JP2014177621A - Polyurethane resin having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin having a fluorene skeleton having flexibility, handling ability, adhesiveness, scratch resistance and high refractive index.SOLUTION: There is provided a polyurethane resin obtained by reaction of a fluorene compound represented by the formula (1) and a polyisocyanate compound. In the formula (1), where Zand Zrepresent aromatic hydrocarbon rings, R, R, Rand Rrepresent substituents, R, R, Rand Rrepresent alkylene groups, k1 and k2 represent each 0 to 4, n1 and n2 represent each 1 or more, m11, m12, m21, m22, p1 and p2 represent each an integer of 0 or more, but m11+m12+m21+m22 is 3 or more.

Description

  The present invention relates to a polyurethane resin having 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. As a method for expressing such an excellent function of the fluorene skeleton in a resin, a fluorene compound having a reactive group (hydroxyl group, amino group, etc.), for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bis In general, aminophenylfluorene (BAFL), bisphenoxyethanol fluorene (BPEF) or the like is used as a constituent component of the resin, and a fluorene skeleton is introduced into a part of the skeleton structure of the resin.

  A polyurethane using such a polyol having a fluorene skeleton is also known. JP-A-8-3260 (Patent Document 1) discloses 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and specific diisocyanates (hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, etc. Polyurethanes obtained by reaction with) are disclosed.

  JP 2008-101160 A (Patent Document 2) discloses a fluorene skeleton-containing active hydrogen compound [e.g., 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, etc.] and a hydrophilic group. An aqueous polyurethane resin obtained by reacting a containing active hydrogen compound (for example, 2,2-dimethylolpropionic acid) with a polyisocyanate is disclosed.

  However, the polyurethanes of these documents often have insufficient handling properties (for example, poor solvent solubility, poor film formability, etc.), and provide sufficient adhesion to the substrate and sufficient flexibility. It was also difficult.

  On the other hand, JP 2000-44646 A (Patent Document 3) discloses polyisocyanate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, and a specific dihydroxy compound (for example, polybutanediol). ) Are obtained by reacting with (A). In this document, a structure derived from a specific dihydroxy compound is introduced into the polyurethane skeleton in order to maintain strength in a low temperature region. However, even with the polyurethane of this document, there are still cases where handling properties and adhesion to a substrate cannot be improved.

  In 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), the 9,9-bisphenylfluorene skeleton and the hydroxyl group are bonded via an oxyethylene group as an oxyalkylene group. However, some conventional patent documents disclose a structure that assumes not only an oxyalkylene group but also a polyoxyalkylene group as a broad concept including such BPEF. To do.

  For example, JP 2007-91870 A (Patent Document 4) discloses a compound represented by the following formula as a polyfunctional (meth) acrylate constituting a polymerizable composition.

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group, and k 1 and k 2 represent The same or different and an integer of 0 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3, n1 and n2 are the same or different and represent an integer of 0 or 1 and p1 and p2 are the same Or it is different and represents an integer of 1 to 4, where m1 + p1 and m2 + p2 are each an integer of 1 to 5)
However, most of those specifically synthesized in the examples including the above-mentioned Patent Document 4 are only those having an oxyethylene group, and the synthesis and physical properties of an alcohol having a structure bonded via a polyoxyethylene group. The current situation is that no detailed examination has been made.

JP-A-8-3260 (Claims, Examples) JP 2008-101160 A (Claims, Examples) JP 2000-44646 A (Claims, Examples) JP 2007-91870 A (Claims, Examples)

  Accordingly, an object of the present invention is to provide a polyurethane resin having a high handling property (or handling property) even if it contains a fluorene skeleton (9,9-bisarylfluorene skeleton).

  Another object of the present invention is to provide a polyurethane resin having excellent adhesion to a substrate.

  Still another object of the present invention is to provide a polyurethane resin capable of improving or imparting scratch resistance.

  Although the conventional polyol having a fluorene skeleton is defined in a wide range of the number of oxyalkylene groups added as described above, its significance is not known. And practically, there are almost no examples in which the number of oxyalkylene groups added is increased from the viewpoints of high heat resistance and high refractive index, which are required characteristics when a 9,9-bisarylfluorene skeleton is introduced. The current situation is not.

