JP2014193945A - Polyol mixture and method for producing polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a polyurethane which has high peelability and excellent homogeneity and less coloration and is extremely useful for applications such as an elastic fiber, a film and clothes, and to provide a polyol mixture having excellent homogeneity and high transparency.SOLUTION: There is provided a method for producing a polyurethane in which a polysiloxane polyol (a) is produced by reacting a polysiloxane polyol (i), a polyether polyol (ii) and an isocyanate compound (iii), followed by reacting the polysiloxane polyol (a), a polyol (b) other than the (A) and an isocyanate compound (c).

Description

  The present invention relates to a polyol mixture and a process for producing polyurethane.

  Polyurethane and polyurethane urea are applied in various fields, and among them, they are often used for applications such as elastic fibers. In particular, a fiber having a polyether urethane urea structure has a high cohesive force due to the use of a polyamine compound as a chain extender, and has excellent elastic properties and stretch recovery properties.

  However, polyurethane-based elastic fibers such as polyurethane and polyurethaneurea have high adhesiveness between the fibers, so that the unwinding property at the time of spinning is poor. Further, since the frictional resistance is large, problems such as yarn breakage are likely to occur in devices in the processing process such as a spinning machine, a warping machine, a knitting machine, and a guide, which are in contact with the yarn.

  Therefore, as a means of solving such problems by reducing the frictional resistance between the processing equipment and the yarn, polyurethane-based elasticity using solid metal soap, oil-soluble polymer, higher fatty acid and amino-modified silicone as an oil agent A method of adding to fiber, a method of dispersing talc, silica, colloidal alumina, titanium oxide, etc. as a smoothing agent in polyurethane elastic fiber, a method of introducing silicon diol or silicon diamine into a part of the polyurethane main chain, etc. are studied. (Patent Document 1).

  However, even with these methods, there are problems that a sufficient anti-adhesion effect cannot be obtained, and that the smoothing agent causes significant wear on the spinning machine, warping machine, knitting machine, guide and the like.

  Also, the oligomers in the yarn extracted by the oil component in the warping and knitting process, or the solid or high-viscosity component in the oil separated as a solid or paste, such as fibers, spinning machines, warping Since a large amount adheres to a machine, a knitting machine, a guide, etc., there is a problem of causing product fouling and clogging of machines and instruments, and the problem has not been solved.

  For this reason, there has been a demand for a method for producing a polyurethane having a low unstickiness and a high unwinding property during spinning, that is, a polyurethane having a high peelability, without using the oil agent and the smoothing agent.

  For example, many examples of improving the properties of polyurethane by using polysiloxane polyol as a raw material of polyurethane have been reported so far. For example, a thermoplastic polyurethane having a high rebound resilience using a modified polysiloxane diol (Patent Document 2), a polyurethane elastic fiber having a soft and good wearing feeling using a ether-modified silicone (Patent Document 3), carvone Examples thereof include polyurethane (Patent Document 4) excellent in transparency and smoothness using polyether-modified silicone obtained by modifying acid-modified silicone with polyether polyol.

  However, the thermoplastic polyurethane described in Patent Document 2 has a problem that the flexibility and transparency of the polyurethane molded product are insufficient because the amount of the modified polysiloxane diol used relative to other polyols is large.

In addition, the method described in Patent Document 3 has a problem that the ether-modified silicone easily falls off from the fiber surface because an ether-modified silicone is added to the obtained polyurethane fiber after the polyurethane is produced. Furthermore, even when the ether-modified silicone is allowed to react during the production of polyurethane, there is a problem that the compatibility with other polyols is insufficient and a homogeneous polyurethane is difficult to produce.

  The method described in Patent Document 4 describes that a polyurethane having excellent compatibility and smoothness can be produced by using polyether-modified silicone as a raw material for polyurethane.

Japanese Patent Laid-Open No. 10-259577 JP 2004-250683 A JP 2004-332126 A JP 2011-174037 A

As a result of investigation by the present inventors, the unsaturated carboxylic acid contained in the polyether-modified silicone described in Patent Document 4 causes coloring during urethanization, and the reaction between the unsaturated carboxylic acid and the polyether. It became clear that the unsaturated monool produced by the above method becomes a terminal blocker and inhibits the urethanization reaction, resulting in poor production efficiency of polyurethane. The unsaturated carboxylic acid is produced as a by-product in the process for producing a carboxylic acid-modified silicone as a polyether-modified silicone raw material.
In view of the present situation, the present invention is a method for efficiently producing polyurethane that is highly peelable and excellent in homogeneity, less colored, and extremely useful for applications such as elastic fibers, films, and clothing, and excellent in homogeneity. An object of the present invention is to provide a highly transparent polyol mixture.

  As a result of intensive studies to solve the above problems, the present inventors obtained a polysiloxane polyol (a) by reacting a polysiloxane polyol (i) and a polyether polyol (ii) with an isocyanate compound (iii). Then, by reacting the polyol (b) other than the polysiloxane polyol (a) and (a) with the raw material containing the isocyanate compound (c), the release property is high, the uniformity is excellent, the coloring is small, and the elastic fiber. The inventors have found that polyurethanes that are extremely useful for applications such as films and clothing can be efficiently produced, and have completed the present invention.

（ｎは１以上の整数を示す。）
［７］ ポリエーテルポリオール（ｉｉ）がポリアルキレンエーテルグリコールである［１］〜［６］に記載のポリウレタンの製造方法。
［８］ イソシアネート化合物（ｉｉｉ）が芳香族ポリイソシアネート化合物である［１］〜［７］に記載のポリウレタンの製造方法。
［９］ ポリウレタン中のポリシロキサン部位の重量割合が、前記ポリシロキサンポリオール（ａ）と前記（ａ）以外のポリオール（ｂ）の合計量に対して０．１〜５重量％である［１］〜［８］に記載のポリウレタンの製造方法。
［１０］ （ａ）以外のポリオール（ｂ）が、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールから選ばれる１種である［１］〜［９］に記載のポリウレタンの製造方法。
［１１］ イソシアネート化合物（ｃ）が芳香族ポリイソシアネート化合物である［１］〜［１０］に記載のポリウレタンの製造方法。
［１２］ ポリシロキサンポリオール（ｉ）と、ポリエーテルポリオール（ｉｉ）とがポリイソシアネート化合物（ｉｉｉ）で連結したポリシロキサンポリオール（ａ）および（ａ）以外のポリオール（ｂ）が含まれるポリオール混合物であって、ポリシロキサンポリオール（ａ）および（ａ）以外のポリオール（ｂ）の合計重量に対するポリシロキサン部位の重量割合が０．１〜５．０重量％であるポリオール混合物。
［１３］ ポリシロキサンポリオール（ａ）および（ａ）以外のポリオール（ｂ）の合計重量に対して、ポリシロキサンポリオール（ａ）の重量割合が、３〜５０重量％である［１２］に記載のポリオール混合物。
［１４］ ［１］〜［１１］に記載のポリウレタンの製造方法により得られるポリウレタン。
［１５］ ［１４］に記載のポリウレタンを含む弾性繊維。
［１６］ ［１４］に記載のポリウレタンを含むコーティング組成物。
［１７］ ［１４］に記載のポリウレタンを含む合成皮革又は人工皮革。 That is, the gist of the present invention is as follows.
[1] After the polysiloxane polyol (a) is produced by reacting the polysiloxane polyol (i), the polyether polyol (ii) and the isocyanate compound (iii), other than the polysiloxane polyol (a) and (a) A method for producing polyurethane, in which a polyol (b) and an isocyanate compound (c) are reacted.
[2] In the polysiloxane polyol (i), polyoxyalkylene alkyl ether groups having a structure of —R ₁ —O— (R ₂ —O) _m —H are linked to both ends of the polysiloxane skeleton [ [1] A process for producing a polyurethane as described in [1]. (R ₁ is an alkylene group having 1 to 15 carbon atoms, R ₂ is an alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 50)
[3] The polysiloxane polyol (a) is produced by reacting the polysiloxane polyol (i) with the isocyanate compound (iii) and then reacting the polyether polyol (ii) [1] or [2 ] The manufacturing method of the polyurethane as described in a.
[4] The method for producing a polyurethane according to [1] to [3], including a step of obtaining a mixed liquid containing at least a polyol (b) other than the polysiloxane polyol (a) and (a).
[5] The method for producing a polyurethane according to [4], comprising a step of reacting the mixed solution and the isocyanate compound (c) to obtain a prepolymer having isocyanate groups at both ends.
[6] The method for producing a polyurethane according to [1] to [5], wherein the polysiloxane polyol (i) is a compound represented by the structure of the following formula (1).

