 to 250°C, more preferably 20 to 150°C, and even more preferably 50 to 120°C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. After that, component (C) is further reacted. The reaction temperature and reaction time are the same as those described above.

[0070] The one-shot method is a method of simultaneously reacting component (A), component (B), and component (C). The reaction temperature is preferably 10 to 250°C, more preferably 20 to 150°C, and even more preferably 50 to 120°C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours.

[0071] The siloxane-modified polyurethane composition of the present invention forms a resin or elastomer having thermoplasticity by curing (thermosetting) depending on its composition, but can also be made into a thermosetting composition by using a polyfunctional isocyanate compound or polyhydric alcohol having three or more functional groups. As the composition of the present invention, those that form a resin or elastomer having thermoplasticity by curing are preferred. Examples of the molding method include a method of cutting into pellets with a twin-screw extruder and then processing into a molded product using various commonly used molding machines, namely, an extrusion molding machine, an injection molding machine, a calender molding machine, a press molding machine, etc. In addition, the composition of the present invention is in a liquid state dissolved in an organic solvent, or in a liquid state such as two-component or three-component liquid in which the prepolymer and the chain extender component are separated, and is preferably used as a primer coating agent or a top coating agent for various plastics such as polyester, nylon, polyvinyl chloride, ABS, OPP, and CPP. Furthermore, it can be used as paints, surface coating materials, sealants, OA rolls, shoes, ski boots, adhesives, wood binders, thermoplastic elastomers, thermosetting elastomers, etc. for various fibers such as elastic fibers, various fiber woven fabrics, non-woven fabrics, paper, natural leather, artificial leather, synthetic leather, wood, etc.

Examples

[0072] Examples of synthesis, examples, and comparative examples are shown below to explain the present invention in more detail. However, the present invention is not limited to the following examples.

[0073] In the following examples, the property evaluations were performed by the following methods. The kinematic viscosity was measured at a temperature of 25 °C using a Cannon-Fenske viscometer according to the method described in JIS Z8803:2011. The hydroxyl value was measured according to JIS K 0070:1992. The tensile strength was measured at a speed of 100 mm / min using a No. 6 dumbbell-shaped specimen punched from a 1-mm-thick cured sheet according to the method described in JIS K 7312:1996. The heat resistance was evaluated by measuring the tensile strength after heating at 120 °C for 3 days. At that time, it was carried out without adding an antioxidant or a heat resistance improver. The reduction rate can be obtained from the following formula. Reduction rate (%) = 100 - (tensile strength after heating ÷ initial tensile strength × 100) The modulus (storage elastic modulus) was measured using a dynamic viscoelasticity measuring device Rheogel-E4000HP (manufactured by UBM Co., Ltd.). The measurement conditions were an elongation test of the test piece of 0.8 to 1.5 mm, an initial elongation of 20 mm, a strain of 5 μm at 10 Hz, and a temperature increase rate of 3 °C / min from -50 °C to 150 °C.

[0074] [Synthesis Example 1] After replacing the inside of the flask with nitrogen, 186.9 g of an unsaturated alcohol compound represented by the following formula (12) and 0.10 g of a Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 70 °C. 363.0 g of a methylhydrogenpolysiloxane represented by the following formula (13) was added dropwise thereto over 35 minutes. After completion of the dropwise addition, the mixture was further stirred at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 2.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 497.0 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (14). The appearance was colorless and transparent, and the kinematic viscosity was 125 mm2 / s, the hydroxyl value was 112 mg KOH / g.

[0075] [Chemical formula]

[0076] [Synthesis Example 2] After replacing the inside of the flask with nitrogen, 446.9 g of an unsaturated alcohol compound represented by the following formula (15) and 0.23 g of a Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 60°C. 742.8 g of the methylhydrogenpolysiloxane represented by the above formula (13) was added dropwise thereto over 22 minutes. After completion of the dropwise addition, the mixture was further stirred at 110°C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220°C / 400 Pa). 5.9 g of activated carbon was added, and after stirring at room temperature for 2 hours, filtration was performed using a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 1074.2 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (16). The appearance was colorless and transparent, the kinematic viscosity was 372 mm 2 / s, the hydroxyl value was 105 mg KOH / g.