  Under such circumstances, the present inventors have intensively studied to achieve the above-mentioned problem, and as a result, synthesized a polyol having a fluorene skeleton in which the number of oxyalkylene groups added was increased. By using it as a component, it is possible to obtain a polyurethane resin excellent in handling property or handleability compared to the case where a polyoxyalkylene chain is introduced into a polymer skeleton simply using polyalkylene glycol in combination with BPEF, The resulting polyurethane resin has excellent adhesion to the substrate, and also has excellent film-forming properties. Surprisingly, it has scratch resistance, which is a characteristic that is hard to imagine in polyurethane resins having a rigid fluorene skeleton. As a result, 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 compound and a polyisocyanate compound, and the polyol compound contains a fluorene compound represented by the following formula (1).

(Wherein, ^{Z 1} and ^{Z 2} are aromatic hydrocarbon ^{ring, R 1a} and ^{R 1b substituent, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} is an alkylene ^{group, R 3a} and ^{R 3b} are substituents, k1 And k2 are each an integer of 0 to 4, m11, m12, m21 and m22 are each an integer of 0 or more, n1 and n2 are each an integer of 1 or more, and p1 and p2 are each an integer of 0 or more, provided that m11 + m12 + m21 + m22 The average value is 3 or more.)
In the above formula (1), the average value of m11 + m12 + m21 + m22 may be, for example, about 3.5 to 17 (for example, 4 to 15).

Typically, in the formula (1), a ^{Z 1} and ^{Z 2} is a benzene ring or a naphthalene ^{ring, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} are _{C 2-4} alkylene group, the average value of m11 + m12 + m21 + m22 Is about 4.5 to 13, and n1 and n2 may each be 1. In ^{particular, R 2a1,} R ^2b1 is ethylene ^{group, R 2a2} and ^{R 2b2} may be an ethylene or propylene group.

  The polyol compound may further contain another polyol other than the fluorene compound represented by the formula (1) (or not belonging to the category of the fluorene compound represented by the formula (1)). Such other polyols may include, for example, a polyol having a carboxyl group (for example, dihydroxyalkanoic acid), and in particular, may include dimethylolalkanoic acid (for example, dimethylolpropionic acid). . When other polyols are included, the ratio of the fluorene compound and the other polyols may be, for example, the former / the latter (molar ratio) = 95/5 to 20/80.

  The polyisocyanate compound may be an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, or the like, and is particularly selected from araliphatic polyisocyanates and aromatic polyisocyanates. At least one kind may be included.

  The polyisocyanate compound may be a polyisocyanate (particularly diisocyanate) having a relatively large isocyanate group content (for example, about 20 to 60% by weight).

  Typically, the polyisocyanate compound may contain an aromatic diisocyanate having an isocyanate group content of 25 to 55% by weight.

  The present invention also includes a molded body (for example, a film) formed of a polyurethane resin.

  In the present specification, the “fluorene compound represented by the formula (1)” may mean an “aggregate” or “molecular aggregate” of compounds belonging to the category of the formula (1), and m11 + m12 + m21 + m22. Such a value may mean an average value in such “aggregate” or “molecular aggregate”.

  Although the polyurethane resin of the present invention has a fluorene skeleton (9,9-bisarylfluorene skeleton), it has characteristics such as excellent solvent solubility and excellent film formability. (Or sufficient) handling (or handling). And it has the outstanding adhesiveness with respect to a base material. Moreover, even if a polyoxyalkylene group is introduced, characteristics such as a high refractive index derived from a fluorene skeleton are hardly deteriorated. Furthermore, the polyurethane resin of the present invention is surprisingly excellent in scratch resistance. In particular, in the present invention, scratch resistance can be imparted to the polyurethane resin without impairing properties such as a high refractive index. As described above, the polyurethane resin of the present invention has excellent characteristics and is extremely versatile and can be applied to various applications.

  The polyurethane resin of the present invention is a polyurethane resin obtained by a reaction between a specific polyol compound and a polyisocyanate compound.