(N represents an integer of 1 or more.)
[7] The method for producing a polyurethane according to [1] to [6], wherein the polyether polyol (ii) is a polyalkylene ether glycol.
[8] The method for producing a polyurethane according to [1] to [7], wherein the isocyanate compound (iii) is an aromatic polyisocyanate compound.
[9] The weight ratio of the polysiloxane moiety in the polyurethane is 0.1 to 5% by weight based on the total amount of the polysiloxane polyol (a) and the polyol (b) other than (a) [1]. -The manufacturing method of the polyurethane as described in [8].
[10] The method for producing a polyurethane according to [1] to [9], wherein the polyol (b) other than (a) is one selected from polyether polyol, polyester polyol, and polycarbonate polyol.
[11] The method for producing a polyurethane according to [1] to [10], wherein the isocyanate compound (c) is an aromatic polyisocyanate compound.
[12] A polyol mixture containing a polysiloxane polyol (a) in which a polysiloxane polyol (i) and a polyether polyol (ii) are linked by a polyisocyanate compound (iii) and a polyol (b) other than (a). A polyol mixture in which the weight ratio of the polysiloxane moiety to the total weight of the polyol (b) other than the polysiloxane polyols (a) and (a) is 0.1 to 5.0% by weight.
[13] The weight ratio of the polysiloxane polyol (a) is 3 to 50% by weight with respect to the total weight of the polyol (b) other than the polysiloxane polyols (a) and (a). Polyol mixture.
[14] A polyurethane obtained by the method for producing a polyurethane according to [1] to [11].
[15] An elastic fiber comprising the polyurethane according to [14].
[16] A coating composition comprising the polyurethane according to [14].
[17] A synthetic leather or artificial leather comprising the polyurethane according to [14].

  According to the present invention, the method of efficiently producing polyurethane that is highly peelable and excellent in homogeneity, less colored, and extremely useful for applications such as elastic fibers, films, and clothing, and excellent in homogeneity and high transparency. A polyol mixture can be provided.

  In the following, typical embodiments for carrying out the present invention will be specifically described. However, the embodiments are examples (representative examples) of the embodiments of the present invention, and the present invention is described below unless the gist of the present invention is exceeded. It is not limited to an aspect.

  In the polyurethane of the present invention, the polysiloxane polyol (i), the polyether polyol (ii) and the isocyanate compound (iii) are reacted to produce the polysiloxane polyol (a), and then the polysiloxane polyol (a), (a ) Other than the polyol (b) and the isocyanate compound (c).

In the present invention, unless otherwise specified, polyurethane refers to both polyurethane and polyurethane urea that have been conventionally known to have similar physical properties.

  Here, as structural differences between polyurethane and polyurethane urea, polyurethane is a polymer that mainly forms a chain structure by urethane bonds, and polyurethane urea is a polymer that mainly forms a chain structure by urethane bonds and urea bonds. is there. As a difference from the raw material side, polyurethane is produced using a polyol compound as a chain extender, and polyurethane urea is produced using a polyamine compound as a chain extender.

<Polysiloxane polyol (a)>
The polysiloxane polyol (a) used in the present invention is obtained by reacting with a polysiloxane polyol (i), a polyether polyol (ii) and an isocyanate compound (iii).

The ratio of the polysiloxane moiety in the polysiloxane polyol (a) used in the present invention is not particularly limited, but the lower limit is usually 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight. %, More preferably 20% by weight or more, while the upper limit is usually 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, still more preferably 60% by weight or less, particularly preferably 50% by weight. % Or less.
The greater the proportion of the polysiloxane moiety in the polysiloxane polyol (a), the more the release property of the resulting polyurethane tends to improve, and the lower the transparency, the greater the transparency of the polyurethane obtained by improving the compatibility with the polyol (b). And the homogeneity tends to be high. In addition, the ratio of the polysiloxane site | part in polysiloxane polyol (a) is computable by measuring using NMR, for example.

  The number average molecular weight of the polysiloxane polyol (a) is not particularly limited, but the lower limit is usually 500 or more, preferably 1000 or more, more preferably 1800 or more, while the upper limit is usually 6000 or less, preferably It is 5000 or less, more preferably 4500 or less.

  By setting the number average molecular weight to the upper limit or less, the compatibility with the polyol (b) and the solvent used in the production of the polyurethane is improved, and it is easy to produce a homogeneous polyurethane. In addition, when a mixture of polysiloxane polyol (a) and polyol (b) (hereinafter sometimes referred to as a polyol mixture), a prepolymer or a prepolymer solution is formed, their viscosity is prevented from becoming too high. Tend to improve productivity and productivity. By setting it to the lower limit or more, the peelability of the obtained polyurethane polymer can be sufficiently expressed.

  The polysiloxane polyol (a) has a molecular weight of the polysiloxane polyol (a) produced by adjusting the polymerization degree of the polysiloxane polyol (i) and the polyether polyol (ii) according to the physical properties of the target polyurethane resin. It is possible to easily change the weight ratio of the polysiloxane moiety.

  The state of the polysiloxane polyol (a) used in the present invention is not particularly limited. The polysiloxane polyol (a) is usually liquid or waxy at room temperature, but any state can be selected by adding an additive or the like according to the application or form.

The polysiloxane polyol (a) used in the present invention usually has two or more urethane bonds and two or more hydroxyl groups in the molecule. Moreover, it is preferable to have a plurality of ether bonds in the molecule.
In the polysiloxane polyol (a), usually, two or more hydroxyl groups of one molecule of the polysiloxane polyol (i) are composed of at least two molecules of the hydroxyl group of the polyether polyol (ii) and the isocyanate compound (iii). Of the two or more hydroxyl groups possessed by each of the polyether polyols (ii) of at least two molecules bonded together via a urethane bond consisting of a reaction and having two or more urethane bonds in one molecule in total One or more residual hydroxyl groups that do not form urethane bonds have a total of two or more in one molecule.

  The molecular structure of the polysiloxane polyol (a) used in the present invention is not particularly limited as long as a structure derived from the polysiloxane polyol (i), the polyether polyol (ii), and the isocyanate compound (iii) is included.

The polysiloxane polyol (a) used in the present invention has a structure derived from the polysiloxane polyol (i) (referred to as [X]) and a structure derived from the polyether polyol (ii) (referred to as [Y]). Since it is obtained by reacting with an isocyanate compound (iii), it can have a molecular structure of YXY type, XYX type, XXX type, YYY type and XX type, YY type, XY type. Among these, YXY type polysiloxane polyol (a) is preferably used from the viewpoint of compatibility with polyol (b).
In order to preferentially produce the polysiloxane polyol (a) having a YXY structure, the polyether polyol (ii) is obtained by reacting the polysiloxane polyol (i) with the isocyanate compound (iii) to urethanize the hydroxyl group. The method of reacting is preferably used.

  At this time, the molar ratio of the isocyanate compound (iii) used for the reaction with the polysiloxane polyol (i) is preferably 2.0 to 10.0 molar equivalents relative to the polysiloxane polyol (i), 8.0 molar equivalent is more preferable and 2.1-5.0 molar equivalent is still more preferable.

  If the amount of the isocyanate compound (iii) is too small, the production ratio of the YXY type which is a preferred molecular structure may be lowered. If the amount is too large, an undesirable side reaction is likely to occur and the subsequent reaction with the polyether polyol (ii) Occasionally, the YXY type polysiloxane polyol (a) may not be sufficiently obtained.

  The molar ratio of the polyether polyol (ii) is preferably 2.0 to 10.0 molar equivalents, more preferably 2.05 to 8.0 molar equivalents relative to the polysiloxane polyol (i). More preferred is -5.0 molar equivalents.

<Polysiloxane polyol (i)>
The polysiloxane polyol (i) used in the present invention refers to a compound having two or more siloxane moieties and two or more hydroxyl groups.
Specific examples include polyalkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane; and polyarylsiloxanes such as polymethylphenylsiloxane and polydiphenylsiloxane. Among these, polydimethylsiloxane is preferably used from the viewpoint of the flexibility of the urethane obtained.

The polysiloxane polyol (i) is preferably one in which a plurality of polyoxyalkylene alkyl ethers of —R ₁ —O— (R ₂ —O) _m —H are connected to a silicon atom of a polysiloxane skeleton. R ₁ is an alkylene group having 1 to 15 carbon atoms, R ₂ is an alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 50. Among these, polysiloxane polyols in which polyoxyalkylene alkyl ether groups are linked to both ends of the polysiloxane skeleton are more preferably used.

  Moreover, what is marketed may be used for the polysiloxane polyol (i) used in the present invention. For example, carbinol-modified silicones (product names X-22-160AS, KF-6001, KF-6002, KF-6003 etc.) manufactured by Shin-Etsu Chemical Co., Ltd., diol-modified silicones (X-22-176DX, X-22-) 176F, etc.), polyether-modified silicone (X-22-4952, X-22-4272, X-22-6266), carbinol-modified silicone manufactured by Toray Dow Corning Co., Ltd. (product names SF8427, BY16-201, etc.) Etc.

（ｎは１以上の整数を示す。） The polysiloxane polyol (i) in the present invention is particularly preferably a compound represented by the structure of the following formula (1).

(N represents an integer of 1 or more.)

The method for producing the polysiloxane polyol (i) in which both ends of the polysiloxane skeleton are alkylene glycol is not particularly limited as long as it is a known method, but the following methods are exemplified. For example, it can be produced by reacting monoallyl ether such as ethylene glycol or polyoxyalkylene glycol with polydimethylsiloxane as a raw material and hydrosilylating it. In this case, it is necessary to use an excess of monoallyl ether in order to make the hydrosilylation reaction proceed completely, but the excess allyl ether can be easily removed by stripping or the like.
The above method is preferably used from the viewpoint that raw materials that may inhibit the urethanation reaction such as unsaturated carboxylic acid are unnecessary, and that unreacted raw materials hardly remain.

