JP2015199898A - Polyurethane resin having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin excellent in heat resistance and cold resistance and having wide usable temperature range.SOLUTION: A polyol component containing fluorene compound represented by the formula (1) and polycarbonate polyol and polyisocyanate component are reacted to obtain a polyurethane resin. In the formula (1), Zand Zrepresent aromatic hydrocarbon rings, Rand Rrepresent substituents, k1 and k2 represent each an integer of 0 to 4, Rand Rrepresent alkylene groups, m1 and m2 represent each an integer of 0 or more, n1 and n2 represent each an integer of 1 or more, Rand Rrepresent substituents, and p1 and p2 represent each an integer of 0 or more.

Description

  The present invention relates to a polyurethane resin having a polycarbonate unit and a fluorene skeleton (for example, a 9,9-bisarylfluorene skeleton).

  A compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) is known to have an excellent function in terms of refractive index, heat resistance, and the like. A polyurethane resin using a fluorene compound having such an excellent function as a diol component is known.

  For example, JP-A-8-3260 (Patent Document 1) discloses 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) and a specific diisocyanate (hexamethylene diisocyanate, tolylene diisocyanate). And polyurethanes by reaction with xylylene diisocyanate and the like. JP-A-11-158245 (Patent Document 2) describes a polyurethane using 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene instead of BPEF of Patent Document 1. . Japanese Patent Laid-Open No. 11-349657 (Patent Document 3) describes that the polyurethanes described in Patent Documents 1 and 2 are used at a low temperature.

Japanese Patent Application Laid-Open No. 2001-2751 (Patent Document 4) describes a polyurethane using 9,9-bis [hydroxyC _1-10 alkyl] fluorene as a diol component.

  These polyurethanes are excellent in heat resistance and optical properties. In addition, the polyurethanes described in Patent Documents 1 and 2 have improved properties at low temperatures. However, the mechanical properties at low temperatures are still not sufficient.

Japanese Patent Application Laid-Open No. 2000-44644 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2000-44645 (Patent Document 6) describe (1) poly for improving low-temperature characteristics (strength and low shrinkage in a low-temperature region). an isocyanate, (3) polytetramethylene ether glycol (PTMG), or poly C _2-3 by reacting an alkylene glycol to produce a prepolymer, and the prepolymer, the polyurethane is reacted with (2) BPEF It is described to obtain. These documents also describe that the molar ratio of (2) BPEF to (3) dihydroxy compound is 5:95 to 95: 5. Patent Document 5 also exemplifies polycarbonate diol, polyester carbonate diol, polyester diol, and polycaprolactone diol together with PTMG.

  However, even the polyurethanes described in these documents still have insufficient low temperature characteristics. In particular, the mechanical strength at high and low temperatures decreases, and the temperature range (usable temperature range) in which continuous use is possible is limited.

JP-A-8-3260 (Claims, Examples) JP-A-11-158245 (Claims, Examples) JP-A-11-349657 (Claims, Examples) JP 2001-2751 A (Claims, Examples) JP 2000-44644 A (Claims, Examples) JP 2000-44645 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide a polyurethane resin having improved heat resistance and cold resistance and having a wide continuous usable temperature range, and a method for producing the same.

  Another object of the present invention is to provide a polyurethane resin having improved heat resistance and cold resistance even when the content of the fluorene skeleton (9,9-bisarylfluorene skeleton) is small, and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have introduced a fluorene skeleton that is expected to be rigid and have low cold resistance when a polyurethane resin is synthesized by combining a polyol having a fluorene skeleton with a polycarbonate polyol. However, the temperature range (usable temperature range) that can be continuously used has been greatly expanded, and it has been found that high mechanical properties can be maintained even at high and low temperatures, and the present invention has been completed.

  That is, the polyurethane resin of the present invention is a polyurethane resin obtained by a reaction between a polyol component and a polyisocyanate component, and the polyol component contains a fluorene compound represented by the following formula (1) and a polycarbonate polyol. Yes.

(In the formula, Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b are substituents, k1 and k2 are integers of 0 to 4, R ^2a and R ^2b are alkylene groups, and m1 and m2 are respectively An integer of 0 or more, n1 and n2 are each an integer of 1 or more, R ^3a and R ^3b are substituents, and p1 and p2 are each an integer of 0 or more)

In the formula (1), Z ¹ and Z ² may be a benzene ring, a naphthalene ring, a biphenyl ring, or the like; k1 and k2 may be 0 or 1, and R ^2a and R ^2b are the same as each other Or different C _2-4 alkylene groups, m1 and m2 may each be an integer of 1 to 20, n1 and n2 may each be 1; R ^3a and R ^3b may be alkyl groups or aryl groups, and p1 and p2 may be 0 to 0 It may be an integer of 2.

The polycarbonate polyol may be a diol comprising a single or copolymerized polycarbonate diol having C _2-12 alkylene-carbonate units. The molar ratio between the fluorene compound represented by the formula (1) and the polycarbonate polyol may be, for example, the former / the latter = 1/99 to 50/50.

  The polyisocyanate component may contain, for example, at least one selected from aromatic polyisocyanates and araliphatic polyisocyanates.

  The present invention also provides a method for producing a polyurethane resin by reacting a molded article formed of the polyurethane resin; a fluorene compound represented by the formula (1); a polyol component containing a polycarbonate polyol; and a polyisocyanate component. Include.