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

(Wherein, ^{Z 1} and ^{Z 2} are aromatic hydrocarbon ^{ring, R 1a} and ^{R 1b substituent, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} is an alkylene ^{group, R 3a} and ^{R 3b} are substituents, k1 And k2 are each an integer of 0 to 4, m11, m12, m21 and m22 are each an integer of 0 or more, n1 and n2 are each an integer of 1 or more, and p1 and p2 are each an integer of 0 or more, provided that m11 + m12 + m21 + m22 The average value of is 3 or more.)
In the above formula (1), examples of the aromatic hydrocarbon rings Z ¹ and Z ² include a benzene ring and a condensed polycyclic arene ring. As the condensed polycyclic arene ring, a condensed bicyclic arene (for example, a C _8-20 condensed bicyclic arene ring such as naphthalene, preferably a C _10-16 condensed bicyclic arene) ring, a condensed tricyclic arene (For example, anthracene, phenanthrene, etc.) Condensed bi- to tetracyclic arene rings such as a ring are included. Preferred examples of the condensed polycyclic arene ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable.

Typical aromatic hydrocarbon rings are a benzene ring and a naphthalene ring. Z ¹ and Z ² may be the same or different aromatic hydrocarbon rings, and may usually be the same.

In the formula (1), examples of the groups R ^1a and R ^1b include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a carboxyl group, a hydrocarbon group [for example, an alkyl group, an aryl group ( And a hydrocarbon group described later such as a C _6-10 aryl group such as a phenyl group], and the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-12} alkyl group _{(e.g., C 1-8} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. In addition, when k1 or k2 is plural (2 to 4), the plural groups R ^1a or R ^1b may be different from each other or the same. In addition, the groups R ^1a and R ^1b may be the same or different. Moreover, the bonding position (substitution position) of the groups R ^1a and R ^1b is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k1 or k2 is 0 to 1, in particular 0. The substitution numbers k1 and k2 may be the same or different.

In the formula ^(1), the alkylene group represented by ^{R 2a1,} R ^2a2, R ^2b1 and ^{R 2b2,} for example, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl A C _2-6 alkylene group such as a group or a tetramethylene group, preferably a C _2-4 alkylene group, more preferably a C _2-3 alkylene group, particularly an ethylene group or a propylene group. Incidentally, when the coefficient m11, m12, m21 and m22 is 2 or more, ^{respectively, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} may be formed of repeating units of the same or different oxyalkylene groups, typically, the same In many cases, the repeating unit of the oxyalkylene group is formed.

^{Also, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} may be different, the same ^{(e.g., R 2a1, R 2a2, R} 2b1 and ^{R 2b2} is ethylene group). ^Usually, when ^{R 2a1} and ^{R 2b1, R 2a2} and ^{R 2b2} are each the same is large ^{(e.g., R 2a1} and ^{R 2b1} is ethylene ^group, if ^{R 2a2} and ^{R 2b2} is an ethylene group or a propylene group Many). In addition, m11, m12, m21 and m22 which are the number of substitutions of oxyalkylene groups corresponding to these alkylene groups may be the same or different.

Oxyalkylene groups ^{(OR 2a1, OR 2a2, OR} 2b1 and ^{OR 2b2)} number (addition molar number) of m11, m12, m21 and m22, respectively, may be a integer of 0 or more, for example, 0 to 15 (e.g. 0 to 13), for example, may be 1 or more (eg, 1 to 11, preferably 1 to 9, more preferably 1 to 7), or 2 or more (eg, 2 to 10). , Preferably 2-6, more preferably 2-4). M11 and m21 may each be 1 to 3 (for example, 1), and m12 and m22 may be about 1 to 15 (for example, 2 to 10, preferably 2 to 5), respectively. Also good.

  Here, in the present invention, the total of m11, m12, m21, and m22 is adjusted to a specific range with respect to the entire fluorene compound represented by formula (1) (the molecular assembly of the compound represented by formula (1)). To do. The sum of m11, m12, m21 and m22 (m11 + m12 + m21 + m22) may be an average (arithmetic average or arithmetic average) value in a range exceeding 2 (for example, 2.3 or more). , 2.5 or more (for example, 2.7 or more), for example, 3 or more (for example, 3 to 20), preferably 3.5 or more (for example, 3.5 to 18), more preferably It may be about 4 or more (for example, 4.5 to 13).

