JP2011173936A - Polyurethane molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane molded article excellent in peelability and very useful for applications such as an elastic fiber and film and clothing. <P>SOLUTION: The polyurethane molded article is obtained from an organopolysiloxane (a), a polyether polyol (b), a polyisocyanate compound (c) and a chain extender (d), wherein Si/C which is a relative abundance ratio of silicon atoms to carbon atoms existing in a surface of the polyurethane molded article is 0.03-0.5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel polyurethane molded product.

  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 polyurethane urea structure generally uses a polyether polyol as a soft segment component and a polyamine compound having a high cohesive force as a hard segment, so that it has excellent elastic properties and stretch recovery properties. Have.

  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. In addition, since the frictional resistance is large, problems such as yarn breakage are likely to occur in equipment in a processing process such as a spinning machine, a warping machine, a knitting machine, and a guide with which the yarn comes into contact. Therefore, as a conventional technique for solving such problems by reducing the frictional resistance between the processing equipment and the yarn, solid metal soaps, oil-soluble polymers, higher fatty acids, amino-modified silicones, etc. are used as polyurethanes. A method of adding to elastic fibers, a method of dispersing talc, silica, colloidal alumina, titanium oxide or the like as a smoothing agent in polyurethane-based elastic fibers, a method of introducing silicon diol or silicon diamine into a part of the polyurethane main chain, etc. Has been studied (for example, 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. In addition, a large amount of oligomers in the yarn extracted by the oil component in the warping and knitting process and solid or high-viscosity components separated in the solid or paste form adhere to the product. There are problems such as 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 low tackiness and high unwinding property during spinning, that is, a polyurethane having high peelability, without using such an oil agent or a smoothing agent.

  On the other hand, many examples of using an organopolysiloxane as a raw material for polyurethane have been reported so far. For example, a polyurethane resin (Patent Document 2) that uses an ether-modified silicone with a short polyether chain to improve the unraveling property and running smoothness of the elastic fiber production process, and a soft and good wearing feeling using an ether-modified silicone And polyurethane elastic fiber (Patent Document 3) having However, the former has a problem that since the polyether chain of the ether-modified silicone is short, the compatibility with the polyether polyol is poor and it is difficult to form a homogeneous polyurethane. In the latter case, since polyurethane elastic fiber is produced by adding ether-modified silicone after producing polyurethane, there is a problem that ether-modified silicone is easily dropped from the fiber surface. Even if the modified silicone is allowed to react, there is a problem that the compatibility with other polyols is insufficient, and a homogeneous polyurethane is difficult to produce.

Japanese Patent Laid-Open No. 10-259577 Japanese Patent Laid-Open No. 7-165868 JP 2004-332126 A

  The present invention is a polyurethane molded body that is extremely useful in applications such as elastic fibers, films, and clothing having excellent homogeneity and high releasability, in view of the above-mentioned current situation, and silicon atoms relative to carbon atoms present on the surface of the polyurethane molded body. An object of the present invention is to provide a polyurethane molded product having a relative abundance ratio in a specific range.

As a result of intensive studies to solve the above problems, the present inventors have found that when the Si / C, which is the relative abundance ratio of silicon atoms to carbon atoms present on the surface of the polyurethane molded body, is within a specific range, polyurethane molding It has been found that it exhibits high peelability as a body and has completed the present invention.
That is, the gist of the present invention is a polyurethane molded product obtained from an organopolysiloxane (a), a polyether polyol (b), a polyisocyanate compound (c) and a chain extender (d). It exists in the polyurethane molded object whose Si / C which is a relative abundance ratio of the silicon atom with respect to the carbon atom which exists is 0.03-0.5.

  The polyurethane molded product of the present invention is extremely useful for applications such as elastic fibers, films and clothing because Si / C, which is the relative abundance ratio of silicon atoms to carbon atoms present on the surface of the polyurethane molded product, is in a specific range. It is possible to provide a polyurethane molded article having high releasability.

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.
The polyurethane molded product of the present invention is a molded product composed of polyurethane using as raw materials an organopolysiloxane (a), a polyether polyol (b), a polyisocyanate compound (c) and a chain extender (d). Here, the “molded body” is applicable as long as it has a solid surface, and its shape is not particularly limited. In other words, “polyurethane molded product” means polyurethane in a solid state. Therefore, it is not limited to the molded object shape | molded by the specific shaping | molding method. Moreover, the shaping | molding method of a molded object is not specifically limited, What is necessary is just to select a well-known shaping | molding method according to a use.

First, the polyurethane constituting the polyurethane molded product of the present invention will be described.
1. 1. Production of polyurethane 1-1. Raw material for producing polyurethane The polyurethane targeted by the present invention (hereinafter sometimes referred to as the polyurethane of the present invention) is an organopolysiloxane (a), a polyether polyol (b), a polyisocyanate compound (c), and a chain extender. (D) is obtained as a raw material.

  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 a difference in structural characteristics between the two, polyurethane is a polymer that forms a chain structure mainly by urethane bonds, and polyurethane urea is a polymer that forms a chain structure mainly by urethane bonds and urea bonds. The difference from the raw material side is that polyurethane is produced using a short chain polyol as a chain extender, and polyurethane urea is produced using a polyamine compound as a chain extender.

The composition ratio of each raw material is usually that the total number of moles of hydroxyl groups of the organopolysiloxane (a) and the polyether polyol (b) is A, the number of moles of isocyanate groups of the polyisocyanate compound (c) is B, and the chain extender. When the number of moles of the active hydrogen substituent (hydroxyl group and / or amino group) in (d) is C, A: B is usually from 1:10 to 1: 1, preferably from 1: 5 to 1: 1.05. More preferably 1: 3 to 1: 1.1, still more preferably 1: 2.5 to 1: 1.2, particularly preferably 1: 2 to 1: 1.2, and (B -A): C is usually 1: 0.1 to 1: 5, preferably 1: 0.8 to 1: 2, more preferably 1: 0.9 to 1: 1.5, still more preferably 1: It is in the range of 0.95 to 1: 1.2, particularly preferably 1: 0.98 to 1: 1.1.

1-1-1. Organopolysiloxane (a)
The organopolysiloxane (a) used in the present invention is a compound in which an organic group is introduced into the polysiloxane moiety, and known compounds can be used. The structure is not limited as long as an organic group is introduced into the polysiloxane moiety, the organic group is introduced into the side chain of the polysiloxane moiety, the polysiloxane moiety is introduced into both ends, or one end of the polysiloxane moiety. And those introduced only at both ends and side chains of the polysiloxane moiety. Among these, an organopolysiloxane represented by the following structural formula (2) in which an organic group (—R ₁ —X in the structural formula (2)) is introduced at both ends of the polysiloxane moiety is preferable.

In the structural formula (2), R ₁ is a divalent organic group, R ₂ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group or an allyl group, a phenyl group, a tolyl group, etc. Or a cycloalkyl group such as a cyclohexyl group, or a group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group or the like. R ₂ is preferably an alkyl group, and a methyl group is particularly preferable among them. X
Is an organic group selected from a hydroxyl group, a carboxyl group, an amino group, an amide group, an epoxy group, a phenol group, a polyether group, an ester group into which a polyether chain is introduced, a mercapto group, an aralkyl group, a methacryl group, and the like. M is an integer of 5 or more.

