JP2525181B2 - Silicone-modified polyurethane and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a silicone-modified polyurethane and a method for producing the same, more specifically, a silicone-modified polyurethane showing excellent antithrombogenicity without lowering the mechanical strength originally possessed by polyurethane. The present invention relates to polyurethane and a method for producing the same.

[Technical Background of the Invention and Problems Thereof] It has been conventionally practiced to modify a polydiorganosiloxane for the purpose of imparting water repellency, oil repellency, low friction property or antithrombotic property to polyurethane. Is. Originally, polydiorganosiloxane is a polymer having poor compatibility with polyurethane, and the mere polymer blending method as a method for imparting the above-mentioned various properties of polydiorganosiloxane to polyurethane is adopted because of the bleeding phenomenon of polydiorganosiloxane on the surface of the mixture. Can not.

Therefore, by using a polydiorganosiloxane having a silanol group, an alcohol group or an isocyanate group at both terminals, a polydiorganosiloxane chain is introduced into the main chain of polyurethane to form a block copolymer (for example, JP-A-60-238315). ), A method of introducing a polydiorganosiloxane chain to the terminal of a polyurethane by using a polydiorganosiloxane having a silanol group at one end, or a method of introducing a polydiorganosiloxane of an addition reaction type into a so-called polydiorganosiloxane Various ideas have been made such as a method of forming an interpenetrating network structure (hereinafter referred to as IPN) (for example, JP-A-58-189257).

However, in these methods, a. In the case of a block copomer in which a polydiorganosiloxane chain is introduced into the main chain of polyurethane, the mechanical strength is reduced due to the polysiloxane chain, and a polydiorganosiloxane chain is introduced into the terminal of polyurethane. In the case of b.IPN, the latter is less compatible with polyurethane and polydiorganosiloxane. It is not easy to form an IPN dispersed in the polymer, and therefore the mechanical strength is deteriorated, and sufficient property improvement cannot be obtained unless the polydiorganosiloxane is used in a considerably large proportion.

Further, the general formula (B) described in Japanese Patent Application No. 61-67962 of the present inventors. (In the formula, Me represents a methyl group, and n is an integer of 0 to 4000) In the case of a polyurethane obtained by using the silicone compound as a part of the hydroxyl group-containing compound, Since the two hydroxyl groups of the compound are primary and secondary, respectively, the reactivity is different and it is difficult to obtain stable physical properties.

The present inventors have conducted research to solve the problems of the prior art and provide a polyurethane having desirable properties such as low friction, water repellency, oil repellency, and antithrombogenicity.

As a result, when a polyisocyanate and a polyhydroxyl compound are reacted according to a known method, a part of the polyhydroxyl compound is represented by the following general formula (A) described in Japanese Patent Application No. 62-23888. (In the formula, R is H, Me or Et, and Me is a methyl group
Represents an ethyl group, and n is 0 to 4000). When the reaction is carried out by substituting with a silicone compound, it is known that a polyurethane having excellent physical properties as described above can be obtained. Completed the invention.

As is clear from the above description, an object of the present invention is to provide a method for producing a polyurethane having good physical properties as described above.

[Means for Solving the Problems] That is, the present invention provides a polyurethane obtained from a compound having at least two isocyanate groups and a compound having at least two hydroxyl groups, which is used in the reaction for forming a urethane bond. As a part of the hydroxyl group-containing compound, the following general formula (A) (In the formula, R is H, Me or Et, and Me is a methyl group
Are each an ethyl group, and n is 0 to 4000). The method for producing a silicone-modified polyurethane is characterized by using a silicone compound represented by the formula:

Hereinafter, the configuration and effects of the present invention will be described in more detail.

With regard to the compound having at least two isocyanate groups or the compound having at least two hydroxyl groups used in the present invention, any compound which can be used as a usual raw material for producing polyurethane can be used without any limitation. .

That is, as a compound having at least two isocyanate groups, a compound which is a basic raw material of polyurethane and is commonly called diisocyanate, for example, tolylene diisocyanate, diphenylmethane diisocyanate,
Dianisidine diisocyanate, diphenyl ether diisocyanate, pentylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate methyl ester, metaxylene diisocyanate,
2,2,4-trimethylhexamylene diisocyanate, dimer acid diisocyanate, isopropylidene bis.
(4-cyclohexyl diisocyanate), cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tolylene diisocyanate dimer, etc., and triphenylmethane triisocyanate, triisocyanate phenyl thiophosphate or the above diisocyanates and trimethylol propane, trimethylol ethane, tri The compound which has three or more isocyanate groups, such as an adduct with polyhydric alcohols, such as methylol methane, can also be mentioned.