  The polysiloxane polyol (i) used in the present invention needs to have two or more hydroxyl groups, and the number thereof is preferably 3 or less, more preferably 2. When the number of hydroxyl groups is in the above range, it is easy to obtain a polyurethane having a target molecular weight by preventing the polyurethane from becoming highly viscous.

  The position of the hydroxyl group of the polysiloxane polyol (i) used in the present invention is not particularly limited. Examples include those having a hydroxyl group at the side chain of the molecule, those having both ends of the molecule, those having one end and side chain of the molecule, and those having two or more only at one end of the molecule. Among these, a polysiloxane polyol having hydroxyl groups at both ends of the polysiloxane is particularly preferable because a polyurethane having a sufficient molecular weight is easily obtained.

  The polysiloxane polyol (i) used in the present invention preferably has an ether bond outside the polysiloxane skeleton, and more preferably has a plurality of ether bonds outside the polysiloxane skeleton. The position of the ether bond in the molecule is not particularly limited, but it is preferable to have ether bonds at both ends of the linear polysiloxane polyol. In order to improve the compatibility of the polysiloxane polyol (a), a larger number of ether bonds tends to be preferable, but the compatibility is determined by the molecular weight of the polyether polyol (ii) linked to the polysiloxane polyol (i). It can be adjusted. The optimum number of ether bonds is not specified, but 1 to 50 is preferable.

  The number average molecular weight of the polysiloxane polyol (i) used in the present invention is not particularly limited, but the lower limit is usually 300 or more, preferably 500 or more, more preferably 700 or more, while the upper limit is Usually, it is 4000 or less, preferably 2000 or less, more preferably 1500 or less.

  When the polysiloxane polyol (i) is produced by reacting with the polyether polyol (ii) or the isocyanate compound (iii) by setting the number average molecular weight of the polysiloxane polyol (i) below the upper limit, the polyether polyol is used. Not only the compatibility with (ii) and the isocyanate compound (iii) is improved and the urethanization reaction proceeds easily, but the compatibility with the polyol (b), chain extender, and solvent used in the production of the polyurethane is deteriorated. This makes it easier to produce a homogeneous polyurethane. In addition, the molecular weight is prevented from becoming too large, and the viscosity when a mixture of polysiloxane polyol (a) and polyol (b) (hereinafter sometimes referred to as polyol mixture), prepolymer, or prepolymer solution is formed. Suppressing and improving operability and productivity.

  On the other hand, by setting the number average molecular weight of the polysiloxane polyol (i) to be equal to or higher than the lower limit, the polysiloxane moiety content in the polysiloxane polyol (a) is increased and the release property of the resulting polyurethane polymer is sufficiently expressed. Can be made.

  In addition, the state of polysiloxane polyol (i) used in the present invention is not particularly limited. The polysiloxane polyol (i) is usually liquid or waxy at room temperature, but any state can be selected by adding an additive or the like according to the application or form. Usually, it is used in liquid form because of its good handling properties.

<Polyether polyol (ii)>
The polyether polyol (ii) used in the present invention is usually a hydroxy compound having two or more ether bonds in the main skeleton in the molecule. Here, the polyether polyol (ii) does not include a chemical structure corresponding to the polysiloxane polyol (i). The repeating unit in the main skeleton may be either a saturated hydrocarbon or an unsaturated hydrocarbon, and may be linear, branched or cyclic.

  Examples of the repeating unit in the main skeleton in the polyether polyol (ii) include 1,2-ethylene glycol unit, 1,2-propylene glycol unit, 1,3-propanediol (trimethylene glycol) unit, and 2-methyl. 1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 1,4-butanediol (tetramethylene glycol) unit, 2-methyl-1,4-butanediol unit, 3- Methyl-1,4-butanediol unit, 3-methyl-1,5-pentanediol unit, neopentyl glycol unit, 1,6-hexanediol unit, 1,7-heptanediol unit, 1,8-octanediol unit 1,9-nonanediol unit, 1,10-decanediol unit and 1,4-cyclohexa Dimethanol units, and the like. Among these, a polyalkylene ether glycol having a repeating unit having a main chain length of 2 to 12 carbon atoms is preferably used from the viewpoint of the elastic modulus and availability of polyurethane.

  As the polyether polyol (ii), among the polyether polyols having the above repeating unit in the main skeleton, reaction of polytetramethylene ether glycol, polytrimethylene ether glycol, 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran Copolymer polyether polyols obtained by the reaction (for example, product names “PTG-L1000”, “PTG-L2000”, “PTG-L3500”, etc., manufactured by Hodogaya Chemical Co., Ltd.) and copolymers obtained by reaction of neopentyl glycol with tetrahydrofuran Polyether glycol is preferred.

  These polyether polyols (ii) can be used alone or in admixture of two or more, and may be variously selected according to the desired properties of the polyurethane. In order to obtain a homogeneous polyurethane, it is preferable to use the same polyether polyol as the polyol (b) used in the production of the polyurethane.

  The molecular weight of the polyether polyol (ii) used in the present invention is preferably a number average molecular weight of 200 or more, more preferably 300 or more, and even more preferably 500 or more. Further, it is preferably 3,000 or less, more preferably 2,500 or less, and further preferably 2,100 or less.

  By making the number average molecular weight of the polyether polyol (ii) not more than the above upper limit, the viscosity of the resulting polysiloxane polyol (a) is prevented from becoming too high, and the operability and productivity during polyurethane production are improved. Can do. Moreover, it can prevent that the polyether site | part content in polysiloxane polyol (a) becomes high too much, and can fully exhibit the peelability of a polyurethane.

  On the other hand, by setting the number average molecular weight of the polyether polyol (ii) to be the above lower limit or more, the content of the polyether moiety in the polysiloxane polyol becomes sufficient, and the compatibility with the polyol (b) is good, and a homogeneous polyurethane is obtained. Can be generated.

<Isocyanate compound (iii)>
The isocyanate compound (iii) used in the present invention is not particularly limited as long as it has a partial structure of -N = C = O. For example, 2,4- or 2,6-tolylene Aromatic diisocyanates such as isocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, paraphenylene diisocyanate, 1,5-naphthalene diisocyanate and tolidine diisocyanate; α, α, α ′, α ′ -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate; methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate and 1,6 Aliphatic diisocyanates such as hexamethylene diisocyanate; and 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate And alicyclic diisocyanates such as isopropylidene dicyclohexyl-4,4′-diisocyanate, etc., and some of the NCO groups of these isocyanate compounds are urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc. In addition, the polynuclear substance may contain an isomer other than those described above. These may be used alone or in combination of two or more.

In the present invention, aromatic diisocyanates having high reactivity are particularly preferable, and among them, tolylene diisocyanate and diphenylmethane diisocyanate are more preferable.
The polysiloxane polyol (a) may contain a compound other than the polysiloxane polyol (i), the polyether polyol (ii), and the isocyanate compound (iii).

<Method for producing polysiloxane polyol (a)>
The polysiloxane polyol (a) in the present invention can be obtained by reacting the polysiloxane polyol (i), the polyether polyol (ii), and the isocyanate compound (iii). The above reaction is a urethanization reaction with —N═C═O group and hydroxyl group.
<Urethane catalyst>

  Although the urethanization reaction can be carried out in a system in which no urethanization catalyst is present, a urethanization catalyst may be used in order to allow these reactions to proceed smoothly. The catalyst that can be used as the urethanization catalyst is not limited as long as it is a known catalyst that is generally considered to have urethanization ability.

  It should be noted that the catalyst type can be changed or the amount of catalyst used can be changed by the urethanation reaction between the polysiloxane polyol (i) and the isocyanate compound (iii) and the subsequent urethanation reaction with the polyisocyanate compound (iii). Also good.

  Examples of the urethanization catalyst include amine-based catalysts, metal catalysts, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid, and amine-based catalysts and metal catalysts are preferred.

  For example, triethylamine or tributylamine is preferably used as the amine catalyst. Moreover, as a metal catalyst, organic tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dineodecanate, stannous octylate; inorganic tin such as metastannic acid, stannic oxide; Examples thereof include titanium-based catalysts such as tetrabutoxy titanium. Among metal-based catalysts, organotin catalysts are preferable, and dioctyltin dilaurate and dioctyltin dineodecanate are preferably used from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

  In addition, the amount of the urethanization catalyst used at that time varies depending on the type of the catalyst, but in the case of an organotin catalyst, it is usually 10 ppm by weight or more, preferably 30 wt. The lower limit is usually 1000 ppm by weight or less, preferably 500 ppm by weight or less.

  By making the usage-amount of a catalyst more than the said minimum, the time concerning polysiloxane polyol formation can be shortened. Moreover, it can prevent that a catalyst shows the excessive reaction promotion effect | action with respect to a polyurethane-ized reaction by setting it as the said upper limit or less.

  The urethanization catalyst may remain in the polysiloxane polyol (a), but if too much catalyst remains, the urethanization reaction with the isocyanate compound (c) may be accelerated more than expected. There is not preferable. The amount of catalyst remaining in the polysiloxane polyol (a) is usually 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less. The amount of the remaining compound or metal can be measured by a known method.

<Urethaneization reaction>
The polysiloxane polyol (a) in the present invention can be produced by urethanizing the polysiloxane polyol (i), the polyether polyol (ii), and the isocyanate compound (iii). The urethanization reaction may be performed at the same time by mixing the raw materials (i) to (iii) above. However, the polysiloxane polyol (i) is reacted with 2 equivalents or more of the isocyanate compound (iii) to urethanize and be terminated with an isocyanate. It is preferable to produce a polysiloxane polyol (a) by forming a compound having a group and further subjecting this compound to a urethanization reaction with 2 equivalents or more of a polyether polyol (ii).