  Since the polyurethane resin of the present invention uses a combination of the fluorene polyol of the formula (1) and the polycarbonate polyol as the polyol component, the heat resistance and cold resistance are improved, and the continuous usable temperature range can be greatly expanded. For example, mechanical properties at room temperature (eg, tensile strength, elastic modulus, elongation at break, etc., particularly tensile strength) can be maintained even after a thermal history in a low temperature environment. In particular, even when the content of the rigid fluorene skeleton (9,9-bisarylfluorene skeleton) is small, heat resistance and cold resistance can be improved.

[Polyol component]
(Fluorene compound)
The polyol component contains a fluorene compound (fluorene polyol) represented by the following formula (1).

(In the formula, Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b are substituents, k1 and k2 are integers of 0 to 4, R ^2a and R ^2b are alkylene groups, and m1 and m2 are respectively An integer of 0 or more, n1 and n2 are each an integer of 1 or more, R ^3a and R ^3b are substituents, and p1 and p2 are each an integer of 0 or more)

In the above formula (1), examples of the aromatic hydrocarbon rings Z ¹ and Z ² include a benzene ring, a condensed polycyclic arene ring, and a ring assembly arene ring. Examples of the condensed polycyclic arene ring include a condensed bicyclic arene ring (for example, a C _10-16 condensed bicyclic arene ring such as a naphthalene ring), a condensed tricyclic arene ring (for example, an anthracene ring, a phenanthrene ring, etc.) And fused bicyclic to tetracyclic arene rings. Examples of the ring assembly arene ring include bi or ter C _6-10 arene rings such as a biphenyl ring, a terphenyl ring, and a binaphthyl ring. Representative aromatic hydrocarbon rings Z ¹ and Z ² are a benzene ring, a naphthalene ring, an anthracene ring, and a biphenyl ring (particularly, a benzene ring, a naphthalene ring, and a biphenyl ring). Note that the types of Z ¹ and Z ² may be the same or different from each other.

In the formula (1), the groups R ^1a and R ^1b include a substituent inert to the reaction, such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a carboxyl group, an alkyl group (methyl). Group, C _1-6 alkyl group such as ethyl group, propyl group, isopropyl group, butyl group and t-butyl group), aryl group (C _6-10 aryl group such as phenyl group) and the like. The groups R ^1a and R ^1b are often alkyl groups (eg, C _1-4 alkyl groups, particularly C _1-3 alkyl groups such as methyl groups) and the like. The bonding positions of the groups R ^1a and R ^1b may be, for example, the 2-position, 7-position, 2- and 7-position of the fluorene ring. Further, the types of R ^1a and R ^1b may be the same or different from each other.

  The coefficients k1 and k2 are each an integer of 0 to 4 (preferably an integer of 0 to 2, particularly 0 or 1). k1 and k2 may be the same or different from each other.

In the formula (1), examples of the alkylene group represented by R ^2a and R ^2b include an ethylene group, a propylene group, a trimethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, and a tetramethylene group. C _2-6 alkylene group (preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group).

The coefficients m1 and m2 may each be an integer of 0 or more (for example, an integer of about 0 to 20), and are usually 0 or an integer of 1 to 15 (preferably an integer of 0 or 1 to 10, more preferably May be about 0 or an integer of 1 to 6, particularly about 0 or an integer of 1 to 5. The coefficients m1 and m2 may be the same or different from each other. When the coefficients m1 and m2 are each 2 or more, R ^2a and R ^2b may form the same or different repeating units of oxyalkylene groups. From the viewpoint that cold resistance can be imparted due to the flexible molecular structure of the oxyalkylene group (particularly, Tg can be lowered), the coefficients m1 and m2 are each an integer of 2 or more (for example, an integer of 2 to 20, preferably 3). It is preferable that it is an integer of 10 to 10, more preferably an integer of 3 to 7 (for example, 4 or 5).

  When the oxyalkylene group forms a plurality of repeating units, the coefficients m1 and m2 may be average values. The coefficients m1 and m2 may each be 0 or more (for example, about 0 to 20) as an average value, and usually 0 to 15 (preferably 0 to 10, more preferably 0 to 6, particularly 0 to 5). ) Degree. From the viewpoint that cold resistance can be imparted due to the flexible molecular structure of the oxyalkylene group (particularly, Tg can be lowered), the average values of the coefficients m1 and m2 are each 2 or more (for example, 2 to 20, preferably It is preferable that it is 3-10, More preferably, it is 3-7 (for example, 4-5).

The types of R ^2a and R ^2b may be the same or different from each other. For example, the groups [— (R ^2a O) _m1 —H] and [— (R ^2b O) _m2 —H] in the formula (1) are represented by the following formulas (1a-1) and (1b-1), respectively. You can also

^Wherein R ^2a1 and R ^2a2 correspond to R ^2a in the formula (1) and represent different alkylene groups, and R ^2b1 and R ^2b2 correspond to R ^2b in the formula (1) and different alkylene And m11, m12, m21 and m22 represent an integer of 1 or more)

Examples of combinations of different alkylene groups include, for example, a combination of a linear alkylene group such as an ethylene group (first alkylene group) and a branched alkylene group such as a propylene group (second alkylene group), an ethylene group And a combination of a C _2-3 alkylene group having a small carbon number (first alkylene group) and a C _4-6 alkylene group having a large carbon number (second alkylene group). In the formula (1a-1) and (1b-1), R ^2a1 and R ^2b1 may be one alkylene group of the first alkylene group and a second alkylene group, R ^2a2 and R ^2b2 are The other alkylene group may be used. For ^{example, R 2a1} and ^{R 2b1} may be an ethylene ^{group, R 2a2} and ^{R 2b2} may be a propylene group.