[0077] [Chemical formula]

[0078] [Synthesis Example 3] After replacing the inside of the flask with nitrogen, 231.1 g of an unsaturated alcohol compound which is a mixture of a compound represented by the following formula (17) and a compound represented by the following formula (18) (the content ratio of the compound of formula (17) to the compound of formula (18) is formula (17) / formula (18) = 86 / 14 mol%).), 0.11 g of a Karstedt catalyst (platinum concentration 0.5% by mass) was charged and heated to 70°C. 363.0 g of the methylhydrogenpolysiloxane represented by the above formula (13) was added dropwise thereto over 44 minutes. After completion of the dropwise addition, the mixture was further stirred at 110°C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 3.0 g of activated carbon was added, and after stirring at room temperature for 2 hours, filtration was performed using a filter plate (NA-500, manufactured by Advantec Co., Ltd.), and 536.0 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (19) was obtained. In the product, the content ratio of primary hydroxyl groups and secondary hydroxyl groups was the same as the content ratio of the compound of formula (17) and the compound of formula (18). The appearance was colorless and transparent, and the kinematic viscosity was 283 mm 2 / s, and the hydroxyl value was 92.2 mg KOH / g.

[0079]

Chemical formula

[0080] [Synthesis Example 4] After replacing the inside of the flask with nitrogen, 160.0 g of an unsaturated alcohol compound represented by the following formula (20) and 0.07 g of a Karstedt catalyst (platinum concentration 0.5 mass%) were charged and heated to 70 °C. 219.0 g of the methylhydrogenpolysiloxane represented by the above formula (13) was added dropwise thereto over 38 minutes. After completion of the dropwise addition, stirring was further performed at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 2.0 g of activated carbon was added, and after stirring at room temperature for 2 hours, filtration was performed using a filter plate (NA-500, manufactured by Advantec Co., Ltd.), and 340.6 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (21) was obtained. The appearance was colorless and transparent, and the kinematic viscosity was 408 mm 2 / s, and the hydroxyl value was 98.7 mg KOH / g.

[0081]

Chemical formula

[0082] [Synthesis Example 5] After replacing the inside of the flask with nitrogen, 203.0 g of the unsaturated alcohol compound represented by the following formula (22) and 0.11 g of Karstedt catalyst (platinum concentration 0.5% by mass) were charged, and the mixture was heated to 70°C. 325.2 g of the methylhydrogenpolysiloxane represented by the above formula (13) was added dropwise thereto over 20 minutes. After completion of the dropwise addition, the mixture was further stirred at 110°C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220°C / 400 Pa). 2.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 467.1 g of the hydroxyl group-containing organopolysiloxane represented by the following formula (23). The appearance was colorless and transparent, and the kinematic viscosity was 290 mm 2 / s, and the hydroxyl value was 109 mg KOH / g.

[0083]

Chemical formula

[0084] [Comparative Synthesis Example 6] After replacing the inside of the flask with nitrogen, 64.7 g of allyl glycol and 0.15 g of Karstedt catalyst (platinum concentration 0.5% by mass) were charged, and the mixture was heated to 70°C. 150.0 g of the methylhydrogenpolysiloxane represented by the above formula (13) was added dropwise thereto over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at 110°C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (120°C / 400 Pa). 1.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 171.9 g of the hydroxyl group-containing organopolysiloxane represented by the following formula (24). The appearance was colorless and transparent, and the kinematic viscosity was 35.0 mm 2 / s, and the hydroxyl value was 115 mg KOH / g.

[0085]