  The molecular structure of the organopolysiloxane (a) is not particularly defined as long as an organic group is introduced into the polysiloxane moiety, but other raw materials described later, that is, a polyether polyol (b), a polyisocyanate compound (c) and It is preferable that the molecular structure be such that it is introduced into the polyurethane molecule when reacted with the chain extender (d) to form polyurethane. This is to suppress bleed-out of organopolysiloxane during polyurethane molding. Therefore, the organopolysiloxane (a) desirably has a functional group that can react with at least one of the polyether polyol (b), the polyisocyanate compound (c), and the chain extender (d).

  Specific examples of the organic group are as described above, and among them, an organopolysiloxane containing a hydroxyl group in the molecule, that is, a polysiloxane polyol is preferable. Since this has the same hydroxyl group as the polyether polyol (b), it easily reacts with the polyisocyanate compound (c), and not only the polysiloxane polyol is introduced into the polyurethane structure but also undesirable in polyurethane formation. This is because the possibility of causing a side reaction is low. Further, in order to obtain a block copolymer polyurethane, a polysiloxane polyol having hydroxyl groups introduced at both ends of the polysiloxane is particularly preferred.

The organopolysiloxane (a) used in the present invention has an Si / C (hereinafter, abbreviated as “relative abundance ratio”), which is a relative abundance ratio of silicon atoms to carbon atoms on the surface of the polyurethane molded body, of 0. If it becomes 03-0.5, the kind will not be specifically limited. As the organopolysiloxane (a), those obtained by known production methods (for example, the method described in Japanese Patent Publication No. 5-29706) or commercially available organopolysiloxanes can be used as they are.

  The number average molecular weight of the organopolysiloxane (a) is not particularly limited, but the lower limit is usually 500 or more, preferably 700 or more, more preferably 1000 or more, and the upper limit is usually 5000 or less, preferably 4500 or less, more preferably 4000 or less. If the number average molecular weight exceeds the upper limit, the polyether polyol (b) used in the production of the polyurethane and the compatibility with the solvent tend to be difficult, and it becomes difficult to produce a homogeneous polyurethane, and the organopolysiloxane and the polyether polyol (b) When a mixture (hereinafter sometimes referred to as a polyol mixture), a prepolymer, or a prepolymer solution is formed, the viscosity thereof tends to be too high, and the operability and productivity tend to deteriorate. If it is less than the said minimum, there exists a tendency for the peelability of the polyurethane polymer obtained not to fully express.

The properties of the organopolysiloxane (a) used in the present invention are not particularly limited, but are liquid or waxy at room temperature, and various properties and forms of the organopolysiloxane can be selected depending on the application. It ’s fine.
In order to achieve improved compatibility with the polyether polyol (b) and solvent during polyurethane production, improved transparency of the polyurethane film and high releasability, ether modification of the organopolysiloxane (a) is required. Silicone is preferably used. This is because the physical properties of polyurethane have in the molecule a polyether moiety that contributes to improving transparency and a polysiloxane moiety that contributes to improving peelability.
Particularly preferred is an ether-modified silicone represented by the structural formula (1) shown below. Depending on the properties of the polyurethane to be obtained, the length of the polysiloxane moiety (n in the structural formula (1) below) or the length of the polyether moiety is preferred. Ether-modified silicones having different (y in the following structural formula (1)) may be used.

(In the formula, two R ₁ are independently an alkylene group having 1 to 15 carbon atoms, two R ₂ are independently an alkylene group having 2 to 6 carbon atoms, x is an integer of 0 or 1, 2 y Are independently an integer of 5-50,
n is an integer of 1-100. )
Hereinafter, the ether-modified silicone which is a preferable embodiment of the organopolysiloxane (a) will be described in detail by taking the ether-modified silicone represented by the structural formula (1) which is a particularly preferable embodiment as an example.

In the structural formula (1), x is an integer of 0 or 1, and these values are determined by the method for producing the ether-modified silicone. Y in the structural formula (1) is 5 to 50, the lower limit is usually 5 or more, preferably 7 or more, particularly preferably 10 or more, and the upper limit is usually 50 or less, preferably 40 or less, particularly preferably, 30 or less. When the value of n is constant, the greater the value of y, the higher the compatibility with the polyether polyol (b) and the easier it is to produce a homogeneous polyurethane. However, when the upper limit is exceeded, the molecular weight of the ether-modified silicone increases. If it becomes too much, a viscosity will become high and the operativity at the time of polyurethane manufacture and productivity will worsen. On the other hand, if the value of n is constant, the lower the value of y, the more the polysiloxane skeleton content in the ether-modified silicone increases, so the peelability of the resulting polyurethane polymer improves. The number of carbon atoms of R ₂ in the structural formula (1) is 2 to 6, 2 to 4 is preferred from the effects and versatility of the physical properties of the polyurethane. The polyoxyalkylene moiety may be formed from a single oxyalkylene group or may be formed from a plurality of oxyalkylene groups having different carbon numbers.

  In the structural formula (1), the repeating number n of the dimethylsiloxane skeleton is an integer of 1 to 100, and when the value of y is constant, the larger this value is, the higher the peelability of the resulting polyurethane polymer. Tends to improve. On the other hand, the smaller the value of n, the higher the compatibility with the polyether polyol and the easier it is to produce a homogeneous polyurethane. In general, the addition of a silicone compound is effective for improving the peelability of the polyurethane, but the silicone compound is used in the production of polyurethane with the polyether polyol (b), which is another main raw material, and a solvent. The compatibility is poor. For this reason, there was a problem that the polyurethane produced was clouded and it was difficult to produce a homogeneous film or fiber. On the other hand, when using the ether-modified silicone of the structural formula (1) having a polyether moiety composed of oxyalkylene groups having 5 or more repeating units as the organopolysiloxane (a), in the production of polyurethane, The compatibility of the mixture of the organopolysiloxane (a) and the polyether polyol (b) is improved, and it becomes easy to produce a homogeneous and transparent film or fiber.

  The ratio of the polysiloxane moiety in the ether-modified silicone represented by the structural formula (1) is not particularly limited, but the lower limit is usually 5% by weight or more, preferably 10% by weight or more, More preferably, it is 15 weight% or more, More preferably, it is 20 weight% or more, Most preferably, it is 25 weight% or more. The larger the lower limit value, the more the polyurethane peelability tends to be improved. On the other hand, 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, and particularly preferably 55% by weight or less. The smaller the upper limit value, the higher the transparency and homogeneity of the polyurethane obtained by improving the compatibility with the polyether polyol. The ratio of the polysiloxane moiety in the ether-modified silicone can be easily calculated by measuring NMR, for example.

In the ether-modified silicone represented by the structural formula (1), x is 0, that is, when an alkylene group bonded to the polysiloxane moiety and a plurality of oxyalkylene groups are connected by an ether bond, the ether-modified silicone As the silicone, those commercially available or those obtained by a known method (for example, the method described in JP-B-5-29706) can be used. In the ether-modified silicone represented by the structural formula (1), x is 1, that is, an ether in which an alkylene group bonded to the polysiloxane skeleton and a plurality of oxyalkylene groups are connected by an ester bond. The modified silicone is not only a known method of reacting a terminal unsaturated ester with an organo (poly) siloxane having at least one hydrogen atom bonded to a silicon atom (Japanese Patent Laid-Open No. 9-278891). Can be used.
The ether-modified silicone when x is 1 in the structural formula (1) has a polysiloxane skeleton and has a plurality of carboxyl groups (1) [hereinafter, “polycarboxylic acid having a polysiloxane skeleton ( 1) ". And a polyether polyol (2) can also be obtained by an esterification reaction between the carboxyl group of the former (1) and the hydroxyl group of the latter (2).