  Further, m11 and m21 (and m12 and m22) may each have an average value of about 1 to 15, and may be usually about 1 to 10, and preferably about 1 to 8. Specifically, for example, m11 and m21 may each be about 1 to 10 (for example, 1 to 5, preferably 1 to 3) as an average value, and m12 and m22 may each be an average value. It may be about 1 to 15 (for example, 2 to 10, preferably 2 to 8). In addition, the said average value is an arithmetic average value or arithmetic average value from the consumption of reaction components (alkylene oxide, haloalkanol, etc.) in the usual method, for example, the synthesis | combination of the fluorene compound represented by Formula (1). It can be calculated.

In the above formula (1), the number of substitutions n1 and n2 can be selected from the range of about 1 to 4, respectively, depending on the type of Z ¹ and Z ² , for example, and is usually 1 or 2, particularly 1. May be. The substitution position of the group [H— (OR ^2a ) _m1 —O—] or [H— (OR ^2b ) _m2 —O—] (sometimes referred to as a hydroxyl group-containing group) depends on the type of Z ¹ or Z ² , etc. Can be substituted at an appropriate position, for example, when Z ¹ or Z ² is a benzene ring and n1 or n2 is 1, substitution at the 2-position to 6-position (particularly 4-position) of the phenyl group And when Z ¹ or Z ² is a naphthalene ring and n1 or n2 is 1, the 4-position to 8-position (eg, 4-position, 5-position, 6-position) of the naphthyl group ) In many cases.

Examples of the substituent R ^3a and R ^3b include an alkyl group (for example, a C _1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group), a cycloalkyl group (a cyclohexyl group). C _5-8 cycloalkyl group, etc.), aryl groups (eg, C _6-10 aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, etc.), aralkyl groups (C, such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as _6-10 aryl-C _1-4 alkyl group); alkoxy groups (such as C _1-6 alkoxy groups such as methoxy group, ethoxy group), cycloalkyloxy groups (C such as cyclohexyloxy group) _5-8 cycloalkyloxy groups, etc.), aryloxy groups (C _6-10 aryloxy groups such as phenoxy groups), aralkyl Oxy group (C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group); alkylthio group (such as C _1-8 alkylthio group such as methylthio group); acyl group (C _1-6 such as acetyl group) An alkoxycarbonyl group (such as a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a nitro group; a cyano group; dialkylamino group (e.g., di-C _1-4 alkylamino group such as dimethylamino group); dialkyl carbonyl amino group (e.g., di-C _1-4 alkyl, such as di-acetylamino group - carbonyl amino group), and others .

Preferred groups R ^3a and R ^3b are, for example, a C _1-6 alkyl group (preferably a C _1-4 alkyl group (especially a methyl group)), a C _5-8 cycloalkyl group, a C _6-10 aryl group (especially a phenyl group). Group), a C _6-8 aryl-C _1-2 alkyl group, a C _1-4 alkoxy group, and the like. When the groups R ^3a and R ^3b are aryl groups, the groups R ^3a and R ^3b may form the ring assembly arene ring together with the ring Z ¹ and the ring Z ² , respectively. Furthermore, the types of R ^3a and R ^3b may be the same or different from each other.

  Each of the substitution numbers p1 and p2 may be, for example, an integer of 0 to 4 (eg, an integer of 0 to 3), preferably an integer of 0 to 2 (eg, 0 or 1). The substitution numbers p1 and p2 may be the same or different from each other.

Representative compounds in which m1 and m2 are each “0” in formula (1) include (a) 9,9-bis (hydroxyarene) fluorene in which n1 and n2 are “1”, for example, 9,9 -Bisphenolfluorene (BPF), 9,9-biscresol fluorene (BCF), 9,9-bisxylenol fluorene (BXF), 9,9-bisnaphthol fluorene (9,9-bis (6-hydroxy-2-naphthyl) ) 9,9-bis (hydroxy C _6-12 arene) optionally substituted by groups R ^3a and R ^3b such as BNF), such as fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene Fluorene; 9,9-bis (C _6-12 aryl) such as 9,9-bis (4-phenyl-3-hydroxyphenyl) fluorene (BOPPF) Le - hydroxy _{C 6-12} aryl) fluorene; (b) n1 and n2 is 2 9,9-bis (hydroxymethyl arene) fluorene, e.g., 9,9-bis catechol fluorene [e.g., 9,9-bis Examples include 9,9-bis (dihydroxyC _6-12 aryl) fluorene such as (3,4-dihydroxyphenyl) fluorene and the like.

As a typical compound in which m1 and m2 are each an integer of 1 or more in the formula (1), an alkylene oxide adduct (or a reaction product of a hydroxyalkylarene and fluorene, a reaction with a haloalkanol with respect to the compound exemplified above) Products), for example, (c) 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), 9,9-bis (5- (2-hydroxyethoxy) naphthyl) fluorene [9, 9,9-bis [((9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, etc.)) Hydroxyethoxy) C _6-12 aryl] fluorene, 9,9-bis (4-phenyl-3- (2-hydroxyethoxy) fe Nyl) fluorene and other hydroxyethoxy compounds such as 9,9-bis (C _6-12 aryl- (hydroxyethoxy) C _6-12 aryl) fluorene; and hydroxypropoxy compounds and hydroxybutoxy compounds corresponding to these compounds _2-6 alkoxy forms; Furthermore, (d) hydroxy-polyoxy C _2-6 alkoxy forms corresponding to these compounds can be exemplified.