Chemical formula

[0086] [Example 1] After replacing the inside of the flask with nitrogen, 71.1 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 1 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 36.5 g of hexamethylene diisocyanate was added thereto, and the mixture was stirred at 80 °C for 2 hours. After cooling to 35 °C or lower, 12.8 g of 1,4-butanediol was added and stirred for 5 minutes. Then, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0087] [Example 2] After replacing the inside of the flask with nitrogen, 72.7 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 2 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 35.0 g of hexamethylene diisocyanate was added thereto, and the mixture was stirred at 80 °C for 2 hours. After cooling to 35 °C or lower, 12.2 g of 1,4-butanediol was added and stirred for 5 minutes. Then, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0088] [Example 3] After replacing the inside of the flask with nitrogen, 76.7 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 3 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 32.4 g of hexamethylene diisocyanate was added thereto, and the mixture was stirred at 80 °C for 2 hours. After cooling to 35 °C or lower, 11.3 g of 1,4-butanediol was added and stirred for 5 minutes. Then, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0089] [Example 4] After replacing the inside of the flask with nitrogen, 75.0 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 4 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 33.9 g of hexamethylene diisocyanate was added thereto, and the mixture was stirred at 80 °C for 2 hours. It was cooled to 35 °C or lower, 11.9 g of 1,4-butanediol was added, and the mixture was stirred for 5 minutes. Thereafter, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0090] [Example 5] After replacing the inside of the flask with nitrogen, 71.8 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 5 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 36.0 g of hexamethylene diisocyanate was added thereto, and the mixture was stirred at 80 °C for 2 hours. It was cooled to 35 °C or lower, 12.6 g of 1,4-butanediol was added, and the mixture was stirred for 5 minutes. Thereafter, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0091] [Comparative Example 1] After replacing the inside of the flask with nitrogen, 70.3 g of the hydroxyl group-containing organopolysiloxane of Comparative Synthesis Example 6 and 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, and 37.0 g of hexamethylene diisocyanate was added thereto, followed by stirring at 80 °C for 2 hours. After cooling to 35 °C or lower, 13.0 g of 1,4-butanediol was added and stirred for 5 minutes. Thereafter, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained lump was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 1.

[0092] [Table 1] The blending amounts were such that the ratio of the hydroxyl group-containing organopolysiloxane:hexamethylene diisocyanate: 1,4-butanediol was 1.0:3.06:2.0 in molar ratio. Also, the addition amount of zirconium tetraacetylacetonate was 25 ppm.

[0093] As shown in Table 1, the cured products (siloxane-modified polyurethane resins) of the siloxane-modified polyurethane compositions of Examples 1 to 5 had higher initial tensile strength and lower reduction rate after heating at 120 °C compared to the cured product of the known composition of Comparative Example 1, and the heat resistance was improved.

[0094] [Synthesis Example 7] After replacing the inside of the flask with nitrogen, 103.5 g of the unsaturated alcohol compound represented by the above formula (15) and 0.22 g of a Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 70 °C. 1012.5 g of the methylhydrogenpolysiloxane represented by the following formula (25) was added dropwise thereto over 15 minutes. After completion of the dropwise addition, stirring was further carried out at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 5.6 g of activated carbon was added, and after stirring at room temperature for 2 hours, filtration was carried out using a filter plate (NA-500, manufactured by Advantec Co., Ltd.), and 1004.0 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (26) was obtained. The appearance was colorless and transparent, and the kinematic viscosity was 244 mm 2 / s, and the hydroxyl value was 23.0 mg KOH / g.

[0095]

Chemical formula

[0096] [Comparative Synthesis Example 8] After purging the inside of the flask with nitrogen, 30.6 g of allyl glycol and 0.18 g of Karstedt catalyst (platinum concentration 0.5 mass%) were charged and heated to 70 °C. 427.8 g of the methylhydrogenpolysiloxane represented by the above formula (25) was added dropwise thereto over 30 minutes. After completion of the dropwise addition, stirring was further carried out at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (120 °C / 400 Pa). 2.3 g of activated carbon was added, and after stirring at room temperature for 2 hours, filtration was carried out using a filter plate (NA-500, manufactured by Advantec Co., Ltd.), and 395.4 g of a hydroxyl group-containing organopolysiloxane represented by the following formula (27) was obtained. The appearance was colorless and transparent, and the kinematic viscosity was 70.0 mm 2 / s, and the hydroxyl value was 24.0 mg KOH / g.

[0097]

Chemical formula

[0098] [Example 6] After replacing the atmosphere in the flask with nitrogen, 102.4 g of the hydroxyl-containing organopolysiloxane of Synthesis Example 7, 16.1 g of 4,4'-diphenylmethane diisocyanate, 0.006 g of zirconium tetraacetylacetonate (Zr(acac)4), and 30 mL of methyl ethyl ketone were charged and stirred at 80°C for 2 hours. The mixture was cooled to 35°C or less, and 3.8 g of 1,4-butanediol was added and stirred for 5 minutes. The contents were then transferred to a Teflon (registered trademark) vat and heated at 120°C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The resulting mass was press molded at 210°C for 8 minutes under a molding pressure of 10 MPa to obtain a 1 mm thick cured sheet, and the tensile strength was measured. The same cured sheet was also used to measure the storage modulus at -30°C and +120°C. The results are shown in Table 2.