(1) Polycarboxylic acid having polysiloxane skeleton Polycarboxylic acid (1) having a polysiloxane skeleton is a compound having a plurality of siloxane sites and a plurality of carboxyl groups. The polysiloxane skeleton is not particularly limited as long as it has a plurality of siloxane skeletons. Examples thereof include polyalkylsiloxanes such as polydimethylsiloxane and polydiethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Of these, polydimethylsiloxane is particularly preferred.

  Moreover, although the carboxyl group may have two or more, it is preferable that it is two. The position of the carboxyl group in the polycarboxylic acid having a polysiloxane skeleton is not particularly limited. Those having a carboxyl group at the molecular side chain, those having both ends of the molecule, those having one end and side chain of the molecule, molecules And the like having only at one end. Among these, dicarboxylic acids having carboxyl groups at both ends of the polysiloxane skeleton are particularly preferable in order to obtain a polyurethane excellent in flexibility and elastic recovery. In addition, the polycarboxylic acid (1) having this polysiloxane skeleton is commercially available, and those known in the art can be used.

  The polycarboxylic acid (1) having a polysiloxane skeleton is one in which a silicon atom has a carboxyl group via a linking group. The linking group is not particularly limited, but for example, methylene Group, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradeca Examples thereof include alkylene groups such as methylene group and pentadecamethylene group, alkenylene groups such as vinylene group and propenylene group, and arylene groups such as phenylene group. Among these, an alkylene group is preferable, and a linear alkylene group having 4 to 12 carbon atoms is particularly preferable.

  The polycarboxylic acid (1) having a polysiloxane skeleton has a number average molecular weight of 600 or more, more preferably 800 or more, particularly 1,000 or more, 5,000 or less, further 4,000 or less. In particular, those of 3,000 or less are preferred. When the number average molecular weight exceeds the upper limit, the molecular weight of the ether-modified silicone produced by the reaction with the polyether polyol (2) becomes too large, and when the polyurethane described later is produced, this ether-modified silicone and the polyether described later are used. When preparing a mixture of the polyol (b), and a prepolymer and a prepolymer solution produced using the mixture, their viscosity tends to be too high, resulting in poor operability and productivity. In addition, the resulting polyurethane tends to be less transparent. On the other hand, if it is less than the lower limit, the resulting polyurethane tends to be insufficiently peelable.

  In addition, the property of polycarboxylic acid (1) having a polysiloxane skeleton is not particularly limited, and a liquid or wax-like material can be used at room temperature. A liquid material is preferable because of good handling properties.

(2) Polyether polyol The polyether polyol (2) used in producing the ether-modified silicone represented by the structural formula (1) is a hydroxy having one or more ether bonds in the main skeleton in the molecule. A compound. The repeating unit in the main skeleton may be either saturated hydrocarbon or unsaturated hydrocarbon, and may be linear, branched or cyclic, for example, 1,2-ethylene glycol unit, 1,2 -Propylene glycol unit, 1,3-propanediol (trimethylene glycol) unit, 2-methyl-1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 1,4-butanediol (Tetramethylone 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, 1,4-cyclohexanedimethanol unit and the like can be mentioned.

  Of these polyether polyols of repeating units, polytetramethylene ether glycol, polytrimethylene ether glycol, copolymer polyether polyols obtained by reaction of 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya) Chemical-manufactured “PTG-L1000”, “PTG-L2000”, “PTG-L3500”, etc.) or copolymer polyether glycols obtained by the reaction of neopentyl glycol and tetrahydrofuran are preferred. These polyether 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 the same polyether polyol as the polyether polyol (b) used in the production of the polyurethane.

  The polyether polyol (2) has a number average molecular weight of 200 or more, more preferably 300 or more, particularly 500 or more, 3,000 or less, more preferably 2,500 or less, particularly 2,000 or less. Are preferred. When the number average molecular weight exceeds the upper limit, in the production of polyurethane described later, the mixture for producing a mixture of the ether-modified silicone represented by the structural formula (1) and the polyether polyol (b) described later, and When a prepolymer and a prepolymer solution produced using the above are formed, their viscosity becomes too high and the operability and productivity tend to deteriorate, and the properties of the resulting polyurethane at low temperatures tend to deteriorate. On the other hand, if it is less than the lower limit, the resulting polyurethane is hard and sufficient flexibility cannot be obtained, and there are cases where elastic properties such as strength and elongation are not sufficient. Here, the number average molecular weight is determined by the above-described measurement method based on the hydroxyl value (KOH (mg) / g) by the acetylation method based on JIS K1557-1: 2007.

(3) Catalyst When the ether-modified silicone represented by the structural formula (1) is obtained by esterifying the polycarboxylic acid (1) having the polysiloxane skeleton and the polyether polyol (2), a catalyst Although it is possible to carry out the esterification reaction in a system in which no ester exists, in general, in order to make the esterification reaction proceed smoothly, inorganic acids or organic acids; Li, Na, K, Rb, Ca, Mg, Sr , Zn, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Sn, Sb, Pb and other metal chlorides, oxides, hydroxides, or acetic acid, oxalic acid, octyl Fatty acid salts such as acid, lauric acid, and naphthenic acid; sodium methoxide, sodium ethoxide, aluminum triisopropoxide, ethyl titanate, isopropyl titanate Normal esterification reactions such as alcohols such as sodium and n-butyl titanate; phenols such as sodium phenolate; and other organometallic compounds of metals such as Al, Ti, Zn, Sn, Zr, and Pb And any catalyst used in the transesterification reaction. Titanium catalysts such as ethyl titanate, isopropyl titanate, and n-butyl titanate are most preferred because they are readily available, have low toxicity and are widely used in esterification reactions. In this case, the amount of the catalyst used is preferably 0.00001 to 0.5% by weight, more preferably 0.0001 to 0.1% by weight, more preferably 0.0005 to 0.005% by weight based on the total amount of the raw material for preparing the ether-modified silicone. Most preferred is 02% by weight. If this amount is too small, it takes a very long time to form the ether-modified silicone, and the product tends to be colored. On the other hand, if the amount is too large, an excessive reaction promoting action for the polyurethane reaction may be exhibited.

  A conventionally known esterification technique can be employed as a method for producing the ether-modified silicone. For example, the method of reacting the polycarboxylic acid (1) having the polysiloxane skeleton with the polyether polyol (2) under normal pressure, the method of reacting under reduced pressure, the reaction in the presence of an inert solvent such as toluene. There is a method in which condensed water or condensed alcohol and a solvent are azeotroped and removed from the reaction system.

  The reaction temperature of the esterification reaction is usually in the range of 100 to 250 ° C, preferably 120 to 240 ° C, more preferably 140 to 230 ° C, and particularly preferably 160 to 220 ° C. If the reaction temperature is too low, the esterification reaction does not proceed sufficiently, and it takes a long time to cut off the reaction, or there is a tendency that some unreacted raw materials remain and become an inhibitor of the polyurethane formation reaction, If it is too high, side reactions may occur and the coloring of the product may increase. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and can be carried out under normal pressure or reduced pressure depending on the purpose. In order to remove water or alcohol generated during the reaction from the reaction system, an inert gas may be circulated in the reaction system. The reaction time of the esterification reaction varies depending on the amount of catalyst used, the reaction temperature, the substrate to be reacted, the desired properties of the ether-modified silicone to be produced, etc., but the lower limit is usually 0.5 hours, preferably 1 hour, the upper limit. Is usually 30 hours, preferably 20 hours.