  In particular, from the viewpoint of scratch resistance, the average value of m11 + m12 + m21 + m22 is relatively large [eg, 4 or more (eg, 4.5 to 20), preferably 5 or more (eg, 5.5 to 17), more preferably 6 or more (for example, about 6.5 to 15)]. From the viewpoint of heat resistance and the like, the average value of m11 + m12 + m21 + m22 is relatively small [for example, 17 or less (for example, 2.5 to 16), preferably 15 or less (for example, 3 to 14), and more preferably 13 or less. (For example, about 3.5 to 12)]. Therefore, from the viewpoint of imparting good scratch resistance and heat resistance, the average value of m11 + m12 + m21 + m22 is 3 to 17 (eg, 3.5 to 17), preferably 4 to 15, and more preferably 4.5 to It may be about 13.

  The above average (arithmetic average or arithmetic average) can be measured by a conventional method, and the measurement method is not particularly limited. For example, the compound used as a raw material in the synthesis of the fluorene compound represented by the formula (1) From the ratio of the amount of (the compound represented by the formula (A) described later) and the amount of consumed alkylene oxide, it can be easily obtained as an arithmetic average or arithmetic average value.

In the formula (1), group _{^{[H- (OR 2a2) m12 -}} (OR 2a1) m11 -O-] or _{^{[H- (OR 2b2) m22 -}} (OR 2b1) m21 -O -] ( hydroxyl group-containing group The number of substitutions n1 and n2 may be selected according to the types of Z ¹ and Z ² , etc., but for example, 1 to 6 (for example, 1 to 4), preferably 1 to 3, More preferably, it may be 1 to 2, and in particular may be 1 (that is, the compound represented by the formula (1) may be a diol compound). The numbers of substitutions n1 and n2 may be the same or different and are usually the same in many cases. Moreover, the substitution position of the hydroxyl group-containing group is not particularly limited, and may be substituted at an appropriate substitution position depending on the type of Z ¹ or Z ² . For example, when Z ¹ or Z ² is a benzene ring, the hydroxyl group-containing group is an appropriate position (especially at least the 4-position) at the 2-position to 6-position of the benzene ring substituted at the 9-position of fluorene. In particular, when n1 or n2 is 1, it may be substituted at the 4-position. In addition, when Z ¹ or Z ² is a naphthalene ring and n1 or n2 is 1, the substitution position of the hydroxyl group-containing group is often in the 5th to 8th positions, for example, relative to the 9-position of fluorene. Thus, there are many cases where the relationship is the 1,5-position, the 2,6-position, etc. (particularly, the 2,6-position).

Examples of the substituent R ^3a and R ^3b include an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). Cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (eg C _6-10 aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, etc.), aralkyl group Hydrocarbon groups such as (C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group); alkoxy groups (such as C _1-8 alkoxy groups such as methoxy group and ethoxy group), cycloalkoxy groups (such as _{C 5-10} cycloalkyl group such as a hexyloxy group cyclohexylene), _C of such an aryloxy group (phenoxy _{6- 0} aryloxy group), _{C 6-10} aryl _{-C 1-4} in group -OR ⁴ [expression such as alkyl group) such as an aralkyl group (benzyl group, ^{R 4} is hydrocarbon hydrocarbon group (exemplified above A hydrogen group). A group such as an alkylthio group (such as a C _1-8 alkylthio group such as a methylthio group) —SR ⁴ (wherein R ⁴ is as defined above); an acyl group (such as a C _1-6 acyl group such as an acetyl group) ); Alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, And a dialkylamino group such as a dimethylamino group).

Preferred groups R ^3a and R ^3b include, for example, a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group), cycloalkyl group (eg, C _5-8 cycloalkyl group), aryl group (eg, , A C _6-10 aryl group), an aralkyl group (for example, a C _6-8 aryl-C _1-2 alkyl group), an alkoxy group (C _1-4 alkoxy group, etc.), and the like. In particular, R ^3a and R ^3b are preferably an alkyl group [C _1-4 alkyl group (particularly methyl group) and the like], an aryl group [eg C _6-10 aryl group (particularly phenyl group) and the like] and the like. .

In addition, when p1 or p2 is plural, the groups R ^3a or R ^3b may be different from each other or the same. In addition, the groups R ^3a and R ^3b may be the same or different. Further, the preferred substitution numbers p1 and p2 may be, for example, 0 to 4 (for example, 0 to 3), preferably 0 to 2, and more preferably 0 to 1, respectively. The substitution numbers p1 and p2 may be the same or different from each other, and may be usually the same.