In the formula (1), examples of specific compounds in which k1, k2, p1, and p2 are “0” and n1 and n2 are “1” include the compounds shown in Table 1. In Table 1, the substitution position indicates the substitution position of the hydroxy group-containing group with respect to ring Z ¹ and ring Z ² . ^{Also, R 2a1} and ^{R 2b1} and ^{R 2a2} and ^R 2b2, m11 + m21, and m12 + m22 shows the formula (1a-1) each represents an alkylene group and an average value in (1b-1).

In addition, the fluorene compound represented by Formula (1) may use a commercial item, for example, a conventional method, for example, fluorenone and an arene having a hydroxy group or a hydroxyalkyl group corresponding to the hydroxy group-containing group. A method of reacting in the presence of an acid catalyst and a mercapto compound; 9,9-bis (hydroxyaryl) fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene, etc.] and 9,9-bis (hydroxy-alkoxy) aryl) fluorene, alkylene oxide (e.g., corresponding to groups oR ^2a or a group oR ^2b, a method of ethylene oxide, propylene oxide, butylene oxide, etc.) or an alkylene carbonate (e.g., ethylene carbonate, propylene carbonate, the reaction of butylene carbonate) It may be prepared.

(Polycarbonate polyol)
Polycarbonate polyol is preferably used because it is superior to other polyol components such as polyether polyol and polyester polyol in terms of mechanical properties, heat resistance, and heat and humidity resistance when introduced into a polyurethane resin. Furthermore, in the present invention, a polyurethane resin having a wide usable temperature range can be obtained by combining with the fluorene compound represented by the formula (1).

Polycarbonate polyol can be obtained by a conventional method, for example, reaction of polyol diol and alkylene carbonate, and diol is widely used as the polyol. The diol often contains at least an aliphatic diol. Examples of the aliphatic diol include linear or branched diols such as alkane diols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, methylpentanediol, octanediol, nonanediol, decanediol, dodecanediol, and other _C2-16 alkanediols, preferably _C2-12 alkanediols, more preferably _C2-10 alkanediols) And polyalkane diols (for example, di- or tri-C _2-4 alkane diols such as diethylene glycol, dipropylene glycol, and triethylene glycol). These diols can be used alone or in combination of two or more.

  If necessary, the aliphatic diol may be an alicyclic diol (for example, a cycloalkanediol such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, an alkylene oxide adduct of hydrogenated bisphenols, etc. ), Aromatic diols (1,4-benzenedimethanol, bisphenols, alkylene oxide adducts of bisphenols, etc.) may be used in combination.

Examples of the alkylene carbonate include C _2-6 alkylene carbonate (preferably C _2-4 alkylene carbonate, particularly C _2-3 alkylene carbonate) such as ethylene carbonate, propylene carbonate, and butylene carbonate. These alkylene carbonates can also be used alone or in combination of two or more. In addition, you may use diphenyl carbonate etc. together as needed.

  The polycarbonate polyol (particularly, diol) may have a cycloalkylene carbonate unit or an arylene carbonate unit, if necessary, and may be a homopolymer or a copolymer. Specific examples of the polycarbonate polyol (particularly diol) include polybutylene carbonate, polyhexamethylene carbonate, polymethylpentylene carbonate, polyoctamethylene carbonate, polynonamethylene carbonate, and the like. These polycarbonate polyols (particularly diols) can be used alone or in combination of two or more.

Preferred polycarbonate polyols usually comprise polycarbonate diols having at least alkylene carbonate units (C _2-12 alkylene-carbonate units, preferably C _4-12 alkylene-carbonate units, more preferably C _6-10 alkylene-carbonate units). It is out. Further, the polycarbonate diol is often a single or copolymerized polycarbonate diol of the diol component and / or alkylene carbonate.

  The number average molecular weight of the polycarbonate polyol is not particularly limited, and may be, for example, about 100 to 10000 (for example, 200 to 7000), preferably about 300 to 5000 (for example, 400 to 3000).

  From the viewpoint of heat resistance and cold resistance, the ratio (molar ratio) between the fluorene compound represented by the formula (1) and the polycarbonate polyol is, for example, the former / the latter = 1/99 to 50/50 (for example, 5 / 95-50 / 50), preferably 10 / 90-45 / 55 (for example, 15 / 85-45 / 55), more preferably about 20 / 80-40 / 60 (for example, 25 / 75-40 / 60) It may be. If the amount of the fluorene compound represented by the formula (1) is too small, the heat resistance and mechanical properties are not improved so much, and the mechanical properties easily change with respect to the thermal history. It may be difficult to maintain the characteristics (particularly, tensile strength). On the other hand, if the amount is too large, the ratio of the rigid fluorene skeleton increases, so that the glass transition temperature (Tg) increases and the cold resistance may decrease.

Polycarbonate polyol is polymer polyol such as polyether polyol (polyether diol such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene oxide-polypropylene oxide block copolymer), polyester polyol (polyethylene if necessary). Ring-opening polymers such as adipate, polydiethylene adipate, polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, polycaprolactone, polyester diols such as these copolymers), polyolefin polyols (polybutadiene diol, poly It may be used in combination with isobutylene diol etc.). The number average molecular weight of the polymer polyol may be, for example, 200 to 7000 (for example, 250 to 5000), preferably about 300 to 3000. Furthermore, the polycarbonate polyol is optionally a low molecular weight reaction component (polyol) such as alkanediol (ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, C _2-12 alkanediols such as 1,7-heptanediol and 1,8-octanediol), polyalkanediols (eg, diethylene glycol, triethylene glycol, etc.), cycloalkanediols (cyclohexanediol, cyclohexanedimethanol, etc.); Alkanetriol (eg, glycerin, trimethylolethane, trimethylolpropane, etc.); Amines (alkylamines such as methylamine, alkylenediamines such as ethylenediamine, diethano Ruamine, etc.); may be used in combination with dihydroxyalkanecarboxylic acid such as 2,2-dimethylolpropionic acid. The molecular weight of the low molecular weight reaction component may be, for example, about 66 to 200 (for example, 66 to 150), preferably about 66 to 120.