  Since removal of a titanium-based catalyst or the like from an ether-modified silicone product usually involves complicated steps, the produced ether-modified silicone is generally used as it is for the production of polyurethane as it is without separating the titanium-based catalyst. . However, it is preferable to deactivate the titanium catalyst in the ether-modified silicone depending on the content of the catalyst and the use of polyurethane. Examples of the method for deactivating the titanium-based catalyst in the ether-modified silicone include a method in which the ether-modified silicone is brought into contact with water under heating, and the ether-modified silicone is a phosphorous compound such as phosphoric acid, phosphoric acid ester, phosphorous acid, and phosphorous acid ester. The method of processing etc. can be mentioned. And, in the case of the former method of contacting with water, for example, adding 1% by weight or more of water to ether-modified silicone and heating at a temperature of 70 to 150 ° C., preferably 90 to 130 ° C. for about 1 to 3 hours. Good. The deactivation treatment by heating at that time may be performed under normal pressure or under pressure, and when the system is depressurized after the deactivation treatment, the water used for deactivation can be removed smoothly from the ether-modified silicone. it can.

  The production of the ether-modified silicone represented by the structural formula (1) is prepared by charging the polycarboxylic acid (1) having the polysiloxane skeleton, the polyether polyol (2), the titanium catalyst (3), and the like. The reaction is preferably carried out at a reaction temperature of 160 to 220 ° C. under normal pressure. In order to prevent the unreacted polycarboxylic acid from remaining, the polyether polyol may be reacted in a small excess amount. In this case, the ether-modified silicone produced by this method and the unreacted polyether polyol (2) are used as they are. It can be used for mixing with the ether polyol (b).

  The ether-modified silicone is produced by an esterification reaction of a polycarboxylic acid and a polyether polyol, and contains a structure such as the structural formula (1) in which the polyether polyol is bonded to both ends of the polycarboxylic acid as a main component. It is expected that some polyester-type polyols having a plurality of alternating structures of polysiloxane units and polyether units are also produced. However, even if a part of the ether-modified silicone having such a structure is produced, it is unlikely to cause a problem in the preparation of a polyol mixture or polyurethane, and is included in the present invention.

1-1-2. Polyether polyol (b)
The polyether polyol (b) used in the present invention is a hydroxy compound having one or more ether bonds in the main skeleton in the molecule, and excludes those included in the organopolysiloxane (a). . The repeating unit in the main skeleton may be either saturated hydrocarbon or unsaturated hydrocarbon, and may be linear, branched or cyclic, for example, 1,2-ethylene glycol unit, 1,2 -Propylene glycol unit, 1,3-propanediol (trimethylene glycol) unit, 2-methyl-1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 1,4-butanediol (Tetramethylone 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, 1,4-cyclohexanedimethanol unit and the like can be mentioned.

  Of these polyether polyols of repeating units, polytetramethylene ether glycol, polytrimethylene ether glycol, copolymer polyether polyols obtained by reaction of 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya) Chemical-manufactured “PTG-L1000”, “PTG-L2000”, “PTG-L3500”, etc.) or copolymer polyether glycols obtained by the reaction of neopentyl glycol and tetrahydrofuran are preferred. These polyether 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.

  As the polyether polyol (b) used in the present invention, the molecular weight is a number average molecular weight, the lower limit is usually 500 or more, further 800 or more, particularly 1000 or more, and the upper limit is usually 4000 or less. Further, it is preferably 3700 or less, particularly 3500 or less. When the number average molecular weight exceeds the upper limit, in the production of polyurethane described later, the mixture used for preparing the mixture of the organopolysiloxane (a) and the polyether polyol (b) described above, and the prepolymer produced using the mixture. When a polymer or prepolymer solution is formed, the viscosity thereof becomes too high and the operability and productivity tend to deteriorate, and the properties of the resulting polyurethane at low temperatures tend to deteriorate. On the other hand, when the amount is less than the lower limit, the obtained polyurethane is hard and sufficient flexibility cannot be obtained, or the elastic performance such as strength and elongation is not sufficient. Here, the number average molecular weight is determined by a hydroxyl value (KOH (mg) / g) measurement method by an acetylation method based on JIS K1557-1: 2007.

  Although the usage-amount of organopolysiloxane (a) and polyether polyol (b) is not specifically limited, As usage-amount of organopolysiloxane with respect to the total weight of organopolysiloxane (a) and polyether polyol (b) The lower limit is usually 0.01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.07% by weight or more, particularly preferably 0.1% by weight or more. The upper limit is usually 10% by weight or less, preferably 8% by weight or less, more preferably 7% by weight or less, still more preferably 6% by weight or less, and particularly preferably 5% by weight or less. As the amount of the organopolysiloxane used increases, the peelability of the resulting polyurethane molded product tends to improve. The smaller the amount used, the worse the peelability of the resulting polyurethane molded product, but the better the elastic properties, stretch recovery properties and homogeneity.

1-1-3. Polyisocyanate compound (c)
The polyisocyanate compound (c) used in the present invention is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, 2,4- or 2,6-tolylene diisocyanate, xylylene Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-MDI, paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, α, α, α ', α'- Aliphatic diisocyanates having an aromatic ring such as tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hex Aliphatic diisocyanates such as methylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'- Examples thereof include alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isopropylidene dicyclohexyl-4,4′-diisocyanate. These may be used alone or in combination of two or more. In the present invention, aromatic polyisocyanate is preferable, and aromatic diisocyanate having high reactivity is particularly preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferable. In addition, a part of the NCO group of the isocyanate compound may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc., and the polynuclear substance contains isomers other than the above. Is also included.

  The amount of these polyisocyanate compounds (c) used is based on 1 equivalent of the total of the hydroxyl groups of the organopolysiloxane (a) and the polyether polyol (b) and the hydroxyl group and amino group of the chain extender (d). In general, 0.1 equivalents to 5 equivalents, preferably 0.8 equivalents to 2 equivalents, more preferably 0.9 equivalents to 1.5 equivalents, still more preferably 0.95 equivalents to 1.2 equivalents, most preferably 0.98 equivalents to 1.1 equivalents. When the amount of the polyisocyanate compound used is too large, the unreacted isocyanate group causes an unfavorable reaction and tends to make it difficult to obtain desired physical properties. When the amount is too small, the molecular weight of polyurethane and polyurethane urea is not sufficiently increased. The desired performance tends not to be expressed. Here, when the organopolysiloxane (a) does not have a hydroxyl group and has another functional group capable of reacting with the polyisocyanate compound (c), or the organopolysiloxane (a) has a hydroxyl group and a polyisocyanate compound ( When other functional groups capable of reacting with c) are also contained, such other functional groups shall be handled in the same manner as the hydroxyl group.

1-1-4. Chain extender (d)
The chain extender (d) used in the present invention is mainly classified into a compound having two or more hydroxyl groups, a compound having two or more amino groups, and water. Among these, a short chain polyol, specifically a compound having two or more hydroxyl groups, is preferable for polyurethane production, and a polyamine compound, specifically a compound having two or more amino groups, is preferable for polyurethane urea production. . In the chain extender (d), water is preferably reduced as much as possible in order to carry out the reaction stably. In the polyurethane of the present invention, it is more preferable from the viewpoint of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less as the chain extender (d) because the rubber elasticity of the polyurethane elastomer is improved. These chain extenders (d) may be used alone or in combination of two or more.

  Here, as the compound having two or more hydroxyl groups, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 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-butanediol, 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- Examples thereof include aliphatic glycols such as octanediol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene.