At this time, when unreacted polyether polyol (ii) remains, it is used as a raw material for the subsequent urethanization reaction in the state of a mixture of polysiloxane polyol (a) and unreacted polyether polyol (ii). May be.

  The reaction temperature of the urethanization reaction in producing the polysiloxane polyol (a) in the present invention is usually preferably 0 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. Moreover, 150 degrees C or less is preferable normally, 100 degrees C or less is more preferable, 90 degrees C or less is still more preferable, and 80 degrees C or less is especially preferable.

  When the reaction temperature is within the above range, polyurethane can be efficiently produced in a short reaction time while suppressing side reactions of the isocyanate compound, and a uniform reaction can be performed by lowering the viscosity of the reaction system.

  The urethanization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. Although the reaction pressure is arbitrary, it can be carried out at normal pressure, slightly elevated pressure or slightly reduced pressure depending on the purpose.

  The reaction time of the urethanization reaction varies depending on the amount of the urethanization catalyst used, the reaction temperature, the substrate to be reacted, the physical properties of the polysiloxane polyol to be produced, etc., but is usually 1 hour or more, preferably 3 hours or more, The upper limit is usually 12 hours or less, preferably 10 hours or less.

<Polyols other than (a) (b)>
The polyol (b) other than (a) used in the present invention is a polyol having a chemical structure that is not the same as the polysiloxane polyol (a). The polyol (b) needs to have a plurality of hydroxyl groups that can be used in the urethanization reaction. Examples include polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols, polythioether polyols, silicon-containing polyols, and phosphorus-containing polyols. These two or more types of mixtures and copolymers can be used.

  Examples of the polyether polyol include the same substances as those described in <Polyether polyol (ii)>.

Polyester polyols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their ester-forming derivatives and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene). Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol 1,6-hexanediol, 2- Til-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2- Aliphatic glycols such as butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol; fats such as bishydroxymethylcyclohexane Cyclic glycols; glycols having aromatic rings such as xylylene glycol and bishydroxyethoxybenzene; those obtained by polycondensation with “alkyl dialkanolamines such as alkyldiethanolamines” having 1 to 18 carbon atoms, such as polyethylene Adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene A polylactone diol obtained by ring-opening polymerization of one or more lactones using the glycols as an initiator, such as polycaprolactone diol, polymethylvalerolactone diol, etc. The terminal is a hydroxyl group.

  Polyether ester polyols include those obtained by reacting a mixture of an ether group-containing diol or other glycol with the dicarboxylic acid or an ester-forming derivative thereof, or by reacting polyester glycol with an alkylene oxide. Among the (polytetramethylene ether) adipate and the like, there may be mentioned those whose both ends are hydroxyl groups.

  Examples of the polycarbonate polyol include those obtained by dealcoholization or deglycolization reaction from the glycol or various polymer diols and dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc., such as poly (1,6-hexylene) carbonate, Among the poly (3-methyl-1,5-pentylene) carbonates and the like, there may be mentioned those whose both ends are hydroxyl groups.

  Examples of the polyolefin polyol include hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and polybutadiene polyol.

  As the polythioether polyol, it is particularly preferable to use thioglycol alone or a condensation product thereof with other glycols.

  Of these, polyether polyol, polyester polyol, and polycarbonate polyol are preferable, polyether polyol is more preferable, and polyalkylene ether glycol is still more preferable.

  These polyols may be used alone or in combination of two or more, and may be variously selected according to the desired physical properties of the polyurethane.

  In order to obtain a homogeneous polyurethane, it is preferable to use, as the polyol (b), the same polyether polyol as the polyether polyol (ii) used in the production of the polysiloxane polyol (a). In particular, polytetramethylene ether glycol, polytrimethylene ether glycol, copolymer polyether polyols obtained by the reaction of 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran (for example, “PTG-L1000” manufactured by Hodogaya Chemical Co., “ PTG-L2000 "and" PTG-L3500 ") and copolymer polyether glycols obtained by the reaction of neopentyl glycol and tetrahydrofuran are preferred.

  The molecular weight of the polyol (b) used in the present invention is preferably a number average molecular weight of 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more. Further, it is preferably 5,000 or less, more preferably 4,000 or less, and further preferably 3,500 or less.

  By making the number average molecular weight of the polyol (b) not more than the above upper limit, in the production of polyurethane described later, a mixture of the above-mentioned polysiloxane polyol (a) and this polyol (b), and a prepolymer produced using the same When forming a prepolymer solution, it is possible to suppress an excessive increase in viscosity, improve operability and productivity, suppress crystal orientation of the resulting polyurethane, and improve elasticity recovery and the like. .

On the other hand, by setting the number average molecular weight of the polyol (b) to be equal to or higher than the lower limit, the obtained polyurethane can be prevented from being hardened, sufficient flexibility can be obtained, and sufficient elastic performance such as strength and elongation can be obtained. It is done.

  The amount of polysiloxane polyol (a) and polyol (b) used is not particularly limited, but the amount of polysiloxane polyol (a) is based on the total weight of polysiloxane polyol (a) and polyol (b). The amount used is usually preferably 0.5% by weight or more, more preferably 1% by weight or more, while the upper limit is usually preferably 30% by weight or less, and 25% by weight or less. Is more preferable, and it is still more preferable that it is 20 weight% or less.

  By making the usage-amount of polysiloxane polyol (a) more than the said minimum, it becomes the tendency for the peelability of the polyurethane obtained to improve. When the amount used is less than or equal to the above upper limit, the elastic properties and stretch recovery properties of the resulting polyurethane tend to be improved.

  When the polyether polyol (ii) remaining as an unreacted product when the polysiloxane polyol (a) is produced is used as a part of the polyol (b) during the polyurethane production, the polyether polyol remaining as an unreacted product is used. The amount of (ii) shall be included in the amount of polyol (b) used.

<Isocyanate compound (c)>
The isocyanate compound (c) used in the present invention is not particularly limited as long as it has a partial structure of -N = C = O. For example, the isocyanate compound described in <isocyanate compound (iii)> mentioned above is mentioned.

  Among them, aromatic diisocyanates having high reactivity are particularly preferable, and tolylene diisocyanate and diphenylmethane diisocyanate are particularly preferable. Moreover, in order to improve the transparency of the obtained polyurethane, it is more preferable that the isocyanate compound is the same as the isocyanate compound (iii) used when the polysiloxane polyol (a) is produced.

  The amount of these isocyanate compounds (c) used is the sum of the hydroxyl groups of the polysiloxane polyol (a) and polyol (b), and, when a chain extender is used, the hydroxyl group and / or amino group. 0.1 to 5 molar equivalents, preferably 0.8 to 2 molar equivalents, more preferably 0.9 to 1.5 molar equivalents, still more preferably 0.95 to 1.1 molar equivalents, relative to molar equivalents, Particularly preferred is 0.98 to 0.99 molar equivalent.

  By making the usage-amount of an isocyanate compound into the said range, it exists in the tendency which prevents that an unreacted isocyanate group raise | generates an unfavorable reaction and obtains a desired physical property easily. In addition, the molecular weight of polyurethane and polyurethane urea can be sufficiently increased, and the effects of the present invention tend to be easily exhibited.

<Chain extender>
In the present invention, a chain extender may be used as necessary. Chain extenders are mainly classified into compounds having two or more hydroxyl groups (excluding polysiloxane polyol (a) and polyol (b)), and compounds having two or more amino groups. In the production of polyurethane, a polyol having 2 to 6 carbon atoms, specifically, a compound having two or more hydroxyl groups is preferred. For the production of polyurethane urea, polyamine compounds are generally used, and specifically, compounds having two or more amino groups are preferred.

In the polyurethane of the present invention, when a compound having a molecular weight (number average molecular weight) of 500 or less is used in combination as a chain extender, the rubber elasticity of the polyurethane is improved. These chain extenders may be used alone or in combination of two or more.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, 2-methyl- 2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,2-butanediol, 1, 3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2, 2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1 6-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol and 1,9 -Aliphatic glycols such as nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; and glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene. Among these, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferable.

  Examples of the compound having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine, and 4,4′-diphenylmethanediamine; ethylenediamine, 1, 2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-pentanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine , Aliphatic diamines such as 1,6-hexanediamine, 2,2,4- or 2,4,4-trimethylhexanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmeta Diamine (hydrogenated MDA), isopropylidene cyclohexyl-4,4'-diamine, alicyclic diamine such as 1,4-diaminocyclohexane and 1,3-bis-aminomethyl cyclohexane. Among these, ethylenediamine, propylenediamine, 1,3-pentanediamine and 2-methyl-1,5-pentanediamine are preferable.

  When these chain extenders are used, the amount used is 1 mol of the absolute value of the equivalent of the isocyanate compound (c) minus the total hydroxyl equivalent of the polysiloxane polyol (a) and polyol (b). When it is defined as equivalent, it is usually preferably 0.1 to 5.0 molar equivalent, more preferably 0.5 to 2.0 molar equivalent, and 0.7 to 1.5 molar equivalent. More preferred is 0.8 to 1.2 molar equivalents.