  In addition, the ratio of the fluorene compound with respect to the whole polyol component can be selected from the range of about 5-60 mol%, for example, Usually, 10-50 mol% (for example, 15-45 mol%), Preferably it is 20-40 mol%. It may be a degree.

[Polyisocyanate component]
As the polyisocyanate component, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate and the like can be used. As the polyisocyanate component, diisocyanate is usually used.

Examples of the aliphatic diisocyanate include C _2-12 alkane-diisocyanate such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. .

  Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate, IPDI), methylene bis (cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate (hydrogenated). MDI), bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), norbornane diisocyanate, and the like.

  Examples of the aromatic diisocyanate include phenylene diisocyanate, tolylene diisocyanate (TDI), 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), and 4,4′-toluidine. Examples include diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenylsulfone diisocyanate, and the like.

  Examples of the araliphatic diisocyanate include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and ω, ω′-diisocyanate-1,4-diethylbenzene.

  The polyisocyanate component may be a modified body, for example, a multimer (such as a dimer or trimer), a carbodiimide body, a biuret body, an allophanate body, or a uretdione body.

  These polyisocyanate components can be used alone or in combination of two or more. Furthermore, you may use trifunctional or more polyisocyanate together as needed.

  A preferred polyisocyanate component is at least one selected from araliphatic diisocyanates (for example, XDI, TMXDI, etc.) and aromatic diisocyanates (for example, MDI, TDI, NDI) from the viewpoint of improving heat resistance. In particular, at least aromatic diisocyanate is often used.

[Polyurethane resin and method for producing the same]
The polyurethane resin of this invention can be manufactured by making the said polyol component (especially diol component) containing the fluorene compound represented by the said Formula (1) and a polycarbonate polyol react with a polyisocyanate component (especially diisocyanate component). . In this reaction, the ratio of the polyol component and the polyisocyanate component is not particularly limited. For example, the ratio of the isocyanate group of the polyisocyanate component is 0.7 to 1. The amount is about 5 mol, preferably about 0.8 to 1.3 mol, particularly about 0.9 to 1.1 mol (approximately 1 mol).

  In such a reaction, one of the fluorene compound and the polycarbonate polyol is reacted with a polyisocyanate component to prepare a prepolymer having an isocyanate group at the terminal, and this prepolymer is reacted with the other polyol component. A polyurethane resin may be prepared. Further, a prepolymer having an isocyanate group at the terminal is prepared by reacting all polyol components including a fluorene compound and a polycarbonate polyol with a polyisocyanate component, and this prepolymer and the low molecular weight reaction component as a chain extender; May be reacted. Furthermore, the polyurethane resin may be prepared by introducing all reaction components into the reaction system and reacting all polyol components including the fluorene compound and polycarbonate polyol with the polyisocyanate component. In addition, you may use a polyisocyanate component for the preparation of a prepolymer in the ratio of about 1.8-2.2 mol as a density | concentration of an isocyanate group with respect to 1 mol of hydroxyl groups of a polyol component.

  The polyurethane resin obtained by such a reaction has at least a structural unit represented by the following formulas (2a) and (2b).

(In the formula, A represents the residue of diisocyanate, R ⁵ represents the residue of diol of polycarbonate polyol, q represents the degree of polymerization of polycarbonate polyol, and is an integer of 1 or more, Z ¹ , Z ² R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1, k2, m1, m2, p1, and p2 are the same as above.)

  The reaction may be performed in the presence of a catalyst. Examples of the catalyst include organometallic catalysts such as organotin compounds (such as tin octylate, dibutyltin diacetate, and dibutyltin dilaurate), metal naphthenates (such as copper naphthenate, zinc naphthenate, and cobalt naphthenate); And the like (for example, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine; cyclic tertiary amines such as pyridine, N, N-dimethylpiperazine, and triethylenediamine). These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used may be, for example, about 0.001 to 3 parts by weight (for example, 0.01 to 1 part by weight) with respect to 100 parts by weight of the total amount of the polyol component and the polyisocyanate component.

  The reaction may be performed in the absence or presence of a solvent. Examples of the solvent include ethers (for example, dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane and tetrahydrofuran), ketones (for example, acetone, methyl ethyl ketone, diisopropyl ketone, isobutyl methyl). Dialkyl ketones such as ketones), esters (eg, acetates such as methyl acetate, ethyl acetate, and butyl acetate), hydrocarbons (eg, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene), halogens System solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene), nitriles (acetonitrile, etc.) and the like. These solvents may be used alone or in combination of two or more.

  The reaction is carried out in an inert atmosphere (atmosphere such as nitrogen, helium, or argon) at room temperature or under heating (for example, 40 to 150 ° C, preferably 50 to 120 ° C, more preferably about 60 to 100 ° C). It may be performed under reflux.

  After completion of the reaction, the polyurethane resin can be separated and purified by a conventional separation method, for example, separation means such as reprecipitation with a poor solvent, concentration and filtration, or a separation means combining these.

  The polystyrene-reduced weight average molecular weight of the polyurethane resin is, for example, about 5000 to 100000 (preferably 10,000 to 80000, more preferably 15000 to 60000, particularly preferably 20000 to 50000) in gel permeation chromatography (GPC). May be.