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

  When the amount of these chain extenders (d) used is 1, the equivalent of the polyisocyanate compound (c) minus the total hydroxyl equivalent of the organopolysiloxane (a) and the polyether polyol (b) is 1. Usually, it is 0.1 equivalent-5.0 equivalent, Preferably it is 0.8 equivalent-2.0 equivalent, More preferably, it is 0.9 equivalent-1.5 equivalent. If the amount of the chain extender (d) used is too large, the resulting polyurethane and polyurethane urea become too hard and the desired properties cannot be obtained, and it tends to be difficult to dissolve in the solvent and difficult to process. It is so soft that sufficient strength, elastic recovery performance and elastic retention performance cannot be obtained, and high temperature characteristics tend to deteriorate. Here, when the organopolysiloxane (a) does not have a hydroxyl group and has another functional group that can react with the chain extender (d), or the organopolysiloxane (a) has a chain extender ( When other functional groups capable of reacting with d) are also contained, such other functional groups are handled in the same manner as hydroxyl groups.

1-1-5. Other additives (e)
In the present invention, for the production of polyurethane, in addition to the above (a) to (d), for the purpose of controlling the molecular weight of polyurethane, a chain terminator having one active hydrogen group is used as necessary. can do. Examples of these chain terminators include aliphatic monools such as ethanol having a hydroxyl group, propanol, butanol and hexanol, diethylamine having amino groups, dibutylamine, n-butylamine, monoethanolamine and diethanolamine. Illustrated. These may be used alone or in combination of two or more.

  Moreover, you may add another additive as needed at the time of polyurethane manufacture. As these additives, “CYANOX1790” (manufactured by Cyanamid), “IRGANOX245”, “IRGANOX1010” (above, manufactured by Ciba Specialty Chemicals), “Sumizer GA-80” (manufactured by Sumitomo Chemical), and Antioxidants such as 2,6-dibutyl-4-methylphenol (BHT), “TINUVIN622LD”, “TINUVIN765” (manufactured by Ciba Specialty Chemicals), “SANOLLS-2626”, “SANOL LS-765 ”(Above, Sankyo Co., Ltd.) and other light stabilizers,“ TINUVIN 328 ”,“ TINUVIN 234 ”(above, Ciba Specialty Chemicals Co., Ltd.), etc., UV absorbers, silicon such as dimethylsiloxane polyoxyalkylene copolymer Compound Products, red phosphorus, organic phosphorus compounds, phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc. and reactive flame retardants; pigments and dyes such as titanium dioxide Colorants such as carbon black, hydrolysis inhibitors such as carbodiimide compounds, short glass fibers, carbon fibers, alumina, talc, graphite, melamine, clay, fillers, lubricants, oils, surfactants, other inorganic extenders And organic solvents.

1-2. Production of Polyurethane In the present invention, polyurethane is produced by using organopolysiloxane (a), polyether polyol (b), polyisocyanate compound (c), and chain extender (d) as raw materials for main production. It can be carried out in the absence of a solvent or in the coexistence of a solvent by any production method generally used experimentally / industrially. The solvent used in this case is not particularly limited, but N, N-dimethylacetamide, N, N-dimethylformamide, and a mixture of two or more thereof from the viewpoints of versatility and solubility. Are preferably selected from the group consisting of N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide, and among these, N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable. .

  As an example of the production method, the method (a), the method (b), the method (c) and the method (d) are reacted together (hereinafter referred to as a one-step method). ) In advance to prepare a polyol mixture, further reacting the mixture with the above (c) to prepare a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with the above (d) ( Hereinafter referred to as a two-stage method), a method in which (b) and (c) are reacted and then (a) is mixed and reacted with (d), (b), (c), and The method of mixing (a) after reacting (d) can be mentioned. Among these, the two-stage method is such that a mixture of the organopolysiloxane (a) and the polyether polyol (b) is reacted in advance with one or more equivalents of a polyisocyanate compound (c) to thereby form both ends corresponding to the polyurethane soft segment. This is a process for preparing an intermediate sealed with isocyanate, and after the prepolymer is prepared, it is reacted with the chain extender (d), so that the molecular weight of the soft segment portion is easily adjusted. For this reason, there is a feature that the soft segment and the hard segment are easily phase-separated and the performance as an elastomer is easily obtained. In particular, when the chain extender (d) is a diamine, the reaction rate with the isocyanate group is greatly different from the hydroxyl group of the organopolysiloxane or polyether polyol, which is a preferable production method in the production of polyurethane urea.

  In addition, the polyurethane production method in which the mixture of (a) and (b) and the above (c) are reacted to prepare a prepolymer having isocyanate groups at both ends and then the prepolymer and the above (d) are reacted. Since the organopolysiloxane is incorporated into the molecular structure of the polyurethane, the organopolysiloxane is less likely to bleed out (separate and precipitate) in the polyurethane molding step, and the most preferable method is that the peelability of the formed polyurethane molded product is not impaired. I can say that. On the other hand, as another method for producing polyurethane, for example, there is a method of mixing (a) after reacting (b), (c) and (d). In this method, organopolysiloxane is polyurethane. Since it is not incorporated into the molecular structure, it tends to bleed out in the polyurethane molding process, and the resulting polyurethane molded product tends not to exhibit the desired peelability, and a large amount of organopolysiloxane is required to obtain sufficient peelability. Therefore, the cost tends to increase, which is not preferable.

The method for preparing the polyol mixture with the organopolysiloxane (a) and the polyether polyol (b) is not particularly limited, but when both the organopolysiloxane (a) and the polyether polyol (b) are in liquid form, It is preferable to stir and 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 is not limited, It is preferable to mix at 10-110 degreeC. If the temperature is too high, the polyol mixture may be colored. If the temperature is too low, the polyol may partially solidify and work efficiency may be reduced. There is a tendency that polyurethane cannot be produced stably. If the polyol mixture is prepared in advance, the compatibility between the organopolysiloxane (a) and the polyether polyol (b) is good. It has the characteristic of not causing separation.

  Moreover, when manufacturing the polyurethane of this invention mentioned later, an organopolysiloxane (a) and polyether polyol (b) are introduce | transduced from a separate line, and a polyol mixture can also be made into a polyol mixture by mixing or disperse | distributing. preferable. When each is fed from a separate line, a special grade polyurethane excellent in peelability can be produced simply by adding a tank and a feed line for the organopolysiloxane of the present invention to an ordinary polyurethane production facility. If a polyol mixture is prepared and then introduced into a polyether polyol storage tank in a normal polyurethane production facility, the organopolysiloxane may be mixed when producing normal grade polyurethane, which may impair the homogeneity of the polyurethane. Conceivable. In order to efficiently produce normal grade and special grade polyurethane so that desired physical properties can be obtained, it is preferable to introduce organopolysiloxane (a) and polyether polyol (b) from separate lines in this way. .

1-2-1. One-step method The one-step method is also called a one-shot method, and is a method in which the reaction is carried out by charging the (a), (b), (c), and (d) together. In the reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor. On the other hand, if the temperature is too high, side reactions and polyurethane decomposition 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. Examples of the catalyst in this case include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, and the like. -Dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, tri (dinonylphenyl) phosphite and the like.

1-2-2. Two-stage method The two-stage method is also called the prepolymer method. First, an organopolysiloxane (a) and a polyether polyol (b) are mixed to produce a prepolymer obtained by reacting the polyisocyanate compound (c) with the mixture. Then, a polyisocyanate compound (c) or an active hydrogen compound component such as a polyhydric alcohol or an amine compound can be added to the polyisocyanate compound (c) for a two-step reaction. Particularly useful is a method of reacting at least an equivalent amount of a polyisocyanate compound (c) with a polyol mixture to form an NCO prepolymer at both ends, and then reacting with a short chain diol or diamine as a chain extender to obtain a polyurethane. is there. Since the organopolysiloxane is difficult to bleed out in the production process of the polyurethane molded product, it is most preferable to produce polyurethane by the above method in order to obtain sufficient physical properties as a polyurethane molded product.