[0099] [Comparative Example 2] After replacing the atmosphere in the flask with nitrogen, 99.6 g of the hydroxyl-containing organopolysiloxane of Comparative Synthesis Example 8, 16.3 g of 4,4'-diphenylmethane diisocyanate, 0.006 g of zirconium tetraacetylacetonate (Zr(acac)4), and 30 mL of methyl ethyl ketone were charged and stirred at 80°C for 2 hours. The mixture was cooled to 35°C or less, and 3.8 g of 1,4-butanediol was added and stirred for 5 minutes. The contents were then transferred to a Teflon (registered trademark) vat and heated at 120°C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The resulting mass was press molded at 210°C for 8 minutes under a molding pressure of 10 MPa to obtain a 1 mm thick cured sheet, and the tensile strength was measured. The same cured sheet was also used to measure the storage modulus at -30°C and +120°C. The results are shown in Table 2.

[0100] [Table 2] The compounding ratio was 1.0:3.06:2.0 in terms of the molar ratio of the hydroxyl group-containing organopolysiloxane:4,4'-diphenylmethane diisocyanate:1,4-butanediol. Also, the addition amount of zirconium tetraacetylacetonate was 50 ppm.

[0101] As shown in Table 2, the cured product of the siloxane-modified polyurethane composition of Example 6 (siloxane-modified polyurethane resin) had a higher initial tensile strength and a lower reduction rate after heating at 120 °C compared to the cured product of the known composition of Comparative Example 2, and its heat resistance was improved. Furthermore, the temperature dependence of the storage elastic modulus was low, and it had a stable storage elastic modulus from low temperature to high temperature.

[0102] [Synthesis Example 9] After purging the inside of the flask with nitrogen, 131.0 g of the unsaturated alcohol compound represented by the above formula (15) and 0.12 g of Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 70 °C. 484.2 g of the methylhydrogenpolysiloxane represented by the following formula (28) was added dropwise thereto over 15 minutes. After completion of the dropwise addition, the mixture was further stirred at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 3.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours and then filtered through a filter plate (NA-500, manufactured by Advantec) to obtain 542.1 g of the hydroxyl group-containing organopolysiloxane represented by the following formula (29). The appearance was colorless and transparent, the kinematic viscosity was 216 mm 2 / s, and the hydroxyl value was 55.7 mgKOH / g.

[0103] [Chemical formula]

[0104] [Example 7] After replacing the inside of the flask with nitrogen, 60.4 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 9, 0.003 g of zirconium tetraacetylacetonate (Zr(acac)4), and 20 mL of tetrahydrofuran were charged, and 24.1 g of 4,4'-dicyclohexylmethane diisocyanate was added thereto, followed by stirring at 80 °C for 2 hours. After cooling to 35 °C or lower, a mixed solution of 47.4 g of the amino group-containing organopolysiloxane represented by the following formula (30) and 40 mL of tetrahydrofuran was added dropwise over 35 minutes.

[0105] [Chemical formula]

[0106] Next, 2.7 g of 1,4-butanediol was added and stirred for 5 minutes. Then, the content was transferred to a Teflon (registered trademark) vat, and the solvent was removed under reduced pressure at 50 °C. After that, it was heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 3.

[0107] [Example 8] After replacing the inside of the flask with nitrogen, 17. of the hydroxyl group-containing organopolysiloxane of Synthesis Example 2. 6g , 80.5 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 7, and 0.012 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, and 17.0 g of hexamethylene diisocyanate was added thereto, followed by stirring at 80 °C for 2 hours. After cooling to 35 °C or lower, 5.9 g of 1,4-butanediol was added and stirred for 5 minutes. Then, the content was transferred to a Teflon (registered trademark) vat, and it was heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet with a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 3.

[0108] [Example 9] After replacing the atmosphere in the flask with nitrogen, 83.9g of the hydroxyl-containing organopolysiloxane of Synthesis Example 7, 6.5g of polytetramethylene glycol (molecular weight 250), 0.006g of zirconium tetraacetylacetonate (Zr(acac)4), and 40mL of methyl ethyl ketone were charged, and 22.1g of hexamethylene diisocyanate was added thereto and stirred at 80°C for 2 hours. The mixture was cooled to 35°C or less, and 7.7g of 1,4-butanediol was added and stirred for 5 minutes. The contents were then transferred to a Teflon (registered trademark) vat, and the solvent was removed under reduced pressure at 50°C, followed by heating at 120°C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained block was press molded at 210° C. for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 3.