In addition, it is a prepolymer of these isocyanate group-containing compounds and polyhydric alcohols or compounds having two or more amino groups and has two or more isocyanate groups, such as a compound having two or more isocyanate residues. Almost any compound can be used, and so-called blocked isocyanates obtained by blocking these isocyanate groups with a compound having active hydrogen such as phenols, oximes, lactams or sodium bisulfate can also be used. .

The compound having at least two hydroxyl groups used in the present invention includes ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopetyl glycol, 1 , 5-pentadiol, 2-methyl-2,4-pentadiol, alkanediols such as 1,6-hexanediol and 2,5-hexanediol, glycerin, trimethylolpropane, trimethylolethane, trimethylolmethane, Polyhydric alcohols having three or more hydroxyl groups such as pentaerythritol and sorbitol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers of polyethylene glycol and polypropylene glycol such as polyethylene glycol. Oxyalkylene glycols, polyhydric alcohols such as glycerin or 2
Polyether polyols obtained from a compound having at least one amino group and an alkylene oxide, or a hydroxyl group-containing compound as exemplified above and adipic acid, maleic anhydride, fumaric acid, succinic anhydride, itaconic acid, So-called polyester polyols obtained by reacting with polybasic acids such as sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, pyromellitic anhydride,
Alternatively, a polylactone ester polyol obtained by ring-opening ε-caprolactam is exemplified.

As a matter of course, there is no problem in mixing and using two or more of each of the above-mentioned isocyanate group-containing compound and hydroxyl group-containing compound.

Formula (A) used as a modifier in the present invention (In the formula, R is H, Me or Et, and Me is a methyl group
Each represent an ethyl group, and n is 0 to 4000), and the silicone compound represented by the following can be obtained by the method described in Japanese Patent Application No. 62-23888. Is.

First, 2- (2-propenyloxy) methyl-2-alkylpropane-1,3-diol (II) and hexamethyldisilazane (III) are reacted in the presence of trimethylchlorosilane to give 1,3-bis (Trimethylsiloxy)-
2- (2-Propenyloxy) methyl-2-alkylpropane (IV) is synthesized. Next, the polydimethylsiloxane compounds (V) and (IV) having one end modified with hydrogenene (hereinafter abbreviated to one end with Si—H) are added in the presence of an addition reaction catalyst such as a platinum complex in an inert gas atmosphere. Let it react,
By converting the polydimethylsiloxane derivative of the formula (VI) into a trimethylsilyl derivative of the formula (VI), the desired polysiloxane compound (I) modified with a dihydroxyl group at one end is obtained. This is shown as a reaction formula as follows.

The one-terminal Si-H modified polydimethylsiloxane of the formula (V) is obtained by subjecting hexamethylcyclotricycloxane to living polymerization with lithium trimethylsilanolate or sodium trimethylsilanolate, and using dimethylchlorosilane as a chain terminator to obtain a desired average degree of polymerization. You can get things. The one-terminal Si-H modified polysiloxane thus synthesized has a controlled molecular weight and molecular weight distribution, and can be freely synthesized if the average molecular weight is 80,000 or less. The compound of the formula (V) where n = 0 is pentamethyldicycloxane, which can be easily obtained regardless of the above production method. In the reaction of the one-terminal Si-H modified polydimethylsiloxane compound (V) with the propenyloxymethylalkylpropane diol derivative (IV), the latter is used in an equimolar amount or more, preferably 1.2 times equivalent amount or more.

As the catalyst of this hydrosilylation reaction, a complex compound of a metal element of Group VIII of the Periodic Table can be generally mentioned, and a compound obtained by dissolving chloroplatinic acid in an alcohol or a carbonyl compound, or a mixture of various olefins and platinum or rhodium. Complex and the like are preferably used.
The detrimethylsilylation reaction of the compound of the formula (VI) can be carried out using a lower alcohol such as methanol or ethanol or hydrochloric acid. When using alcohol (VI)
By adding alcohol to polysiloxane of formula and heating under reflux for several hours, or when using hydrochloric acid (VI), by adding appropriate amount of hydrochloric acid and stirring at room temperature for several hours, detrimethylsilylation can be easily carried out. It can be carried out.