  The polyurethane resin of the present invention usually forms a polyurethane elastomer and has high heat resistance and cold resistance and flexibility. For example, a decrease in mechanical strength at a high temperature (for example, a temperature of 80 ° C. or higher) and a low temperature (for example, a temperature of 0 ° C. or lower) can be suppressed. In particular, since the polyol component contains the fluorene polyol represented by the formula (1) in addition to the polycarbonate polyol, the mechanical properties (tensile strength, elastic modulus) can be improved, and the polyurethane resin using the polycarbonate polyol is effective. Can be modified. The tensile strength is, for example, about 0.2 to 30 MPa, preferably about 0.3 to 10 MPa, and more preferably about 0.4 to 1 MPa when measured by returning from −20 ° C. (for example after storage for 280 hours) to room temperature. There may be.

Furthermore, the polyurethane resin of the present invention is not easily affected by thermal history particularly in a low temperature (for example, −20 ° C.) environment, and has mechanical properties (for example, tensile strength, elastic modulus, elongation at break, especially tensile strength). Easy to hold. When the tensile strength of the polyurethane resin measured at −20 ° C. (for example after storage for 280 hours) after returning to room temperature is T ₋₂₀ and the tensile strength at room temperature is T _rt , the tensile strength ratio T ₋₂₀ / T _rt may be, for example, about 0.5 to 2.0, preferably about 0.7 to 1.7, and more preferably about 0.9 to 1.4.

In addition, the polyurethane resin of the present invention has relatively high heat resistance even if it contains (poly) oxyalkylene units (— (OR ^2a ) _m1 — and — (OR ^2b ) _m2 —) in formula (1). doing. The glass transition temperature of the polyurethane resin is, for example, 40 ° C. or less (for example, −50 ° C. to 35 ° C.), preferably 30 ° C. or less (for example, −50 ° C. to 30 ° C.), and more preferably −10 ° C. or less (for example, It may be about −50 ° C. to −20 ° C.). Furthermore, the glass transition temperature of the polyurethane resin having higher cold resistance is, for example, 0 ° C. or lower (for example, −70 ° C. to −5 ° C.), preferably −15 ° C. or lower (for example, −65 ° C. to −20 ° C.). ), More preferably about −25 ° C. or less (for example, −60 ° C. to −30 ° C.).

[Molded body]
Since the polyurethane resin of the present invention is excellent in heat resistance and cold resistance, it can be formed and used in various applications. The shape of the molded body is not particularly limited, and may be, for example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular shape, rod shape, tube shape, hollow shape, etc.), etc. Good.

  What is necessary is just to form a molded object with the said polyurethane resin, and may form it with the resin composition containing the said polyurethane resin. Such resin compositions include various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat Stabilizers, etc.), mold release agents, antistatic agents, dispersants, leveling agents, surface modifiers, heat resistance improvers, carbon materials, etc.]. These additives may be used alone or in combination of two or more.

  The molded body can be produced using, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, or the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In the examples, various physical properties and evaluations were performed as follows.

(Molecular weight)
The weight average molecular weight Mw (polystyrene conversion) was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8320GPC type, eluent: tetrahydrofuran (reagent special grade)). In addition, the analytical sample prepared the tetrahydrofuran solution which contains a polyurethane by the density | concentration 0.1%, and filtered and used it with the membrane filter (0.45 micrometer). A differential refractometer and an ultraviolet-visible detector (254 nm) were used as the detector, and the measurement flow rate was 1.00 mL / min.

(Glass-transition temperature)
The glass transition temperature Tg was measured with a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., EXTAR DSC 6220). The sample was placed in an aluminum pan and measured at a temperature range of -30 ° C to 150 ° C.

(Tensile strength, elastic modulus and elongation at break)
Using a precision universal testing machine (Shimadzu Corporation “AGS-J 10 kN”), a tensile test was performed on the dumbbell specimen specified in JIS K 7162-5A, and the above characteristics were measured. The measurement was performed at room temperature (20 ° C.) and at −20 ° C. for 280 hours and then returned to room temperature. The elastic modulus was measured at an initial tensile displacement of 2 to 4 mm. In the breaking elongation test, the breaking elongation (unit: mm) of the test piece with respect to the distance of 47 mm between the gripping jigs was measured in the measurement range of 0 to 500 mm.

Comparative Example 1
When a polycarbonate diol (Ube Industries, Ltd., PCD (UH-100)) 160 g and chlorobenzene 1500 ml were added to a separable flask and stirred and dissolved in an argon (Ar) gas stream, the solution temperature reached 94 ° C. Then, a solution of 64.06 g of diphenylmethane diisocyanate (MDI) / 100 ml of chlorobenzene was added. The reaction was started when the solution temperature reached 100 ° C., and sampled after 2.5 hours and 5 hours. GPC was measured to confirm that the MDI peak had disappeared, and heating was stopped 7 hours after the start of the reaction. After allowing to cool, the reaction mixture was quenched by adding 100 ml of methanol. The reaction solution was concentrated to obtain 215.9 g of a viscous product. Since the concentrated product was very viscous, a total of 723 g of dichloromethane was added and dissolved by heating under reflux for a total of 17 hours, and the solution was filled in a bottle. Thereafter, the solution was spread on an aluminum plate covered with a Teflon (registered trademark) sheet, and dried at 100 ° C. under reduced pressure overnight to obtain a plate-like object.