  The two-stage method can be carried out without a solvent or in the presence of a solvent. When carried out in the presence of a solvent, from the viewpoint of versatility and solubility, amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, and mixtures of two or more thereof, N-methylpyrrolidone , N-ethylpyrrolidone, and a solvent selected from the group consisting of dimethyl sulfoxide are preferably used, and among these, N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable.

When synthesizing a prepolymer, <1> the polyisocyanate compound (c) and the polyol mixture may be directly reacted without using a solvent to synthesize the prepolymer and used as it is, or <2><1> The prepolymer may be synthesized by the method and then used after being dissolved in a solvent, or <3> the polyisocyanate compound (c) and the polyol mixture may be reacted using a solvent from the beginning. In the case of <1>, in the present invention, when acting with the chain extender (d), the chain extender (d) is dissolved in a solvent, or the prepolymer and the chain extender (d) are simultaneously introduced into the solvent. It is important to obtain polyurethane in the form of coexistence with a solvent by such a method.

  As for the reaction equivalent ratio of NCO / active hydrogen group (polyol mixture), the lower limit is usually 1, preferably 1.05, and the upper limit is usually 10, preferably 5, more preferably 3. If this ratio is too large, excessive isocyanate groups tend to adversely affect the physical properties of the polyurethane due to side reactions. If it is too small, the molecular weight of the resulting polyurethane does not increase sufficiently, and the strength and thermal stability are increased. Tend to cause problems. Further, the amount of the chain extender (d) used is not particularly limited, but the lower limit is usually 0.1, preferably 0.8 relative to the equivalent of the NCO group contained in the prepolymer, and the upper limit is Usually in the range of 5.0, preferably 2.0.

In the chain extension reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the temperature is too low, the progress of the reaction is too slow, and the solubility of the raw materials and the polymer is low, so that the productivity is poor. On the other hand, if the temperature is too high, side reactions and polyurethane decomposition 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. Examples of the catalyst in this case include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, and the like. -Dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, tri (dinonylphenyl) phosphite and the like. 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. Further, a monofunctional organic amine or alcohol may coexist during the reaction.

2. Properties of polyurethane Polyurethane obtained by the above production method is usually reacted in the presence of a solvent, so it is generally obtained in a state dissolved in a solution, but it is not limited in a solution state or a solid state. .
In the present invention, the weight average molecular weight (Mw) of polyurethane by gel permeation chromatography (GPC) varies depending on the application, but is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000. Particularly preferred is 150,000 to 300,000. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) as a standard of the molecular weight distribution is preferably 1.5 to 3.5, more preferably 1.7 to 3 0.0, particularly preferably 1.8 to 3.0. Moreover, the smaller the peel strength at the time of film formation of the polyurethane film in the present invention, the better. The upper limit of peel strength is usually 30 g / cm or less, preferably 20 g / cm or less, more preferably 10 g / cm or less. When the upper limit is exceeded, the release property of the polyurethane polymer is insufficient.

  Moreover, the polyurethane obtained by the above production method preferably contains 1 to 20% by weight, more preferably 3 to 15% by weight, and still more preferably the amount of hard segments with respect to the total weight of the polyurethane. It is 4 to 12% by weight, and particularly preferably 5 to 10% by weight. When the amount of the hard segment is too large, the resulting polyurethane does not exhibit sufficient flexibility and elastic performance, or when a solvent is used, it tends to be difficult to dissolve and difficult to process. On the other hand, if the amount of hard segment is too small, polyurethane tends to be too soft and difficult to process, and sufficient strength and elastic performance tend not to be obtained.

In the present invention, the hard segment refers to P.I. J. et al. Flory, Journal of American Chemical Society, 58, 1877-1885.
Based on (1936), the weight of the isocyanate and chain extender binding part 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 / (number of moles of hydroxyl group of polyether polyol + number of moles of hydroxyl group of organopolysiloxane)
Mdi = Number average molecular weight of polyisocyanate compound Mda = Number average molecular weight of chain extender Mp = Number average molecular weight of polyol mixture composed of organopolysiloxane and polyether polyol

  The polyurethane solution obtained in the present invention is less prone to gelation, has a good storage stability such as a small change in viscosity with time, and has a low thixotropy, which is convenient for processing into films, fibers, etc. . The polyurethane concentration of the polyurethane solution is usually 1 to 99% by weight, preferably 5 to 90% by weight, more preferably 10 to 70% by weight, particularly preferably 15 to 50% by weight, based on the total weight of the solution dissolved in the solvent. %. If the amount of polyurethane is too small, it will be necessary to remove a large amount of solvent and the productivity will tend to be low.On the other hand, if the amount is too large, the viscosity of the solution will be too high and the operability and processability will tend to be poor. Become. In addition, when storing a polyurethane solution for a long period of time, it is preferable to preserve | save in inert gas atmosphere, such as nitrogen and argon, at normal temperature or the temperature below it.

3. Polyurethane molded product The polyurethane molded product of the present invention is a molded product composed of the polyurethane. As described above, in the present invention, the polyurethane molded product means a solid state polyurethane, and thus the solid polyurethane itself obtained by the production method exemplified above also corresponds to the polyurethane molded product of the present invention. Furthermore, the molded object obtained by shape | molding this polyurethane by a well-known method also corresponds. The molding method and form are not particularly limited, but include those molded into a sheet, film, fiber, or the like by a molding method such as extrusion molding or injection molding.

  The polyurethane molded article of the present invention is characterized in that the atomic composition of the molded article surface is specific. That is, 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 usually 0.03 or more, preferably 0.05 or more, more preferably 0.06 or more, Preferably, it is 0.07 or more, particularly preferably 0.08 or more. If it is less than the lower limit value, the peelability of the polyurethane molded product becomes insufficient, such being undesirable. On the other hand, the upper limit is usually 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less, and particularly preferably 0.15 or less. Exceeding the upper limit is not preferable because flexibility and transparency of the resulting molded product tend to be low.

In the present invention, the relative abundance ratio of silicon atoms to carbon atoms present on the surface of the molded body is measured by ESCA (Electron Spectroscopy for Chemical Analysis) or XPS (X-ray Photoelectron Spectroscopy). In addition, the relative abundance ratio of the surface of the molded body can be changed by changing the addition amount of organopolysiloxane (a) or polyether polyol (b), changing the order of addition of organopolysiloxane, or using organopolysiloxanes with different molecular structures. Etc. can be adjusted.

4). Uses of polyurethane The polyurethane produced in the present invention and its urethane prepolymer solution can express various properties, for example, resin, rubber, thermoplastic elastomer, and various shapes. Solid, foam, liquid, etc. molded into fiber, film, paint, adhesive, functional parts, etc., clothing, sanitary goods, packaging, civil engineering, architecture, medical care, automobiles, home appliances, etc. Used in a wide range of industrial parts. In particular, it is preferable to take advantage of the elastic performance and moisture permeability characteristics of the polyurethane produced in the present invention to be used as a fiber or a film. Specific examples of these applications include elastic fibers for clothing, medical and hygiene products, It is preferably used for artificial leather and the like.