Generally, in polyurethane, a compound having at least two isocyanate groups and a compound having at least two hydroxyl groups are appropriately combined to form a urethanization reaction accelerating catalyst, a foaming agent, a pigment, a curing agent (crosslinking agent), a chain extender. Produced under a wide variety of conditions, such as by properly mixing auxiliary materials such as stabilizers, using a solvent in some cases, and selecting various reaction conditions or post-treatment conditions, elastomers, foams, paints, adhesives, It is widely applied to sealants, binders, elastic fibers and the like, and the production method of the silicone-modified polyurethane of the present invention will be described for the case where an elastomer is used as a typical example among these applications.

Incidentally, the method for producing polyurethane is basically from the viewpoint of how to react the isocyanate group-containing compound as the main raw material with the hydroxyl group-containing compound, basically, all the raw materials are charged at the same time and heated. There is a method of reacting, and a method of forming one or both of an isocyanate group-containing compound or a hydroxyl group-containing compound as a prepolymer, and then sequentially reacting it through two or more steps. . In the present invention, either of the above methods can be used, but when the reaction is carried out in a single step, the silicone compound (A) may be used as a part of the hydroxyl group-containing compound as a raw material. Since the weight ratio of the silicone compound in the generated polyurethane is relatively small, no special device is required for the reaction, but since the compatibility between the silicone compound (A) and the generated polyurethane is poor, the silicone compound (A) is uniformly dispersed. It is preferable to use a solvent for the reaction.

When a method of first reacting with a prepolymer and then sequentially reacting is used, a compound having at least two isocyanate groups is added to the silicone compound (A) to obtain a terminal isocyanate type prepolymer. Even if it is used in excess, the weight ratio of the silicone compound (A) becomes a considerably large value, so that the use of a solvent is indispensable for carrying out a uniform and complete reaction.

As a solvent which is inactive to isocyanate groups and capable of dissolving polyurethane, monochlorobenzene,
Aromatic halides such as dichlorobenzene, esters such as methyl isobutyl acetate and methoxybutyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, dibutyl ether, dioxane, anisole, methoxytoluene, propylene glycol dimethyl ether, ethers such as diethylene glycol dimethyl ether. The kind is illustrated.

In the presence of such a solvent, in order to produce an isocyanate type prepolymer by using an excess of a compound having at least two isocyanate groups with respect to the silicone compound (A), the silicone compound (A ) To a molar ratio of 1.2 or higher and a temperature of 5
Heat reaction at 0 ° C or higher.

Then, the prepolymer solution thus obtained is used as a part of the compound having at least two isocyanate groups after distilling off the solvent, and at least 2
It is possible to produce a silicone-modified polyurethane by reacting with a so-called polyol compound having a number of hydroxyl groups, and without distilling the solvent, a solvent is obtained after reacting with a separately produced polyol type urethane prepolymer. It is also possible to obtain a silicone-modified polyurethane by distilling off.

The silicone-modified polyurethane obtained as described above is a diisocyanate compound, a triisocyanate compound, a dihydroxy compound, a polyol, a diamine, in the presence of a chain extender or a cross-linking agent such as water, and other polyurethane not silicone-modified. Further, it can be used as a modifier by a method such as a copolyaddition reaction using an extruder, for example.

In the case of a chain extension reaction using a prepolymer during a polyurethane production reaction or a copolyaddition reaction between polyurethanes, a catalyst for promoting the reaction, such as an inorganic acid,
Acid catalysts such as phosphoric acid or boric acid esters or paratoluene sulfonic acid, M-methylmorpholine, triethylamine, N, N-dimethylbenzylamine, N, N'-dimethylpiperazine, triethylenediamine, N, N, N ', N ′
-Tetramethylethylenediamine, N, N, N ', N'-Tetramethylhexamethylenediamine, N, N, N', N ", N"-
Amine catalysts such as pentamethyldiethylenetriamine, hexamethylenetetramine, etc., or cobalt naphthenate, lead naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tri-n-butyltin acetate, trimethyltin hydroxide , Dimethyltin dichloride,
It is common practice to use a metal catalyst such as dibutyltin dilaurate, stannous octylate, tetraoctyl titanate, cobalt octylate, antimony trichloride and the like, and there is no problem in the present invention.