  By setting the amount of the chain extender within the above range, it is possible to prevent the unreacted chain extender from remaining in the obtained polyurethane and polyurethane urea, and to cause side reactions of the unreacted chain extender and bleed out after processing. There is a tendency to be able to suppress such. Moreover, sufficient strength, elastic recovery performance and elastic retention performance can be obtained without the polyurethane obtained being too soft, and good high temperature characteristics tend to be obtained.

<Solvent>
In the present invention, a solvent may be used as necessary. Solvents used are amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide and mixtures of two or more thereof from the viewpoint of versatility and solubility; N-methylpyrrolidone, N-ethyl A solvent selected from the group consisting of pyrrolidone and dimethyl sulfoxide is preferably used, and among these, N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable.

<Other additives>
In the production method of the polyurethane of the present invention, a chain terminator, an antioxidant, a light stabilizer, an ultraviolet absorber, a reactive flame retardant, a colorant, a hydrolysis inhibitor, a filler, a lubricant, an oil, Additives such as surfactants and inorganic extenders can be added.

For example, aliphatic monoamines such as methanol, ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine and morpholine having an amino group Stopper; “CYANOX1790” (manufactured by Cyanamid),
Antioxidation of “IRGANOX245”, “IRGANOX1010” (manufactured by Ciba Specialty Chemicals), “Sumilizer GA-80” (manufactured by Sumitomo Chemical), 2,6-dibutyl-4-methylphenol (BHT), etc. Light stabilizers such as “TINUVIN622LD”, “TINUVIN765” (manufactured by Ciba Specialty Chemicals), “SANOL LS-2626” and “SANOL LS-765” (manufactured by Sankyo), “TINUVIN328 ”And“ TINUVIN234 ”(manufactured by Ciba Specialty Chemicals), silicon compounds such as dimethylsiloxane polyoxyalkylene copolymer, red phosphorus, organic phosphorus compounds, phosphorus and halogen-containing organic compounds, Contains bromine or chlorine Addition of organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc. and reactive flame retardants, pigments such as titanium dioxide, dyes, colorants such as carbon black, hydrolysis inhibitors such as carbodiimide compounds, short glass fibers , Carbon fiber, alumina, talc, graphite, melamine, clay, fillers, lubricants, oils, surfactants, and other inorganic extenders. These may be used alone or in combination.

<Production method of polyurethane>
In the present invention, a polyurethane is obtained by reacting the polysiloxane polyol (a), the polyol (b), and the isocyanate compound (c). Each raw material can be used in the amounts described above and can be carried out in the absence of a solvent or in the presence of a solvent by a known production method.

  In the present invention, the ratio of the raw materials for producing the polyurethane is usually the total number of moles of hydroxyl groups of the polysiloxane polyol (a) and the polyol (b) is A, and the number of moles of isocyanate groups of the isocyanate compound (c). Is preferably in the range of 1: 1 to 1:10, more preferably in the range of 1: 1.05 to 1: 5, and 1: 1.1 Is more preferably in the range of ˜1: 3, particularly preferably in the range of 1: 1.2 to 1: 2.5, most preferably in the range of 1: 1.2 to 1: 2. .

  As an example of the production method, the method (a), the method (b), the method (c) and, if necessary, a chain extender are reacted together (hereinafter referred to as a one-step method). (B) is mixed, the mixture and the above (c) are reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer and, if necessary, a chain extender are reacted (hereinafter referred to as “a”). (Referred to as a two-stage method), a method in which (b) and (c) are reacted and then (a) is mixed and, if necessary, reacted with a chain extender, (b), (c) and A method of mixing the above (a) after reacting with a chain extender if necessary, a mixture of (b) after reacting (a) and (c), and optionally a chain extender A reaction with (a), (c) and, if necessary, a chain extender. A method of mixing said (b) are mentioned in the after.

Among these, the two-stage method prepares an intermediate sealed with isocyanate at both ends corresponding to the soft segment of polyurethane by reacting polyol (b) with an isocyanate compound (c) exceeding 1 molar equivalent in advance. It goes through a process. The two-stage method is characterized in that the molecular weight of the soft segment portion can be easily adjusted by preparing a prepolymer once and then reacting it with a chain extender.

  In particular, when the chain extender is a diamine, the reaction rate with the isocyanate group is much higher than the hydroxyl group of the polyol such as (a) or (b), so that the structure design and the molecular weight adjustment can be achieved by the one-step method. It may be difficult to carry out, and it is preferable to produce polyurethane urea by a two-stage method.

  Also, after reacting the mixture of (a) and (b) and (c) to prepare a prepolymer having isocyanate groups at both ends, the polyurethane is reacted with the prepolymer and, if necessary, a chain extender. In the production method, since the polysiloxane polyol (a) is incorporated in the molecular structure of the polyurethane, the polysiloxane polyol is difficult to bleed out (separate and precipitate) in the polyurethane molding step, and the peelability of the formed polyurethane molded product is not impaired. Therefore, it is preferably used.

  The method for producing the polyol mixture with the polysiloxane polyol (a) and the polyol (b) is not particularly limited, but when both the polysiloxane polyol (a) and the polyol (b) are in liquid form, they are stirred. It is preferable to mix them. Moreover, when one or both is a solid or a highly viscous liquid, it can be heated and mixed as a liquid having a low viscosity.

  Although the temperature at the time of mixing a polysiloxane polyol (a) and a polyol (b) is not limited, It is preferable to mix at 10-110 degreeC. By mixing the polysiloxane polyol (a) and the polyol (b) in the above temperature range, it is possible to prevent the polyol mixture from being colored and to prevent the polyol mixture from partially solidifying and to improve the working efficiency. At the same time, non-uniform mixing is prevented, and polyurethane having excellent peelability and homogeneity tends to be stably produced.

  If the polyol mixture is prepared in advance, the compatibility between the polysiloxane polyol (a) and the polyol (b) is good. Therefore, even when the mixture is stored for a long period of time, the phase separation is performed. This is a preferred embodiment because it is difficult to cause.

  Further, when the polyol mixture is produced, the polysiloxane polyol (a) and the polyol (b) may be introduced from separate lines and mixed or dispersed to form a polyol mixture.

  When the polysiloxane polyol (a) and the polyol (b) are introduced from separate lines, the production of the present invention can be achieved by simply adding a tank and a feed line for the polysiloxane polyol (a) of the present invention to an ordinary polyurethane production facility. The polyurethane obtained by the method can be produced.

  If the polyol mixture is prepared and then introduced into a polyol storage tank of a normal polyurethane production facility, the polysiloxane polyol may be mixed in the production of a normal grade polyurethane, which may impair the homogeneity of the polyurethane.

  In order to efficiently produce the polyurethane obtained by the production method of the present invention in combination with the production of the normal grade polyurethane so as to obtain the desired physical properties, the polysiloxane polyol (a) and the polyol (b ) Are preferably introduced from separate lines.

[One-step method]
The one-stage method is also called a one-shot method, and is a method in which the reaction is carried out by adding together the (a), (b), (c) and, if necessary, a chain extender. In general, it is preferable to react each component at 0 to 250 ° C.

  The reaction temperature varies depending on the amount of solvent, the reactivity of raw materials used, reaction equipment, and the like. If the temperature is too low, the progress of the reaction will be slow, and the solubility of raw materials and polymers will be low, so the productivity will tend to deteriorate.If it is too high, side reactions and polyurethane will tend to decompose. This is not preferable.

  The above reaction may be performed while degassing under reduced pressure.

  In the above reaction, a urethanization catalyst, a stabilizer and the like can be added as necessary. As the catalyst at that time, for example, those described in the above <urethanization catalyst> are used.

  Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, tri (dinonylphenyl) phosphite, and triisooctylphosphine. Such as fights.

[Two-stage method]
The two-stage method is also called a prepolymer method. First, the polysiloxane polyol (a) and the polyether polyol (b) are mixed to produce a prepolymer obtained by reacting the isocyanate compound (c) with the polyol mixture. Next, when both ends of the prepolymer are hydroxyl groups, the prepolymer is subjected to a chain extension reaction using an isocyanate compound as a chain extender. When both ends of the prepolymer are isocyanate groups, a polyhydric alcohol or A chain extension reaction is performed by using an active hydrogen compound component such as an amine compound.

  Among them, a method is useful in which a polyol mixture is reacted with an equivalent amount or more of an isocyanate compound (c) to form a prepolymer having isocyanate groups at both ends, and then a chain extender is allowed to act to obtain a polyurethane.

The method for producing the polyurethane according to the present invention is not particularly limited, but typical methods are described below.
(1) A prepolymer is synthesized by directly reacting an isocyanate compound (c) and a polyol mixture without using a solvent and used as it is.
(2) A prepolymer is synthesized by the method of (1) and then dissolved in a solvent for use.
(3) The isocyanate compound (c) is reacted with the polyol mixture using a solvent from the beginning.

  In the case of (1), in the present invention, when the chain extender is allowed to act, the polyurethane is added to the solvent by a method such as dissolving the chain extender in the solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is preferable to obtain the coexisting form.

  The reaction equivalent ratio of NCO / active hydrogen group (polyol mixture) is usually preferably more than 1, and more preferably 1.05 or more. Moreover, it is usually preferably 10 or less, more preferably 5 or less, and further preferably 3 or less.