Example 1
Polycarbonate diol (Ube Industries, Ltd., PCD (UH-100)) 245.76 g, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) 4.49 g, chlorobenzene 1400 ml, MDI 64 The reaction was carried out in the same manner as in Comparative Example 1 using a 0.06 g / chlorobenzene 100 ml solution, and the heating was stopped 7 hours after the start of the reaction. After cooling, the reaction was quenched by adding 100 ml of methanol. The viscous material obtained by concentrating the reaction solution was 339.9 g. Then, the viscous body was developed on an aluminum plate with a Teflon sheet and dried under reduced pressure at 100 ° C. overnight to obtain a plate-like target product.

Example 2
Polycarbonate diol (Ube Industries, Ltd., PCD (UH-100)) 204.80 g, BPEF 22.45 g, chlorobenzene 1400 ml, MDI 64.06 g / chlorobenzene 100 ml solution was reacted in the same manner as in Comparative Example 1 and reacted. Heating was stopped in 5 hours from the start. After cooling, the reaction was quenched by adding 100 ml of methanol. The viscous body obtained by concentrating the reaction liquid was 316.5 g. Since the concentrated product was extremely viscous, a total of 656 g of tetrahydrofuran (THF) was added and dissolved by heating under reflux for a total of 8 hours, and filled into a bottle. Thereafter, the solution was spread on an aluminum plate with a Teflon sheet and dried under reduced pressure at 100 ° C. overnight to obtain a plate-like target product.

Example 3
As in Comparative Example 1, a polycarbonate diol (Ube Industries, Ltd., PCD (UH-100)) 153.60 g, BPEF 44.90 g, chlorobenzene 1400 ml, MDI 64.06 g / chlorobenzene 100 ml solution was used in a separable flask. The reaction was continued, and heating was stopped in 7.2 hours from the start of the reaction. After cooling, the reaction was quenched by adding 100 ml of methanol. The viscous body obtained by concentrating the reaction liquid was 324.8 g. Since the concentrated product was very viscous, a total of 710 g of THF was added and dissolved by heating under reflux for a total of 25 hours, and filled in a bottle. Thereafter, the solution was spread on an aluminum plate with a Teflon sheet and dried under reduced pressure at 100 ° C. overnight to obtain a plate-like target product.

Example 4
Add 9.78 g of 9,9-bis (cresol) fluorene (BCF), 82.46 g of polycarbonate diol (manufactured by Ube Industries, PCD (UH-100)), 34.38 g of MDI to a separable flask, and add Ar gas. The mixture was heated to about 60 ° C. under an air stream and melted. Then, the internal temperature of the flask was heated to 125 ° C. while stirring, chlorobenzene was added during the reaction process, and the reaction product was dissolved by heating to an internal temperature of 130 ° C. to react for 10 hours. The reaction solution was concentrated to remove about 300 mL of chlorobenzene, and then reprecipitation with about 2 L of methanol and decantation were repeated twice. The polymer layer was spread on a Teflon sheet and dried overnight at 100 ° C. under reduced pressure and dried by heating to obtain 125.3 g of a brown solid.

Example 5
9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) 1 in the same manner as in Example 1 of JP-A-2001-139651 9 mol of ethylene oxide (EO) was reacted with respect to mol to obtain an ethylene oxide adduct (hereinafter simply referred to as BPEF-9EO).

  BPEF-9EO 28.67 g, polycarbonate diol (manufactured by Ube Industries, PCD (UH-100)) 136.49 g, MDI 42.7 g, chlorobenzene were weighed and added to a separable flask and stirred under an Ar gas stream The temperature was raised to 120 ° C. to start the reaction, and the reaction was completed within 5 hours from the start of the reaction. The solution was concentrated to remove 409.6 mL of chlorobenzene, and then reprecipitated with about 2 L of methanol and decanted. About 2 L of methanol was again added to the white viscous material (polymer) remaining in the container, kneaded and washed, and then decanted. The polymer layer was spread on a Teflon sheet, and the product was obtained by drying at 100 ° C. under reduced pressure and heating overnight.

Example 6
BPEF-9EO 57.63 g, polycarbonate diol (manufactured by Ube Industries, PCD (UH-100)) 102.5 g, MDI 42.86 g, chlorobenzene were added to the separable flask and stirred under an Ar gas stream. The reaction was started by raising the temperature to 100 ° C. After 5.5 hours from the start of the reaction, the internal temperature was heated to 120 ° C. for 19 hours to complete the reaction. The solution was concentrated to remove about 500 mL of chlorobenzene, and then reprecipitated with 2 L of methanol and decanted. About 2 L of methanol was added again to the white viscous material (polymer) remaining in the container, kneaded and washed, and then decanted. The polymer layer was spread on a Teflon sheet, and heated and dried under reduced pressure at 100 ° C. overnight to obtain the desired product.

Example 7
In the same manner as in Example 1 of JP-A-2001-139651, 10 mol of propylene oxide (PO) was reacted with 1 mol of BPEF to obtain a propylene oxide adduct (hereinafter simply referred to as BPEF-10PO). .

  BPEF-10PO 34.76 g, polycarbonate diol (manufactured by Ube Industries, PCD (UH-100)) 136.56 g, MDI 42.79 g, chlorobenzene were weighed and added to a separable flask, and stirred under an Ar gas stream. The temperature was raised to 120 ° C. to start the reaction, and the reaction was completed in 6 hours after the start of the reaction. In addition, the ratio of the said component is equivalent to 20 mol% of BPEF-10PO, 80 mol% of polycarbonate diol (PCD (UH-100)), and 100 mol% of MDI.