As described in detail above, the silicone-modified polyurethane of the present invention uses a polydiorganosiloxane whose one end is blocked with an organic group having two hydroxyl groups, so that the polydiorganosiloxane chain is branched to the side chain of the polyurethane. With this structure, unlike the case where a polydiorganosiloxane chain is introduced into the main chain of polyurethane to form a block copolymer, the structure based on the polydiorganosiloxane chain does not decrease without lowering the mechanical strength inherent to polyurethane. Friction, water repellency,
It has become possible to impart characteristics such as oil repellency and antithrombogenicity. Furthermore, in this case, the polyorganosiloxane chain branched in the side chain is not reactive because it has a trimethylsiloxane group at one end, and therefore its movement is not restricted and compatibility with the main chain polyurethane is compatible. It is expected that there will be a tendency to move away from the main chain due to the lack of This action is a molded product formed when the silicone-modified polyurethane of the present invention is used as it is or in a blend with a resin such as a polyurethane homopolymer, a film, a coating film, or a molded product formed when used as a binder. It is considered that the polydiorganosiloxane chain appears as a floating phenomenon on the surface of the same as in the case of a mere polymer blend. It is not released as siloxane and the stickiness phenomenon does not occur.

Due to such an effect, in the silicone-modified polyurethane of the present invention, even if the amount of the polydiorganosiloxane blocked at one end with an organic group having two hydroxyl groups used as a modifier is small, the low friction property, In addition to the slipperiness of the surface, the polydiorganosiloxane is sufficiently imparted with the desirable properties.

Since the silicone-modified polyurethane of the present invention has the preferable properties as described above, it is a component of a coating material for release paper as a material for moldings that require low friction, such as a belt for a belt conveyor. As a component of a paint required to have water repellency or oil repellency, a component of a paint for a magnetic tape binder or a back coat, or a molding material in the medical field requiring antithrombogenicity, It can be used.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (1) General formula And 10 parts of a polyorganosiloxane having a molecular weight of about 1000 (n = 9.5), 5 parts of 4,4'-methylenebis (phenylisocyanate) (MDI) was added to 35 parts of a 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 15 parts of the solution of (1) and 83 parts of the solution of (2), 3.8 parts of 1,4-butanediol was added and further used as a catalyst.
1,8-diazabicyclo [5,4,0] -7-undecene (DB
U) was added at 0.05% by weight to MDI and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, further cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating,
Approximately 1 ml of fresh blood was collected, and the time at which blood coagulated was measured at 37 ° C. The results are shown in Table 1.

Example 2 (1) General formula And 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI) is added to 10 parts of polyorganosiloxane having a molecular weight of about 5000 (n = 64.3) in 26 parts of 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 5.5 parts of the solution of (1) and 83 parts of the solution of (2), 3.4 parts of 1,4-butanediol was added, and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. -Undecen (D.
BU) was added to MDI in an amount of 0.05% by weight and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating was performed, and about 1 ml of fresh blood immediately after blood collection was added, and the time for blood coagulation was measured at 37 ° C. The results are shown in Table 1.

Example 3 (1) General formula And 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI) is added to 10 parts of polyorganosiloxane having a molecular weight of about 5000 (n = 64.3) in 26 parts of 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 5.5 parts of the solution of (1) and 43 parts of the solution of (2), 1.6 parts of 1,4-butanediol was added, and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. -Undecen (D.
BU) was added to MDI in an amount of 0.05% by weight and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating was performed, and about 1 ml of fresh blood immediately after blood collection was added, and the time for blood coagulation was measured at 37 ° C. The results are shown in Table 1.

Example 4 (1) General formula And 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI) is added to 10 parts of polyorganosiloxane having a molecular weight of about 5000 (n = 64.3) in 26 parts of 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) 0.8 part of 1,4-butanediol was added to a mixed solution of 5.2 parts of the solution of (1) and 19 parts of the solution of (2), and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. -Undecen (D.
BU) was added to MDI in an amount of 0.05% by weight and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating was performed, and about 1 ml of fresh blood immediately after blood collection was added, and the time for blood coagulation was measured at 37 ° C. The results are shown in Table 1.