4-1. Polyurethane film Although the thickness using the polyurethane of this invention is not specifically limited, Usually, 10-1000 micrometers, Preferably it is 10-500 micrometers, More preferably, it is 10-100 micrometers. If the film is too thick, sufficient moisture permeability tends not to be obtained, and if it is too thin, pinholes are likely to be formed, and the film tends to be blocked and difficult to handle. Moreover, this film 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 film may be thinner than 10 μm. Further, as tensile properties, the breaking strength is usually 5 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and further preferably 30 MPa or more, and the breaking elongation is usually 100% or more, preferably 200% or more. Preferably it is 300% or more, More preferably, it is 500% or more.

  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 film is applied or cast on a support or a release material, and a solvent or other soluble material is extracted 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 or decompression. The support used when forming the film is not particularly limited, and polyethylene film, polypropylene film, glass, metal, paper or cloth coated with a release agent, and the like are used. The application method is not particularly limited, and any known method such as a knife coater, a roll coater, a spin coater, or a 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, preferably room temperature to 300 ° C. Preferably it is the range of 60 to 200 degreeC.

4-2. Polyurethane fiber The physical properties of the polyurethane film and the fiber have a very good correlation, and the physical property values obtained in the film test and the like 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, processability, etc., for example, leg, pantyhose, diaper cover, paper diaper, It is preferably used for sports clothing, underwear, socks, stretch clothing excellent in fashionability, swimwear, leotard and the like. The excellent moisture permeability of the elastic fiber using the polyurethane of the present invention is characterized by being hard to be stuffy and comfortable to wear when used in clothing. In addition, the characteristic of low stress fluctuation rate or modulus is that, for example, the sleeve can be passed with a small force when worn on the body as clothing, and it is very easy for small children and the elderly to attach and detach. have. In addition, because of the good fit and movement following ability, it can be used for sports clothing and more fashionable clothing. Further, since the elastic retention rate in the repeated extension test is high, the elastic performance is not easily impaired even after repeated use.

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 and comparative examples were performed according to the following methods.

<Number average molecular weight of polysiloxane polyol>
When the polyether polyol (2) is present in an amount of 2 equivalents or more relative to the polycarboxylic acid (1) having a polysiloxane skeleton, the number average molecular weight of the polysiloxane polyol as the organopolysiloxane (a) is as follows from the molecular weight of the raw material: [Equation 1]. The number average molecular weights of the polysiloxane polyols 1 and 2 used in the examples were calculated by [Formula 1]. The number average molecular weight of the polysiloxane polyols 4 and 5 can be calculated by [Equation 2] using the charged weights of the carbinol-modified silicone and ε-caprolactone as raw materials. The number average molecular weight of the polysiloxane polyols 4 and 5 was calculated by [Formula 2]. However, since the polysiloxane polyols 3 and 6 used in the examples are commercially available products, the number average molecular weight is described by the manufacturer's catalog value.

[Formula 1]
Number average molecular weight of polysiloxane polyols 1 and 2 = (molecular weight of polycarboxylic acid (1) having a polysiloxane skeleton) + (molecular weight of polyether polyol (2)) × 2− (molecular weight of water) × 2

[Formula 2]
Number average molecular weight of polysiloxane polyols 4 and 5 = molecular weight of carbinol-modified silicone + {(charge weight of ε-caprolactone) / (molecular weight of ε-caprolactone)} / {(charge weight of carbinol-modified silicone) / (carbi Molecular weight of diol-modified silicone)} × (molecular weight of ε-caprolactone)
<Number average molecular weight of polyether polyol (b)>
The number average molecular weight 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 (two)]. The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Peel test method>
Two molded films were superposed, a test piece having a length of 4 cm and a width of 1 cm was punched out, and a superposed portion of 2.5 cm from one end in the length direction was subjected to 200 g / kg under 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 the pressure of cm ² was applied for 10 minutes, the peel strength when the crimped portion was peeled off at a tensile rate of 300 mm / min was measured. .

<Physical properties of film>
The polyurethane or polyurethane urea test piece is a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm, and in accordance with JIS K6301, using a tensile tester (product name “Tensilon UTM-III-100” manufactured by Orientec Co., Ltd.). The tensile breaking strength at a temperature of 23 ° C. (relative humidity 55%), tensile breaking elongation, and strength at 100% elongation and 300% elongation were measured at a chuck distance of 50 mm and a tensile speed of 500 mm / min.

<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 was determined by ESCA (Electron Spectroscopy for 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 (angle of the detector from the sample normal): 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.

Example 1
<Production of polysiloxane polyol 1>
In a 100 mL four-necked round bottom flask equipped with a stirrer, 4.4 mg of tetraethyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.), carboxylic acid-modified silicone (manufactured by Toray Dow Corning, “BY16-750”, number average molecular weight 1, 500) 30.0 g (20.0 mmol) and 27.4 g (42.2 mmol) of polytetramethylene ether glycol (number average molecular weight 650, manufactured by Mitsubishi Chemical Corporation) were weighed. A distillation tube and a nitrogen introduction tube were attached, and the distillation part was kept at 120 ° C. by a tape heater. The reaction vessel was immersed in an oil bath, heated to 200 ° C. in 30 minutes, and reacted at 200 ° C. for 7 hours to obtain polysiloxane polyol 1 (number average molecular weight 2764, polydimethylsiloxane content 40 wt%).

<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 1972, manufactured by Mitsubishi Chemical Corporation) ) 109 parts by weight and 0.55 parts by weight of the polysiloxane polyol 1 synthesized above as organopolysiloxane (a) were added and mixed, and this mixture was used as a raw material for polyurethane production. The ratio of polyester polyol 1 to this mixture was 0.5% by weight. Thereafter, 22.3 parts by weight of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) previously heated to 40 ° C. was added as the polyisocyanate compound (c). The reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) at this time 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. After 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%, the oil bath was removed, and the flask was charged with N , N-dimethylacetamide (hereinafter sometimes abbreviated as “DMAC”; manufactured by Kanto Chemical Co., Inc.) 198 parts by weight 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 the chain extender (d) was 0.6% DMAC of ethylenediamine (EDA) / diethylamine (DEA) = 89/11 (molar ratio). A solution was prepared. The polyurethane prepolymer solution cooled and held at 10 ° C. was added to this 0.6% DMAC solution while stirring at a high speed to obtain a DMAC solution of polyurethane urea 1 having a polymer concentration of 20% and good transparency.

  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 216,000 and Mw / Mn was 2.5. Moreover, the ratio of the hard segment of the obtained polyurethane urea 1 was 7.7% by weight. The polyurethaneurea 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 peeled, the peel strength was 1.0 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and Si / C of the surface atomic composition was 0.120.

Example 2
<Production of polysiloxane polyol 2>
Instead of polytetramethylene ether glycol (number average molecular weight 650, manufactured by Mitsubishi Chemical Corp.) as polyether polyol (2), polytetramethylene ether glycol (number average molecular weight 1,009, manufactured by Mitsubishi Chemical Corp.) 33.8 g (33 .8 mmol), the amount of tetraethylorthotitanate was 5.2 mg, and the amount of carboxylic acid-modified silicone (“BY16-750” manufactured by Toray Dow Corning Co., Ltd.) as polycarboxylic acid (1) having a polysiloxane skeleton Was made in the same manner as in Example 1 except that 24.1 g (16.1 mmol) was used, to prepare polysiloxane polyol 2 (number average molecular weight 3482, polydimethylsiloxane content 32 wt%).

<Production of polyurethane urea 2>
A polyurethaneurea 2 solution was produced in the same manner as in Example 1 except that 0.67 g of the polysiloxane polyol 2 synthesized above was used as the organopolysiloxane (a).
After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 2 had an Mw measured by GPC of 231,000 and Mw / Mn of 2.4. Moreover, the ratio of the hard segment of the obtained polyurethane urea 2 was 7.8% by weight. When a film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted, the peel strength was 1.1 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and Si / C of the surface atomic composition was 0.127.