Typical examples of the compound represented by the formula (1) include 9,9-bis (hydroxy- (mono or poly) oxyalkoxyaryl) fluorene, [for example, 9,9-bis (hydroxy- (mono or poly)). Oxy C _2-6 alkoxyaryl) fluorene, preferably 9,9-bis (hydroxy- (mono or poly) oxy C _2-4 alkoxyaryl) fluorene, more preferably 9,9-bis (hydroxy- (mono Or poly) oxy C _2-3 alkoxyaryl) fluorene and the like], 9,9-bis (hydroxy- (mono or poly) oxyalkoxy (mono or poly) oxyalkoxyaryl) fluorene, [for example, 9,9-bis ( hydroxy - (mono or poly) oxy _{C 2-6} alkoxy (mono- or poly) oxy _{C 2-6} alkoxyalkyl Lumpur) fluorene, preferably, 9,9-bis (hydroxy - (mono or poly) oxy _{C 2-4} alkoxy (mono- or poly) oxy _{C 2-4} alkoxyaryl) fluorene, and more preferably, 9,9 Bis (hydroxy- (mono or poly) oxy C _2-3 alkoxy (mono or poly) oxy C _2-3 alkoxyaryl) fluorene and the like] and the like.

In particular, in formula (1), Z ¹ and Z ² are benzene rings, n1 and n2 are 1, and the hydroxyl group-containing group is substituted at the 4-position of the benzene ring, in formula (1), Z ¹ and Z ² May be a compound in which n1 and n2 are 1, n1 and n2 are 1, and the positional relationship between the substitution position with respect to the 9-position of fluorene and the hydroxyl group-containing group is in the 2,6-position.

When ring Z ¹ and ring Z ² are benzene rings, a hydroxy group-containing group is substituted at the 3-position or 4-position (particularly the 4-position) of the phenyl group substituted at the 9-position of fluorene. There are many cases. In addition, when ring Z ¹ and ring Z ² are naphthalene rings, the hydroxy group-containing group has a positional relationship of 1, 5 position or 2, 6 position with respect to 9 position of fluorene (especially 2, 6 position). There are many cases.

Specific examples of the compound represented by formula (1) (compounds in which k1, k2, p1, and p2 are 0, 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 . Moreover, m11 + m21 and m12 + m22 each show an average value.

The manufacturing method of the fluorene compound represented by the formula (1) (polyhydroxy compound) is not particularly limited, and polyhydroxy compound represented by the following formula (A), groups OR ^2a2 or a group OR ^2b2 It can obtain by making it react with the alkylene oxide or alkylene carbonate corresponding to. In such a method, a polyhydroxy compound (an assembly of polyhydroxy compounds) having a range of values (or molecular weights) of m12, m22, m12 + m22 in the formula (1) is usually obtained.

(In the formula, Z ¹ , Z ² , R ^1a , R ^1b , R ^2a1 , R ^2b1 , R ^3a , R ^3b , k1, k2, m11, m21, n1, n2, p1, and p2 are the same as above.)
The polyhydroxy compound represented by the formula (A) is prepared by a conventional method, for example, 9-fluorenones and groups [H— (OR ^2a1 ) _m11 —O—] and [H— () on the rings Z ¹ and Z ^2. OR ^{2b2) m22} _-O-] a hydroxy group-containing arene ring compound substituted (e.g., a method of reacting in the presence of 2-phenoxyethanol phenoxy alkanols such like) and an acid catalyst, hydroxy 9-position of the fluorene compound A fluorene compound substituted with an aryl group [eg, 9,9-bis (4-hydroxyphenyl) fluorene, etc.] and an alkylene oxide (eg, ethylene oxide) corresponding to the group OR ^2a1 or OR ^2b1 or an alkylene carbonate (eg, Can be obtained by a method of reacting with ethylene carbonate) It may be.

  Note that in the formula (A), when a compound with m11 = m21 = 1 is used, it is easy to efficiently suppress coloring of the polyhydroxy compound (further, the fluorene compound represented by the formula (1)).