Example 5 (1) General formula The polyorganosiloxane having a molecular weight of about 10,000 (n = 132.8) is added with 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI), and 1,4-
Heated at 80 ° C. for 1 hour in 49 parts of dioxane solvent.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 10.5 parts of the solution of (1) and 86.3 parts of the solution of (2), 3.2 parts of 1,4-butanediol was added, and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. Undecene (DBU) was added at 0.05% by weight to MDI and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating was performed, and about 1 ml of fresh blood immediately after blood collection was added, and the time for blood coagulation was measured at 37 ° C. The results are shown in Table 1.

Comparative Example 1 (1) General formula And 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI) is added to 10 parts of polyorganosiloxane having a molecular weight of about 5000 (n = 64.9) in 26 parts of 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 5.5 parts of the solution of (1) and 43 parts of the solution of (2), 1.6 parts of 1,4-butanediol was added, and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. -Undecen (D.
BU) was added to MDI in an amount of 0.05% by weight and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, further cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating,
Approximately 1 ml of fresh blood was collected, and the time at which blood coagulated was measured at 37 ° C. The results are shown in Table 1.

Comparative Example 2 (1) General formula And 1 part of 4,4'-methylenebis (phenylisocyanate) (MDI) is added to 10 parts of polyorganosiloxane having a molecular weight of about 5000 (n = 64.7) in 26 parts of 1,4-dioxane solvent. Heat at 80 ° C. for 1 hour.

(2) Polytetramethylene ether glycol (PTMG) with a molecular weight of about 2000 was added to 5 parts of MDI in 20 parts of 1,4-dioxane solvent in a reactor different from that of (1) at 80 ° C.
Heated for hours.

(3) To a mixed solution of 5.5 parts of the solution of (1) and 43 parts of the solution of (2), 1.6 parts of 1,4-butanediol was added, and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst. -Undecen (D.
BU) was added to MDI in an amount of 0.05% by weight and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, further cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating,
Approximately 1 ml of fresh blood was collected, and the time at which blood coagulated was measured at 37 ° C. The results are shown in Table 1.

Comparative Example 3 (1) Polytetramethylene ether glycol (PTM
G) With a molecular weight of about 2000, 5 parts of MDI was added to 20 parts, and the mixture was heated in 58 parts of a 1,4-dioxane solvent at 80 ° C. for 1 hour.

0.9 part of 1,4-butanediol was added to 25 parts of the solution of (1), and 1,8-diazabicyclo [5,4,0] -7 was added as a catalyst.
Undecene (DBU) was added at 0.05% by weight to MDI and heated at 80 ° C. for 1 hour.

This reaction liquid was transferred to a large amount of water to precipitate a polymer, which was thoroughly washed with water, dried and then washed with ethanol to obtain a silicone-modified polyurethane of the present invention.

The mechanical properties were measured by pressing this polymer, further cutting out a dumbbell, and using an autograph. Next, the antithrombotic property was measured by using a polymer solution (solid content concentration 5%) in which the inner wall of a test tube having an inner diameter of 10 mm and a length of 100 mm was dissolved in a mixed solvent of 1,4-dioxane / MEK = 7/3. Coating,
Approximately 1 ml of fresh blood was collected, and the time at which blood coagulated was measured at 37 ° C. The results are shown in Table 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 63-161013 (JP, A) JP 62-225516 (JP, A) JP 63-83121 (JP, A) JP 62- 218471 (JP, A) JP 62-202786 (JP, A)

Claims (2)

(57) [Claims] 1. A polyurethane obtained from a compound having at least two isocyanate groups and a compound having at least two hydroxyl groups, which is used as a part of the hydroxyl group-containing compound in the reaction for forming a urethane bond. , The following general formula (A) (Wherein R is H, Me or Et, Me is a methyl group, Et is an ethyl group, and n is 0 to 4000), and a silicone compound represented by the following formula is used. Method for producing polyurethane. 2. As the silicone compound of the general formula (A),
The method for producing a silicone-modified polyurethane according to claim 1, wherein the value of n is 3 to 600.