Example 3
<Production of polyurethane urea 3>
Table 1 except that 0.65 parts by weight of ether-modified silicone (manufactured by Dow Corning Toray, SF8427, number average molecular weight 1860) was used as organopolysiloxane (a).
A polyurethane urea 3 solution was produced in the same manner as in Example 1 with the composition of

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 3 had an Mw measured by GPC of 279,000 and an Mw / Mn of 2.5. Moreover, the ratio of the hard segment of the obtained polyurethane urea 3 was 7.8% by weight. Further, when a film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted, the peel strength was 2.8 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and the surface atomic composition Si / C was 0.09.

Example 4
<Production of polysiloxane polyol 4>
In a 100 mL four-necked round bottom flask equipped with a stirrer, 4.2 mg of tetrabutyl orthotitanate (Tokyo Kasei Co., Ltd.), 62.5 g (34.5 mmol) of carbinol-modified silicone (KF-6001 manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group) Value 62) 10 g (87.6 mmol) of ε-caprolactone (Across) was measured. A reflux pipe and a nitrogen introduction pipe were attached, the reaction vessel was immersed in an oil bath, heated to 190 ° C. in 30 minutes, and reacted at 190 ° C. for 7 hours to react with polysiloxane polyol 4 (number average molecular weight 2100, polydimethylsiloxane content 77 .9 wt%).

<Production of polyurethane urea 4>
A polyurethane urea 4 solution was produced in the same manner as in Example 1 except that 5.14 parts by weight of the polysiloxane polyol 4 synthesized above was used as the organopolysiloxane (a).

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 4 had an Mw measured by GPC of 194,000 and an Mw / Mn of 2.5. Moreover, the ratio of the hard segment of the obtained polyurethane urea 4 was 7.8% by weight. Further, when a film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted, the peel strength was 0.6 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and Si / C of the surface atomic composition was 0.182.

Example 5
<Production of polysiloxane polyol 5>
The amount of tetrabutyl orthotitanate used is 4.2 mg, the amount of carbinol-modified silicone used is 45.0 g (24.9 mmol), and the amount of ε-caprolactone used is 29.6 g (
259 mmol), polysiloxane polyol 5 was produced in the same manner as in Example 4. (Number average molecular weight 3001, polydimethylsiloxane content 54.5 wt%)

<Production of polyurethane urea 5>
A polyurethane urea 5 solution was produced in the same manner as in Example 1 except that 5.40 parts by weight of the polysiloxane polyol 5 synthesized above was used as the organopolysiloxane (a).

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 5 had an Mw measured by GPC of 21.9 million and an Mw / Mn of 2.9. Moreover, the ratio of the hard segment of the obtained polyurethane urea 5 was 7.7% by weight. Further, when a film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted, the peel strength was 1.2 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and Si / C of the surface atomic composition was 0.174.

Example 6
<Production of polyurethane urea 6>
Except that 5.53 parts by weight of carbinol-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-6001, number average molecular weight 1820) was used as the organopolysiloxane (a), the same composition as in Example 1 was used. A polyurethaneurea 6 solution was prepared.

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 6 had an Mw measured by GPC of 188,000 and Mw / Mn of 2.2. Moreover, the ratio of the hard segment of the obtained polyurethane urea 6 was 7.8% by weight. Further, when a film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted, the peel strength was 1.9 g / cm and the peelability was good. Further, the obtained film had physical properties as shown in Table 1, and Si / C of the surface atomic composition was 0.191.

Example 7
<Production of polyurethane urea 7>
A polyurethane urea 7 solution was prepared in the same manner as in Example 1 except that 0.10 parts by weight of carbinol-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-6001) was used as the organopolysiloxane (a). Manufactured.

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 7 had Mw of 214,000 and Mw / Mn of 2.6 measured by GPC. Moreover, the ratio of the hard segment of the obtained polyurethane urea 7 was 7.8% by weight. A film was produced from the polyurethane urea solution thus obtained in the same manner as in Example 1 with the composition shown in Table 1. The physical properties of the film were as shown in Table 1, and the Si / C of the surface atomic composition was 0.071.

Comparative Example 1
<Manufacture of polyurethane urea 8>
Without using the organopolysiloxane (a), a polyurethaneurea 8 solution was produced in the same manner as in Example 1 with the composition shown in Table 1.

  After aging this solution at 25 ° C. overnight, the obtained polyurethane urea 8 had an Mw measured by GPC of 217,000 and an Mw / Mn of 2.5. Moreover, the ratio of the hard segment of the obtained polyurethane urea 3 was 7.8% by weight. A film was formed from the polyurethane urea solution thus obtained in the same manner as in Example 1 and a peel test was conducted. As a result, the peel strength was 46.0 g / cm, and the peelability was poor. Further, the obtained film has physical properties as shown in Table 1, and since the organopolysiloxane (a) is not added, Si / C of the surface atomic composition is 0.

  According to the present invention, it is possible to produce a polyurethane molded body having high peelability and extremely useful for applications such as elastic fibers, films, and clothing. And when using the obtained polyurethane molded body as elastic fiber, cost reduction by reducing the amount of oil and smoothing agent used, improvement of operational stability by reducing product fouling and clogging of machines and instruments, friction resistance Reduction of driving power due to the reduction in power consumption can be expected.

Claims (13)

  A polyurethane molded product obtained from an organopolysiloxane (a), a polyether polyol (b), a polyisocyanate compound (c), and a chain extender (d), wherein silicon atoms are present relative to carbon atoms present on the surface of the polyurethane molded product. A polyurethane molded product having a relative abundance ratio of Si / C of 0.03 to 0.5.   The polyurethane molded article according to claim 1, wherein the organopolysiloxane (a) is a polysiloxane polyol.   The polyurethane molded article according to claim 1 or 2, having a peel strength of 30 g / cm or less.   The polyurethane molded article according to claim 2 or 3, wherein the polysiloxane polyol is an ether-modified silicone. The polyurethane molded article according to claim 4, wherein the ether-modified silicone is a polysiloxane polyol represented by the following structural formula (1).

(In the formula, two R ₁ are independently an alkylene group having 1 to 15 carbon atoms, two R ₂ are independently an alkylene group having 2 to 6 carbon atoms, x is an integer of 0 or 1, 2 y Are independently an integer of 5-50,
n is an integer of 1-100. )   The polyurethane molded article according to any one of claims 1 to 5, wherein the polyether polyol (b) is polytetramethylene ether glycol.   The number average molecular weight of organopolysiloxane (a) is 500-5000, The polyurethane molded object of any one of Claims 1-6.   The polyurethane molded product according to any one of claims 1 to 7, wherein the polyisocyanate compound (c) is an aromatic polyisocyanate.   The polyurethane molded product according to any one of claims 1 to 8, wherein the chain extender (d) is a polyamine compound.   The polyurethane molded object whose molded object of Claims 1-9 is a polyurethane film.   The polyurethane molded object whose molded object of Claims 1-9 is a polyurethane fiber.   After obtaining a polyol mixture by mixing organopolysiloxane (a) and polyether polyol (b), a polyurethane obtained by reacting the mixture with polyisocyanate compound (c) and chain extender (d) is used. The polyurethane molded product according to any one of claims 1 to 11, wherein A polyurethane obtained by using a polyol mixture mixed or dispersed by introducing an organopolysiloxane (a) and a polyether polyol (b) from separate lines is used. The polyurethane molded product according to any one of the above.