Examples of the polyhydroxy compound represented by the formula (A) include compounds corresponding to the formula (1). Specifically, for example, 9,9-bis (hydroxyphenyl) which is a compound in which m11 = m21 = 0. ) Fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl-hydroxyphenyl) fluorene [eg, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene) Hydroxyphenyl) fluorene [e.g., 9,9-bis (mono- or mono-) such as 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene Is diC _6-10 aryl-hydroxyphenyl) fluorene], 9,9-bis (polyhydroxyphenyl) fluorene [eg, 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2 , 4-dihydroxyphenyl) fluorene, etc.], 9,9-bis (hydroxynaphthyl) fluorene [for example, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1) -Naphthyl) fluorene], etc .; 9,9-bis (hydroxyalkoxyphenyl) fluorene {e.g., 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9 which is a compound with m11 = m21 = 1 9,9-bis (hydroxy) such as 1,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene. C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9- 9,9-bis [(hydroxy C ₂₋ ) such as bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene _4- alkoxy) naphthyl] fluorene, etc.}.

The alkylene oxide corresponding to the group ^{OR 2a2} or a group ^{OR 2b2,} ethylene oxide, propylene oxide, _{C 2-6} alkylene oxides such as butylene oxide, preferably _{C 2-4} alkylene oxides, more preferably _{C 2-3} alkylene oxide ( In particular, ethylene oxide, propylene oxide) and the like can be mentioned. The alkylene carbonates corresponding to group ^{OR 2a2} or a group ^{OR 2b2,} ethylene carbonate, propylene carbonate, _{C 2-6} alkylene carbonates such as butylene carbonate, preferably _{C 2-4} alkylene carbonate, more preferably _{C 2-3} alkylene carbonate (Especially ethylene carbonate, propylene carbonate) and the like. Incidentally, when the reaction of alkylene oxide or alkylene carbonate, can be introduced oxyalkylene units (group OR ^2a2 or a group OR ^2b2) via a hydroxyl group of the compound represented by the formula (A). When alkylene carbonate is used, oxyalkylene units are introduced by decarboxylation after addition of alkylene carbonate.

The amount of alkylene oxide or alkylene carbonate corresponding to group ^{OR 2a2} or a group ^{OR 2b2} can be adjusted depending on the value of m12, m22, m12 + m22 in Formula (1). For example, theoretically, for example, (m12 + m22) × (n1 + n2) moles of alkylene oxide or alkylene carbonate may be used with respect to 1 mole of the compound represented by the formula (A).

  The reaction between the compound represented by the formula (A) and alkylene oxide or alkylene carbonate may be carried out in the absence of a catalyst, but can usually be carried out in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used. Base catalysts include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, sodium hydrogen carbonate, etc.) Inorganic bases such as alkali metals or alkaline earth metal hydrogen carbonates of the above; metal alkoxides (such as alkali metal alkoxides such as sodium methoxide), amines [eg, tertiary amines (eg, trialkylamines such as triethylamine, Aromatic tertiary amines such as N, N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc.], carboxylic acid metal salts (alkali metal acetates or alkaline earths such as sodium acetate and calcium acetate) Organic bases such as metal salts). The catalyst (base catalyst) may be used alone or in combination of two or more.

  The usage-amount of a catalyst can be adjusted according to the kind of catalyst, for example, 0.001-1 weight part (for example, 0.003-0.3. 5 parts by weight), preferably 0.005 to 0.3 parts by weight, more preferably about 0.01 to 0.1 parts by weight.

The reaction may be performed in a solvent. The solvent is not particularly limited and can be selected according to the raw material to be used. For example, when using an alkylene oxide, an ether solvent (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, Anisole, etc.), halogen solvents (halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride), hydrocarbon solvents (aromatic hydrocarbons such as benzene, toluene, xylene, etc.). When alkylene carbonate is used, in addition to the solvents exemplified above, alcohols (C _1-4 alcohols such as methanol and ethanol, (poly) C ₂ such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol) are used. _-3 alkylene glycol, etc.) may be used. The solvents may be used alone or in combination of two or more. The amount of the solvent to be used is, for example, 1 to 30 parts by weight, preferably 1.5 to 20 parts by weight, more preferably about 2 to 10 parts by weight with respect to 1 part by weight of the compound represented by the formula (A). It may be.