  The reaction solution was concentrated to remove 367.4 mL of chlorobenzene, and then reprecipitated with about 2 L of methanol and decanted. About 2 L of methanol was again added to the white viscous body of the polymer layer, and the mixture was stirred, washed, and decanted to obtain 203.64 g of a transparent solid. The polymer layer was spread on a Teflon sheet, and the product was obtained by drying at 100 ° C. under reduced pressure and heating overnight.

  The obtained polyurethane resin was jelly or gummy at room temperature. Therefore, it is expected to be used as an elastic body, a heat insulating material, etc. at a low temperature.

Example 8
BPEF-10PO 69.62 g, polycarbonate diol (Ube Industries, Ltd., PCD (UH-100)) 102.59 g, MDI 42.88 g, chlorobenzene were added to the separable flask and stirred under an Ar gas stream. The temperature was raised to 120 ° C. to start the reaction, and the reaction was completed 5 hours after the start of the reaction. In addition, the ratio of the said component is equivalent to 40 mol% of BPEF-10PO, 60 mol% of polycarbonate diol (PCD (UH-100)), and 100 mol% of MDI.

  The reaction solution was concentrated to remove about 400 mL of chlorobenzene, and then reprecipitated with about 2 L of methanol and decanted. About 2 L of methanol was added again to the white viscous material (polymer) remaining in the container, kneaded and washed, followed by decantation. The polymer layer was spread on a Teflon sheet, and the product was obtained by drying at 100 ° C. under reduced pressure and heating overnight.

  The obtained polyurethane resin was jelly or gummy at room temperature. Therefore, it is expected to be used as an elastic body, a heat insulating material, etc. at low temperatures.

  When the characteristic of the polyurethane resin obtained by the Example and the comparative example was measured, the result shown in Tables 2-5 was obtained. In Table 2, “-” in the column of Tg indicates that it was not detected in the measurement temperature range (Tg <−30 ° C.). In Tables 3 to 5, “No measurement” in the columns of tensile strength, elastic modulus, and elongation at break can be measured because the test piece at room temperature is in a jelly or gummy shape, and the test piece is cut by a gripping jig. Indicates no.

  As is apparent from the examples, when a diol having a fluorene skeleton is used as the diol component, the tensile strength and elastic modulus can be improved, the elongation at break is reduced, and the polycarbonate polyol type polyurethane resin can be effectively modified. Further, in Comparative Example 1, the mechanical properties (particularly tensile strength) at room temperature cannot be maintained because voids are generated inside due to the influence of the thermal history at low temperature and necking occurs. In contrast, the embodiment is less susceptible to thermal history at low temperatures, can maintain the mechanical characteristics at room temperature, and greatly expands the temperature range (usable temperature range) that can be used continuously. be able to. Furthermore, when a diol having a fluorene skeleton having a repeating unit of a (poly) oxyalkylene group is used, not only is the fluorene skeleton rigid, but it is not easily affected by heat history, and cold resistance is imparted (lower Tg). ), And the usable temperature range can be expanded to a lower temperature environment.

  The polyurethane resin (or composition thereof) of the present invention can be used in various applications, for example, transport and storage members or units of low-temperature fluids such as liquefied natural gas and natural gas of 0 ° C. or lower [for example, low-temperature fluid piping or piping members , Storage containers, transport vessels, etc.) and coating materials (for example, coating agents for LED (light emitting diode) elements, etc.) Coating), interlayer insulating film, solder resist, photo spacer for liquid crystal display, fuel cell film, optical fiber, optical waveguide, hologram, adhesive [for example, optical bonding of optical lens, prism, optical fiber, optical filter, optical waveguide, etc. Agent], keypad, keyboard, touch panel, paint, ink, fiber (spandex), elastomer Cushioning material (such as automotive cushion), artificial, synthetic leather, it can be used tires, belts, sealing materials and packing, shoe soles, such as in furniture, bedding and miscellaneous goods.

Claims (7)

A polyurethane resin obtained by a reaction between a polyol component and a polyisocyanate component, wherein the polyol component comprises a fluorene compound represented by the following formula (1) and a polycarbonate polyol.

(In the formula, Z ¹ and Z ² are aromatic hydrocarbon rings, R ^1a and R ^1b are substituents, k1 and k2 are integers of 0 to 4, R ^2a and R ^2b are alkylene groups, and m1 and m2 are respectively An integer of 0 or more, n1 and n2 are each an integer of 1 or more, R ^3a and R ^3b are substituents, and p1 and p2 are each an integer of 0 or more)   The polyurethane resin according to claim 1, wherein the molar ratio of the fluorene compound represented by the formula (1) to the polycarbonate polyol is the former / the latter = 1/99 to 50/50. In formula (1), Z ¹ and Z ² are a benzene ring, a naphthalene ring or a biphenyl ring; k1 and k2 are 0 or 1, and R ^2a and R ^2b are the same or different C _2-4 alkylene group, The polyurethane resin according to claim 1 or 2, wherein m1 and m2 are each 0 or 1 to 20, n1 and n2 are each 1; R ^3a and R ^3b are alkyl groups or aryl groups, and p1 and p2 are 0 to 2. . The polyurethane resin according to any one of claims 1 to 3, wherein the polycarbonate polyol contains a single or copolymerized polycarbonate diol having a _C2-12 alkylene-carbonate unit.   The polyurethane resin according to any one of claims 1 to 4, wherein the polyisocyanate component contains at least one selected from an aromatic polyisocyanate and an araliphatic polyisocyanate.   The molded object formed with the polyurethane resin in any one of Claims 1-5. A method for producing a polyurethane resin by reacting a fluorene compound represented by the formula (1) according to claim 1, a polyol component containing a polycarbonate polyol, and a polyisocyanate component.