By setting the reaction equivalent ratio of NCO / active hydrogen group (polyol mixture) to the lower limit or more, sufficient strength and thermal stability tend to be imparted to the resulting polyurethane. Moreover, by setting it as the said upper limit or less, it exists in the tendency for it to prevent that an excessive isocyanate group raise | generates a side reaction and to obtain the physical property of favorable polyurethane with high flexibility.

  In addition, the amount used in the case of using a chain extender is not particularly limited, but it is usually preferably 0.1 or more and 0.5 or more with respect to the molar equivalent of the isocyanate group contained in the prepolymer. Is more preferable and 0.8 or more is still more preferable. Moreover, it is usually preferably 5.0 or less, more preferably 2.0 or less, and further preferably 1.5 or less.

  By making the usage-amount of a chain extender more than the said minimum, the molecular weight of the obtained polyurethane can fully be improved, and sufficient intensity | strength and thermal stability are obtained. Moreover, by setting it as the said upper limit or less, it can prevent that an excessive chain extender raise | generates a side reaction and the physical-property fall of the polyurethane obtained.

  In the chain extension reaction, it is usually preferable to react each component at -20 to 250 ° C. The reaction temperature varies depending on the amount of the solvent, the reactivity of the raw materials used and the reaction equipment, but is 20 to 250 ° C. when the chain extender is an isocyanate compound or a polyhydric alcohol, and −20 when the chain extender is an amine compound. It is preferable to make it react at -30 degreeC.

  If the temperature of the chain extension reaction is too low, the progress of the reaction is too slow, the viscosity of the reaction solution rises and a heterogeneous reaction is likely to occur, or the solubility of raw materials and polymers tends to be low, resulting in poor productivity. It is in. If it is too high, side reactions and polyurethane decomposition tend to occur. The reaction may be performed while degassing under reduced pressure.

  Moreover, a catalyst, a stabilizer, etc. can also be added for reaction as needed. As the catalyst at that time, for example, those described in <Urethaneization catalyst> are used, and as the stabilizer, those described in <One-stage method> are used.

  However, when the chain extender is highly reactive, such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst. In addition, a monofunctional organic amine and alcohol may coexist during the reaction.

<Physical properties of polyurethane>
Since the polyurethane obtained by the above production method is usually reacted in the presence of a solvent, it is generally obtained in a state dissolved in a solvent, but is not limited in a solution state or a solid state.

  Although the weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the polyurethane obtained by the manufacturing method of this invention changes with uses, 10,000-1 million are preferable normally, 50,000-500,000 are more preferable, 10 10,000 to 400,000 is more preferable, and 150,000 to 300,000 is particularly preferable.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) as a standard of molecular weight distribution is preferably 1.5 to 3.5, and preferably 1.7 to 3 .2 is more preferable, and 1.8 to 3.0 is particularly preferable. The number average molecular weight (Mn) can also be measured by the gel permeation chromatography (GPC) described above.

Moreover, it is so preferable that the peeling strength at the time of film forming of the polyurethane obtained by the manufacturing method of this invention is small. The peel strength after laminating the films and placing a weight of 200 g / cm ² and pressure bonding for 10 minutes at room temperature is usually preferably 50 g / cm or less, more preferably 40 g / cm or less, and more preferably 30 g / cm More preferably, it is not more than cm, and particularly preferably not more than 20 g / cm. By setting the peel strength to the above upper limit or less, the peelability of the polyurethane polymer is improved.

  Furthermore, the contact angle at the time of film forming of the polyurethane obtained by the production method of the present invention is preferably as large as possible. The contact angle is preferably 80 ° or more, more preferably 85 ° or more, still more preferably 90 ° or more, and particularly preferably 95 ° or more. By making the contact angle equal to or greater than the above lower limit, the polyurethane peelability tends to be improved.

  The polyurethane obtained by the above production method preferably has a hard segment content calculated by the method described later of 1 to 20% by weight, based on the total weight of the polyurethane, and 3 to 15% by weight. Is more preferable, 4 to 12% by weight is further preferable, and 5 to 10% by weight is particularly preferable.

  By setting the hard segment amount to be equal to or less than the upper limit, the obtained polyurethane exhibits sufficient flexibility and elastic performance, and is easily dissolved and processed when using a solvent. On the other hand, by setting the hard segment amount to be equal to or more than the lower limit, it is possible to prevent the polyurethane from becoming too soft, to be easily processed, and to obtain sufficient strength and elastic performance.

  In the present invention, the hard segment refers to P.I. J. et al. Based on Flory, Journal of American Chemical Society, 58, 1877-1885 (1936), the weight of the isocyanate and chain extender binding portion relative to the total weight is calculated by the following formula.

Hard segment (%) = [(R−1) (Mdi + Mda) / {Mp + R · Mdi + (
R-1) · Mda}] × 100

here,
R = number of moles of isocyanate compound (c) / (number of moles of hydroxyl group of polyol (b) + number of moles of hydroxyl group of polysiloxane polyol (a))
Mdi = Molecular weight of isocyanate compound (c) Mda = Molecular weight of chain extender Mp = Number average molecular weight of polyol mixture comprising polysiloxane polyol (a) and polyol (b) Polyurethane obtained upon reaction in the presence of a solvent Since the solution is less prone to gelation, has good storage stability such as a small change in viscosity with time, and has low thixotropic properties, it is convenient for processing into a film, fiber or the like.

  The polyurethane concentration of the polyurethane solution is usually preferably 1 to 99% by weight, more preferably 5 to 90% by weight, and more preferably 10 to 70% by weight with respect to the total weight of the solution dissolved in the solvent. More preferably, the content is 15 to 50% by weight.

  By setting the concentration of polyurethane to the above lower limit or more, it is possible to secure the solution viscosity necessary for processing or to improve productivity because it is unnecessary to remove a large amount of solvent when processing the polyurethane solution. it can. On the other hand, by setting it to the upper limit or less, the viscosity of the solution can be suppressed, and the operability and workability can be improved.

In addition, when storing the polyurethane solution for a long time, at room temperature or lower temperature,
It is preferable to store in an inert gas atmosphere such as nitrogen and argon.

  The polyurethane obtained by the production method of the present invention preferably has a specific atomic composition on the surface of the molded body. The lower limit of Si / C, which is the relative abundance ratio of silicon atoms to carbon atoms present on the surface of the molded body, is preferably 0.05 or more, more preferably 0.07 or more, and 0.08 or more. More preferably, it is more preferably 0.09 or more, and particularly preferably 0.11 or more. When the Si / C is less than the lower limit, the polyurethane molded article has insufficient peelability, which tends to be undesirable.

  On the other hand, the upper limit of Si / C is preferably 0.4 or less, more preferably 0.3 or less, further preferably 0.25 or less, and more preferably 0.2 or less. More preferably, it is particularly preferably 0.15 or less. When Si / C exceeds the upper limit, the resulting molded article tends to have low transparency.

  The relative abundance ratio of silicon atoms to carbon atoms existing on the surface of the molded body is measured by ESCA (Electron Spectroscopic for Chemical Analysis) or XPS (X-ray Photoelectron Spectroscopy). Therefore, strictly speaking, the relative abundance ratio of surface atoms defined here is not the ratio of the number of atoms on the outermost surface, but the ratio of the number of atoms existing in a thick portion of the analytical measurement region.

  In addition, the relative abundance ratio of the surface of the molded body is such that the addition amount of the polysiloxane polyol (a) or the polyol (b) is changed, the addition order of the polysiloxane polyol is changed, the content of the polysiloxane moiety or the polyoxyalkylene moiety. It can be adjusted by using polysiloxane polyols having different values.

<Uses of polyurethane>
The polyurethane produced in the present invention and the urethane prepolymer solution can exhibit various characteristics. For example, materials such as resin, rubber, and thermoplastic elastomers, and solid, foam, and liquid properties molded into various shapes, such as fibers, films, paints, adhesives, and functional parts Used in a wide range of fields such as clothing, sanitary goods, packaging, civil engineering, architecture, medical care, automobiles, home appliances and other industrial parts.

  In particular, it is preferable to use as a fiber or a film in order to take advantage of the good peelability of the polyurethane produced in the present invention. These specific uses are preferably used for elastic fibers for clothing, medical, hygiene products, artificial leather, and the like.

<Polyurethane film>
The thickness of the film using the polyurethane of the present invention is not particularly limited, but is usually preferably 10 to 1000 μm, more preferably 10 to 500 μm, and more preferably 10 to 100 μm. Is more preferable. By setting the thickness of the film to the above upper limit or less, the solvent can be easily removed and sufficient flexibility can be obtained. Moreover, by setting it as the said minimum or more, while being hard to form a pinhole, a film cannot block easily and it becomes easy to handle.

  The film using the polyurethane of the present invention can be preferably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. The film may be formed by applying to a support such as cloth or nonwoven fabric. In that case, the thickness may be thinner than 10 μm.

  The production method of the film using the polyurethane of the present invention is not particularly limited, and a conventionally known method can be used. For example, a polyurethane solution is applied to or cast on a support or a release material, and a wet film forming method for extracting a solvent or other soluble substance in a coagulation bath, and a polyurethane solution is applied or cast on a support or a release material. And a dry film-forming method in which the solvent is removed by heating and decompression.