  The reaction is often performed at, for example, about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of compound to be added (alkylene oxide, alkylene carbonate) and the like. In particular, when alkylene carbonate is used, in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 70 to 150 ° C, preferably about 80 to 120 ° C. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 2 to 10 hours.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate | occur | produces as needed.

  The target product (compound represented by formula (A)) may be purified from the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

(Other polyols)
The polyol compound may be composed of only the fluorene compound, and may contain other polyol (polyol not belonging to the category of the fluorene compound represented by the formula (1)) as necessary.

Other polyols can be broadly classified into low molecular weight polyols (sometimes referred to as first polyols) and high molecular weight polyols (sometimes referred to as polymer polyols and second polyols). Examples of the low molecular weight polyol include aliphatic diols [for example, alkanediols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. C _2-12 alkane diols such as 1,8-octanediol, preferably C _2-8 alkane diols, more preferably C _2-6 alkane diols), polyalkane diols (eg, diethylene glycol, triethylene glycol, etc.) To tetra-C _2-4 alkanediol, etc.]], alicyclic diol [eg, cycloalkanediol (cyclohexanediol, etc.), di (hydroxyalkyl) cycloalkane (cyclohexanedimethanol etc.), etc., aromatic geo {Eg, di (hydroxyC _1-4 alkyl) C _6-10 arenes such as 1,4-benzenedimethanol, biphenols, bisphenols [eg, bis (hydroxyphenyl) C _1-10 alkanes such as bisphenol A Etc.] or an alkylene oxide adduct thereof (for example, an adduct in which 1 to 5 mol of _C2-4 alkylene oxide is added to 1 mol of hydroxyl group), etc .; a triol compound (for example, glycerin, trimethylol) Ethane, trimethylolpropane, etc.), tetraol compounds (eg, pentaerythritol, etc.), compounds having three or more hydroxyl groups such as sorbitol, xylitol, etc .; diol compounds having a fluorene skeleton {eg, 9,9-bis (4- Hydroxyphenyl) Fluorene compounds not belonging to the category of the above formula (1) such as fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (For example, in the above formula (1), the average value of m11 + m12 + m21 + m22 is 2 or less). The low molecular weight polyols may be used alone or in combination of two or more.

  The molecular weight of the low molecular weight polyol may be, for example, about 66 to 200, preferably 66 to 150, and more preferably about 66 to 120. When a low molecular weight polyol is used, the characteristics of the fluorene compound of the present invention are easily reflected in the polyurethane resin.

  Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polyolefin polyol [particularly polyolefin diol, such as polyalkadiene having hydroxyl groups at both ends (for example, 1,2-polybutadiene, 1,4-polybutadiene, etc.) Polybutadiene, polyisoprene) or hydrogenated products thereof, polyisobutylene having hydroxyl groups at both ends, etc.], polycarbonate polyols (for example, polyols (low molecular weight polyols exemplified above, polyether polyols, polyester polyols, etc.) and dialkyl carbonates Polycarbonate diol (eg, polyhexamethylene carbonate) obtained by reaction with (eg, alkyl carbonate such as dimethyl carbonate). ] And the like.

Polyether polyols (particularly polyether diols) include, for example, polyalkylene oxides [or polyalkylene glycols, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., or copolymers (eg, polyethylene glycol). , polypropylene glycol, polytetramethylene ether glycol, polyethylene oxide - polyoxy _{C 2-6} alkylene glycols such as polypropylene oxide block copolymers (or poly _{(oxy-C 2-6} alkylene)), preferably _{polyoxy-C 2-4} alkylene glycol (Or poly (oxy C _2-4 alkylene)), etc.]], alkylene oxide adducts of bisphenol A or hydrogenated bisphenol A (examples) For example, an adduct obtained by adding 1 to 5 moles of C _2-4 alkylene oxide to a hydroxyl group can be exemplified.