[0109] [Synthesis Example 10] After replacing the atmosphere in the flask with nitrogen, 48.7 g of the unsaturated alcohol compound represented by the above formula (12) and 0.10 g of Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 80° C. To this, 372.0 g of methylhydrogenpolysiloxane represented by the following formula (31) was added dropwise over 5 minutes. After the dropwise addition was completed, the mixture was stirred at 110° C. for an additional 2 hours. Subsequently, unreacted materials were distilled off under reduced pressure (220° C. / 400 Pa). 2.0 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 353.8 g of a hydroxyl-containing organopolysiloxane represented by the following formula (32). The appearance is colorless and transparent, and the dynamic viscosity is 173mm. 2 / s and the hydroxyl value was 38.0 mgKOH / g.

[0110] [ka]

[0111] [Example 10] After replacing the inside of the flask with nitrogen, 88.6 g of the hydroxyl group-containing organopolysiloxane of Synthesis Example 10 and 0.012 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, and 24.1 g of 4,4'-dicyclohexylmethane diisocyanate was added thereto, followed by stirring at 80 °C for 2 hours. The mixture was cooled to 35 °C or lower, 5.4 g of 1,4-butanediol was added, and the mixture was stirred for 5 minutes. Thereafter, the content was transferred to a Teflon (registered trademark) vat and heated at 120 °C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained mass was press-molded at 210 °C for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 3.

[0112]

Table 3

[0113] [Synthesis Example 11] After replacing the inside of the flask with nitrogen, 182.3 g of the unsaturated alcohol compound represented by the above formula (15) and 0.30 g of a Karstedt catalyst (platinum concentration: 0.5% by mass) were charged and heated to 80 °C. 1296.0 g of the methylhydrogenpolysiloxane represented by the following formula (33) was added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at 110 °C for 2 hours. Subsequently, the unreacted substances were distilled off by heating under reduced pressure (220 °C / 400 Pa). 7.4 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 1404.0 g of the hydroxyl group-containing organopolysiloxane represented by the following formula (34). The appearance was colorless and transparent, the kinematic viscosity was 231 mm 2 / s, and the hydroxyl value was 33.0 mg KOH / g.

[0114]

Chemical formula

[0115] [Synthesis Example 12] After replacing the atmosphere in the flask with nitrogen, 80.8 g of the unsaturated alcohol compound represented by the above formula (22) and 0.25 g of Karstedt catalyst (platinum concentration 0.5% by mass) were charged and heated to 80° C. To this, 762.7 g of the methylhydrogenpolysiloxane represented by the above formula (25) was added dropwise over 5 minutes. After the dropwise addition was completed, the mixture was stirred at 110° C. for an additional 2 hours. Subsequently, unreacted materials were distilled off under reduced pressure (230° C. / 400 Pa). 4.5 g of activated carbon was added, and the mixture was stirred at room temperature for 2 hours, and then filtered through a filter plate (NA-500, manufactured by Advantec Co., Ltd.) to obtain 776.0 g of a hydroxyl-containing organopolysiloxane represented by the following formula (35). The appearance is colorless and transparent, and the dynamic viscosity is 191mm 2 / s and the hydroxyl value was 24.5 mgKOH / g.

[0116] [ka]

[0117] [Example 11] After replacing the atmosphere in the flask with nitrogen, 95.2 g of the hydroxyl-containing organopolysiloxane of Synthesis Example 11 and 0.012 g of zirconium tetraacetylacetonate (Zr(acac)4) were charged, 17.8 g of isophorone diisocyanate was added, and the mixture was stirred at 80°C for 2 hours. The mixture was cooled to 35°C or less, and 7.3 g of 1,4-dihydroxymethylcyclohexane was added and stirred for 5 minutes. The contents were then transferred to a Teflon (registered trademark) vat and heated at 120°C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained block was press molded at 210° C. for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 4.