  The support used for forming the film is not particularly limited, and polyethylene film, polypropylene film, polytetrafluoroethylene film, glass, metal, paper or cloth coated with a release agent, and the like are used. The method of application is not particularly limited, and any known method such as knife coater, roll coater, spin coater, and gravure coater may be used.

  The drying temperature can be arbitrarily set depending on the type of solvent, the ability of the dryer, etc., but it is necessary to select a temperature range in which drying is insufficient or rapid desolvation does not occur, and is in the range of room temperature to 300 ° C. It is preferable that the temperature range is 60 ° C to 200 ° C.

<Polyurethane fiber>
The physical properties of the polyurethane film and the fiber have a very good correlation, and the physical property values obtained by a film test or the like often show the same tendency in the fiber. The fiber using the polyurethane of the present invention is excellent in stretch recovery, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, workability and the like.

  The fibers using the polyurethane of the present invention are preferably used for applications such as legs, panties / stockings, diaper covers, paper diapers, sports clothing, underwear, socks, stretch clothing with excellent fashion, swimwear, and leotards. It is done.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. The analysis and measurement in the following examples, reference examples and comparative examples were performed according to the following methods.

<Number average molecular weight of polysiloxane polyol (a)>
When the polyether polyol (ii) has a polysiloxane skeleton and 2 equivalents or more of the polysiloxane polyol (i) having a plurality of ether bonds, the number average molecular weight of the polysiloxane polyol (a) is The molecular weight can be calculated according to the following formula (2). The number average molecular weights of the polysiloxane polyols 1 and 2 used in the examples were calculated by the formula (2).

Formula (2)
Number average molecular weight of polysiloxane polyol (a) = (molecular weight of polysiloxane polyol (i)) + (molecular weight of isocyanate compound (iii)) × 2 + (molecular weight of polyether polyol (ii)) × 2

The content of the polysiloxane polyol (a) in the polysiloxane polyol production liquid was calculated by the following formula (3).
Formula (3)
The number of moles of the raw material polysiloxane polyol (i) is m,
Polysiloxane polyol content (% by weight) =
(Number average molecular weight of polysiloxane polyol (a) × m) / polysiloxane polyol (
a) Total amount of raw materials used during the reaction (g)

<Polysiloxane part ratio in polysiloxane polyol (a)>
The ratio of the siloxane chain site contained in the polysiloxane polyol (a) in this example was calculated as follows.
Polysiloxane polyol ratio (%) in polysiloxane polyol (a) = (number average molecular weight of polysiloxane polyol (a)) − (molecular weight of terminal sites bonded to silicon atoms of polysiloxane skeleton of polysiloxane polyol (i) + Number average molecular weight of polyether polyol (ii) x 2 + molecular weight of isocyanate compound (iii) x 2)) / number average molecular weight of polysiloxane polyol (a) x 100
The terminal site bonded to the silicon atom of the polysiloxane skeleton of the polysiloxane polyol (i) indicates a terminal group such as a polyoxyalkylene ether group bonded to the polysiloxane skeleton.
For example, the molecular weight of the terminal portion of the compound represented by the following formula (1) was calculated as C ₁₀ H ₂₂ O ₄ : 206.3.

<Number average molecular weight of polyether polyol (ii) and polyol (b)>
The number average molecular weight (Mn) was determined by a hydroxyl value (KOH (mg) / g) measurement method by an acetylation method based on JIS K1557-1: 2007.

<Molecular weight of polyurethane and polyurethane urea>
The molecular weight of the obtained polyurethane or polyurethane urea was prepared by preparing a dimethylacetamide solution of polyurethane or polyurethane urea, and using a GPC apparatus [manufactured by Tosoh Corporation, product name “HLC-8220” (column: Tskel GMH-XL (2 pieces)]. The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Transparency test method>
According to JIS-K0101 (“industrial water test method”), kaolin is added to 1 L of purified water at 5 mg, 10 mg, 20 mg, 30 mg, 40 mg, 50 mg, 60 mg, 70 mg, 80 mg, 90 mg, 100 mg, 200 mg, 300 mg, 400 mg, 500 mg, respectively. This was added to obtain a suspension for measurement. The obtained suspension was transferred to a 50 ml glass screw bottle (SV-50A manufactured by Nidec Science Glass Co., Ltd.), respectively, and the kaolin concentration of the measurement suspension closest to the turbidity of the sample solution contained in the screw bottle (5 for 5 mg) was defined as kaolin turbidity.

<Peel test method>
Two molded films were superposed, two test pieces with a length of 4 cm and a width of 1 cm were punched out, and a superposed portion of 2.5 cm from one end in the length direction was subjected to conditions of a temperature of 25 ° C. and a relative humidity of 50%. Using a tensile tester (“Rheometer NRM-2003J” manufactured by FUDOH) for the test piece to which a pressure of 200 g / cm ² was applied for 10 minutes, the peel strength when the crimped portion was peeled T-shaped at a tensile speed of 300 mm / min. It was measured. The lower this value, the better the peelability.

<Relative abundance ratio (surface atomic composition)>
The relative abundance ratio of silicon atoms to carbon atoms existing on the surface of the polyurethane molded body, that is, the surface atom composition is determined by ESCA (Electron Spectroscopy for ESCA).
(Chemical Analysis) measurement. The measurement was performed using an ULVAC-PHI Co., Ltd. ESCA apparatus “ESCA-5800”. The measurement conditions are as follows.

Excitation X-ray: Monochromatic AlKα ray (1486.7 eV)
・ X-ray output: 14kV, 350W (use neutralization gun to prevent charging)
・ Analysis mode (LENS MODE): 5 (minimum area mode)
・ Aperture number: 5
・ Detection angle (sample normal to detector angle): 45 degrees ・ PassEnergy: 23.5 eV
Charge shift correction: The carbon C1s peak binding energy was adjusted to 235.0 eV.

  The relative abundance ratio of oxygen atoms to carbon atoms was calculated by the following formula.

Relative abundance ratio = (peak area of oxygen O1s / peak corrected relative sensitivity coefficient) / (peak area of carbon C1s / peak corrected relative sensitivity coefficient)

  In addition, the area of each peak is the MultiPak Ver. The smoothing process (9 points) using the Savitzky-Golay algorithm was performed using 8.2C software, and it calculated | required using the background correction of shirley. Binding energy of oxygen atom peak and carbon atom peak used for calculation of relative abundance ratio and MultiPak Ver. The correction sensitivity coefficients used in the 8.2C software are as follows.

O1s: binding energy = around 532.5 eV,
-Corrected relative sensitivity coefficient = 13.118
C1s: binding energy = around 285.0 eV,
Corrected relative sensitivity coefficient = 5.220

  Regarding the peak area of carbon C1s, it is derived from the shape of the benzene ring shale up obtained by connecting the local minimum values around 280 eV and 290.5 eV with shirley and the local minimum values near 290.5 eV and 293 eV with shirley. What added the area of the peak (near 291-293 eV) was used.

<Production of polysiloxane polyol (a)>
<Production of polysiloxane polyol 1>
In a 1 L separable flask, 20.0 g (0.022 mmol) of a carbinol-modified silicone (manufactured by Toray Dow Corning, “X-22-160AS”, number average molecular weight 930) as an polysiloxane polyol (i), an isocyanate compound After adding 16.2 g (0.065 mmol) of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) previously heated to 40 ° C. as (iii), the flask was heated to 45 ° C. The oil bath was set in an oil bath, stirred with a vertical stirring blade in a nitrogen atmosphere, and the temperature of the oil bath was raised to 70 ° C. over 1 hour, and then maintained at 70 ° C. for 3 hours.
After confirming that the NCO reaction rate exceeds 99% by reacting the residual NCO groups with an excess amount of dibutylamine and then back titrating the residual dibutylamine with hydrochloric acid, as polyether polyol (ii), A state in which 109.1 g (0.108 mmol) of polytetramethylene ether glycol (hereinafter sometimes abbreviated as “PTMG”) (number average molecular weight 1015, manufactured by Mitsubishi Chemical Corporation) was added and further stirred at 70 ° C. for 3 hours. To obtain polysiloxane polyol 1 (polysiloxane polyol (a) content 51.2% by weight, number average molecular weight 3460, polysiloxane part ratio 21% by weight in polysiloxane polyol).

<Production of polysiloxane polyol 2>
Carbinol-modified silicone (Toray Dow Corning, “BY16-201”, number average molecular weight 1860) 100.1 g (0.054 mmol), MDI 51.2 g (0.205 mmol), PTMG 360.7 g (0.355 mmol) Polysiloxane polyol 2 (polysiloxane polyol (a) content 46.1% by weight, number average molecular weight 4390, polysiloxane part ratio in polysiloxane polyol 32% by weight) in the same manner as polysiloxane polyol 1 except that it was used Got.

<Polysiloxane polyol 3>
Carbinol-modified silicone (manufactured by Toray Dow Corning, “X-22-160AS”, number average molecular weight 930) was designated as polysiloxane polyol 3 (polysiloxane moiety ratio in the polysiloxane polyol 79% by weight).

<Production of polysiloxane polyol 4>
Carbinol-modified silicone (manufactured by Dow Corning Toray Co., Ltd., “BY16-201”, number average molecular weight 1860) was designated as polysiloxane polyol 4 (polysiloxane moiety ratio in polysiloxane polyol 87% by weight).

Example 1
Polytetramethylene ether glycol (hereinafter sometimes abbreviated as “PTMG”) as a polysiloxane polyol polyol (b) in a 50 ml glass screw bottle (SV-50A manufactured by Nichiden Science Glass Co., Ltd.) (number average molecular weight 1015, manufactured by Mitsubishi Chemical Corporation) and 1.66 g of polysiloxane polyol 1 synthesized above as polysiloxane polyol (a) were added, and then mixed well with a spatula and allowed to stand at 45 ° C. overnight. To obtain a polyol mixed solution having a polysiloxane site ratio of 0.82% by weight. The kaolin turbidity of the obtained mixed liquid was 5.

Example 2
A mixed liquid having a polysiloxane site ratio of 4.12% by weight was obtained in the same manner as in Example 1 except that 20.0 g of PTMG and 12.41 g of polysiloxane polyol 1 were added. The kaolin turbidity of the obtained mixed liquid was 40.

Example 3
A mixed liquid having a polysiloxane site ratio of 0.7 wt% was obtained in the same manner as in Example 1 except that 20.0 g of PTMG and 0.99 g of polysiloxane polyol 2 were added. The kaolin turbidity of the obtained mixed liquid was 90.

Comparative Example 1
A mixed liquid having a polysiloxane site ratio of 1.0% by weight was obtained in the same manner as in Example 1 except that 20.0 g of PTMG and 0.26 g of polysiloxane polyol 3 were added. The kaolin turbidity of the obtained mixed liquid was 200.

Comparative Example 2
A mixed liquid having a polysiloxane moiety ratio of 5.0% by weight was obtained in the same manner as in Example 1 except that 20.0 g of PTMG and 1.36 g of polysiloxane polyol 3 were added. The kaolin turbidity of the obtained mixed liquid was 300.

Comparative Example 3
A mixed liquid having a polysiloxane site ratio of 1.0 wt% was obtained in the same manner as in Example 1 except that 20.0 g of PTMG and 0.23 g of polysiloxane polyol 4 were added. The kaolin turbidity of the obtained mixed liquid was 300.

<Manufacture of polyurethane urea>
Example 4
<Production of polyurethane urea 1>
Polytetramethylene ether glycol (hereinafter sometimes abbreviated as “PTMG”) preliminarily heated to 40 ° C. as a polyether polyol (b) in a 1 L flask (number average molecular weight 1962, manufactured by Mitsubishi Chemical Corporation) ) 105.1 g and 5.65 g of polysiloxane polyol 1 were added and mixed, and this mixture was used as a raw material for polyurethane production. The proportion of the polysiloxane moiety content in this mixture was 0.78% by weight.

  Thereafter, 22.7 g of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) previously heated to 40 ° C. was added as the isocyanate compound (c). At this time, the reaction equivalent ratio of NCO / active hydrogen group (polysiloxane polyol and polyether polyol) was 1.6.

  The flask was set in a 45 ° C. oil bath, and the temperature of the oil bath was raised to 70 ° C. over 1 hour while stirring with a vertical stirring blade in a nitrogen atmosphere. Held for hours.

  The residual NCO group was reacted with an excess amount of dibutylamine, and then the residual dibutylamine was back titrated with hydrochloric acid to confirm that the NCO reaction rate exceeded 99%. Then, the oil bath was removed, and N , N-dimethylacetamide (hereinafter sometimes abbreviated as “DMAc”, manufactured by Kanto Chemical Co., Inc.) 199.9 g was added, and the mixture was stirred and dissolved at room temperature to prepare a polyurethane prepolymer solution.

  The polyurethane prepolymer solution was cooled and held at 10 ° C., while, as a chain extender, 1.67 g of ethylenediamine (EDA) and 0.53 g of diethylamine (DEA) were dissolved in 212.1 g of DMAc, The above-mentioned polyurethane prepolymer solution in which the DMAc solution was kept cooled at 10 ° C. was added while stirring at high speed. After the addition, a mixed solution of DEA 0.21 g and DMAc 130.9 g was further added while stirring to obtain a polyurethane urea DMAc solution having a polymer concentration of 20% and a kaolin turbidity of 0.

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 1 was measured for weight average molecular weight (Mw) and number average molecular weight (Mn) by GPC, and the weight average molecular weight ( When the ratio (Mw / Mn) to the number average molecular weight (Mn) of Mw) was calculated, Mw was 178,000 and Mw / Mn was 2.7. Moreover, the ratio of the hard segment of the obtained polyurethane urea 1 was 7.9% by weight.

  The polyurethane urea 1 solution thus obtained was cast on a glass plate and dried at 60 ° C. to obtain a colorless and transparent film having a thickness of about 50 μm. When this film was subjected to a peel test, the peel strength was 16 g / cm.

Comparative Example 4
<Production of polyurethane urea 2>
Using polysiloxane polyol 3 as the polysiloxane polyol (a), polyurethane urea 2 was obtained in the same manner as in Example 4 with the raw material compositions listed in Table 3. Polyurethane urea 2 had a kaolin turbidity of 10 and was clearly a turbid solution compared to polyurethane urea 1. Moreover, Mw was 151,000, Mw / Mn was 2.7, and the hard segment amount was 7.9% by weight. Furthermore, when the peel test of the film obtained by carrying out similarly to Example 4 was done, peel strength was 8 g / cm.

Comparative Example 5
<Production of polyurethane urea 3>
A polyurethaneurea 3 was obtained in the same manner as in Example 4 except that the polysiloxane polyol (a) was used and the raw material compositions listed in Table 3. The kaolin turbidity of polyurethane urea 3 was 0. Moreover, Mw was 181,000, Mw / Mn was 2.9, and the hard segment amount was 7.8% by weight. Furthermore, when the peel test of the film obtained by carrying out similarly to Example 4 was done, peel strength was 114 g / cm.

  Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

  According to the present invention, there is provided a production method for efficiently producing a polyurethane having high peelability, excellent homogeneity, little coloring, and extremely useful for applications such as elastic fibers, films and clothing, and a polysiloxane polyol for the raw material. Can be provided.

  And when producing polyurethane molded products such as elastic fibers and films using the obtained polyurethane and polyurethane urea, cost reduction by reducing the amount of oil and smoothing agent used, product fouling and clogging frequency of machinery and equipment It is expected to improve operational stability by reducing power consumption and reduce driving power to be introduced into machines by reducing frictional resistance.

Claims (17)

  After reacting polysiloxane polyol (i), polyether polyol (ii) and isocyanate compound (iii) to produce polysiloxane polyol (a), polyols other than polysiloxane polyol (a) and (a) (b) ), A method for producing polyurethane by reacting the isocyanate compound (c). Polysiloxane polyol (i) is, in claim 1 in which the polyoxyalkylene alkyl ether groups are linked with _{-R 1 -O- (R 2 -O)} m -H in the structure at both ends of the polysiloxane backbone The manufacturing method of the polyurethane of description. (R ₁ is an alkylene group having 1 to 15 carbon atoms, R ₂ is an alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 50)   The production of polyurethane according to 1 or 2, wherein the polysiloxane polyol (a) is produced by reacting the isocyanate compound (iii) with the polysiloxane polyol (i) and then reacting the polyether polyol (ii). Method.   The manufacturing method of the polyurethane of any one of Claims 1-3 including the process of obtaining the liquid mixture containing polyol (b) other than polysiloxane polyol (a) and (a) at least.   The method for producing a polyurethane according to claim 4, comprising a step of reacting the mixed solution with the isocyanate compound (c) to obtain a prepolymer having isocyanate groups at both ends. The method for producing a polyurethane according to any one of claims 1 to 5, wherein the polysiloxane polyol (i) is a compound represented by the structure of the following formula (1).

(N represents an integer of 1 or more.)   The method for producing a polyurethane according to any one of claims 1 to 6, wherein the polyether polyol (ii) is a polyalkylene ether glycol.   The method for producing a polyurethane according to any one of claims 1 to 7, wherein the isocyanate compound (iii) is an aromatic polyisocyanate compound.   The weight ratio of the polysiloxane moiety in the polyurethane is 0.1 to 5% by weight based on the total amount of the polysiloxane polyol (a) and the polyol (b) other than (a). The manufacturing method of the polyurethane of any one.   The method for producing a polyurethane according to any one of claims 1 to 9, wherein the polyol (b) other than (a) is one selected from polyether polyol, polyester polyol, and polycarbonate polyol.   The method for producing a polyurethane according to any one of claims 1 to 10, wherein the isocyanate compound (c) is an aromatic polyisocyanate compound. A polyol mixture comprising a polysiloxane polyol (a) in which a polysiloxane polyol (i) and a polyether polyol (ii) are linked by a polyisocyanate compound (iii) and a polyol (b) other than (a), The polyol mixture whose weight ratio of the polysiloxane site | part with respect to the total weight of polyol (b) other than polysiloxane polyol (a) and (a) is 0.1 to 5.0 weight%.   The polyol mixture according to claim 12, wherein the weight ratio of the polysiloxane polyol (a) is 3 to 50% by weight with respect to the total weight of the polyol (b) other than the polysiloxane polyols (a) and (a).   The polyurethane obtained by the manufacturing method of the polyurethane of any one of Claims 1-11.   An elastic fiber comprising the polyurethane according to claim 14.   A coating composition comprising the polyurethane of claim 14.   A synthetic leather or artificial leather comprising the polyurethane according to claim 14.