[0118] [Example 12] After replacing the atmosphere in the flask with nitrogen, 100.8 g of the hydroxyl-containing organopolysiloxane of Synthesis Example 12, 0.012 g of zirconium tetraacetylacetonate (Zr(acac)4), and 30 mL of tetrahydrofuran were charged, and 14.0 g of isophorone diisocyanate was added thereto and stirred at 80°C for 2 hours. The mixture was cooled to 35°C or less, and 6.7 g of isophorone diamine was added and stirred for 5 minutes. The contents were then transferred to a Teflon (registered trademark) vat and heated at 120°C for 24 hours under a nitrogen atmosphere to obtain a siloxane-modified polyurethane resin. The obtained block was press molded at 210° C. for 8 minutes under a molding pressure of 10 MPa to obtain a cured sheet having a thickness of 1 mm, and the tensile strength was measured. The results are shown in Table 4.

[0119] [Table 4]

Claims

1. (A) A hydroxyl group-containing organosilicon compound represented by the following general formula (1) (R 1 3 SiO 1 / 2 ) k (R 1 2 SiO 2 / 2 ) p (R 1 SiO 3 / 2 ) q (SiO 4 / 2 ) r (1) [In formula (1), R 1 is, independently of one another, a group selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms and a group represented by the following formula (2), provided that at least one of all the R 1 groups is a group represented by the following formula (2). k, p, q, and r are, respectively, a number where k > 0, a number where p ≥ 0, a number where q ≥ 0, and a number where r ≥ 0, provided that k + p + q is a number where k + p + q ≥ 2. Also, the bonding order of each siloxane unit shown in parentheses is arbitrary. 【Chemical 1】 (In formula (2), R 2 is, independently of one another, a group selected from a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and R 3 is a hydrogen atom or a methyl group. s is an integer from 0 to 4, t is an integer from 2 to 4, and u is a number from 1 to 3. The dashed line represents a bond.)] (B) An isocyanate compound having two or more isocyanate groups in one molecule (C) An organic compound having two or more functional groups capable of reacting with an isocyanate group in one molecule A siloxane-modified polyurethane composition containing the same.

2. The siloxane-modified polyurethane composition according to Claim 1, wherein the group represented by the formula (2) is any one of the groups represented by the following formulas (3) to (5). 【Chemical 2】 (In the formula, t and u are the same as above. The broken line represents a bond.)

3. In the formula (1) of the component (A), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and 2 to 5 of all R 1 The siloxane-modified polyurethane composition according to claim 1, wherein 2 to 5 of the groups are groups represented by the formula (2).

4. The siloxane-modified polyurethane composition according to Claim 1, wherein the component (A) is an addition reaction product of an organohydrogenpolysiloxane represented by the following general formula (6) and a compound containing a hydroxyl group and an aliphatic unsaturated group represented by the following general formula (7). (R 4 3 SiO 1 / 2 ) k (R 4 2 SiO 2 / 2 ) p (R 4 SiO 3 / 2 ) q (SiO 4 / 2 ) r (6) (In formula (6), R 4 is, independently of one another, a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that at least one of all R 4 groups is a hydrogen atom. k, p, q and r are the same as described above. Also, the bonding order of each siloxane unit shown in parentheses is arbitrary.) [Chemical Formula 3] (In formula (7), R 2 , R 3 , s, t, and u are the same as described above.)

5. The siloxane-modified polyurethane composition according to Claim 4, wherein the compound containing a hydroxyl group and an aliphatic unsaturated group represented by the formula (7) is any one of the compounds represented by the following formulas (8) to (10). 【Chemical Formula 4】 (In the formula, t and u are the same as above.)

6. In the above formula (6), k is a number from 2 to 5, p is a number from 2 to 100, q is a number from 0 to 3, r is 0, and 2 to 5 of all R 4 The siloxane-modified polyurethane composition according to claim 4, wherein 2 to 5 of the groups are hydrogen atoms.

7. The siloxane-modified polyurethane composition according to Claim 1, wherein the component (B) is represented by the following formula (11). OCN-Q-NCO (11) (In the above formula, Q is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.)

8. The siloxane-modified polyurethane composition according to Claim 7, wherein in the formula (11), Q is a linear or branched alkylene group or an alkylene group having an alicyclic structure.

9. The siloxane-modified polyurethane composition according to Claim 1, wherein the functional group capable of reacting with the isocyanate group of the component (C) is a group selected from a hydroxyl group, an amino group, a carboxy group, and a mercapto group.

10. A thermoset of the siloxane-modified polyurethane composition according to any one of Claims 1 to 9.

11. The thermoset of the siloxane-modified polyurethane composition according to Claim 10, which has thermoplasticity.

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