Polyester polyols (particularly polyester diols) include dicarboxylic acid components [dicarboxylic acids or derivatives thereof (for example, dicarboxylic acid lower alkyl esters (C _1-2 alkyl esters such as methyl esters), dicarboxylic acid halides, etc.)] and diol components. Reaction products, homopolymers or copolymers (poly-ε-caprolactone, etc.) of lactones (C _3-10 lactones such as ε-caprolactone and δ-valerolactone), etc. In the dicarboxylic acid component, Examples of the dicarboxylic acid include aromatic dicarboxylic acids (for example, dicarboxylic acids such as terephthalic acid and isophthalic acid), aliphatic dicarboxylic acids (for example, linear C _4-10 dicarboxylic acids such as adipic acid and sebacic acid), and the like. In addition, as the diol component, Njioru (above exemplified alkane diols, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, _{C 2-10,} such as neopentyl glycol And polyether-based diols such as alkane diols, preferably C _2-6 alkane diols), polyalkane diols (eg, polyalkane diols exemplified above such as diethylene glycol), etc. These dicarboxylic acid components and diol components include These polyester polyols may be used alone or in combination of two or more, and specific polyester polyols include, for example, polyethylene adipate, polydiethylene adipate, polypropylene adipate, polytetramethylene adipate, Polyhexamethylene adipate, copolymers thereof and the like are included.

  High molecular weight polyols may be used alone or in combination of two or more.

  The molecular weight of the high molecular weight polyol (polymer polyol) is a number average molecular weight, for example, 150 or more (for example, about 180 to 7000), preferably 200 or more (for example, about 230 to 5000), more preferably 250 to 2000, and more Preferably, about 300-1500 (for example, 400-1300) may be sufficient.

  Other polyols include a polyol having a carboxyl group (sometimes referred to as a third polyol). The other polyol may be composed of at least a polyol having a carboxyl group. When such a polyol having a carboxyl group and a fluorene compound are combined, heat resistance and the like can be improved or improved more efficiently. Further, by using a polyol having a carboxyl group, the polyurethane resin can be easily made aqueous. For example, a carboxyl group and a salt of a polyurethane resin using a base (for example, an organic base such as a trialkylamine (such as triethylamine), an alkanolamine (such as triethanolamine or dimethylaminoethanol), or an inorganic base such as sodium hydroxide). A polyurethane resin having water solubility or water dispersibility can be obtained.

The polyol (polyhydroxycarboxylic acid) having a carboxyl group has 1 or more (for example, 1 to 3, preferably 1 to 2, more preferably 1) carboxyl group and 2 or more (for example, 2 to 4, preferably 2). The compound having one hydroxyl group is not particularly limited, and examples thereof include polyhydroxyalkanoic acids (for example, 2,2-dimethylollactic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2, Such as 2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, tartaric acid, dihydroxyadipic acid, etc. Di- or trihydroxy C _3-15 alkane mono- or dicarboxylic acid, etc.), alkyls of these dihydroxy alkanoic acids Examples thereof include lenoxide adducts (for example, adducts in which about 1 to 5 moles of C _2-4 alkylene oxide is added to a hydroxyl group).

Preferred polyols having a carboxyl group include, for example, dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and 2,2-dimethylolpentanoic acid (for example, dimethylol C _{2- 10} mono- or dialkane carboxylic acid, preferably dimethylol C _3-8 mono- or dialkane carboxylic acid, more preferably dimethylol C _3-6 mono-alkane carboxylic acid). The polyol having a carboxyl group may be used alone or in combination of two or more.

  Other polyols may be used alone or in combination of two or more.

  When another polyol (for example, a polyol having a carboxyl group) is used in combination, the ratio of the fluorene compound (the compound represented by the formula (1)) to the other polyol is, for example, the former / the latter (molar ratio) = 99.5 / 0.5 to 5/95 (e.g. 99/1 to 8/92), preferably 98/2 to 10/90 (e.g. 97/3 to 12/88), more preferably 96/4. It may be about 15/85 (for example, 95/5 to 20/80), particularly about 93/7 to 25/75 (for example, 90/10 to 30/70).

  In addition, the ratio of the fluorene compound with respect to the whole polyol compound can be selected from the range of 5 mol% or more, for example, Usually 10 mol% or more (for example, 15-100 mol%), Preferably it is 20 mol% or more (for example, 25-25%). 100 mol%), more preferably 30 mol% or more (for example, 35 to 100 mol%), or 40 mol% or more (for example, 45 to 100 mol%).

  Moreover, the ratio of the fluorene compound with respect to the whole polyol can be selected from the range of 10 weight% or more (for example, 15-100 weight%), for example, 30 weight% or more (for example, 40-100 weight%), Preferably it is 50 weight % Or more (for example, 60 to 100% by weight), more preferably 70% by weight or more (for example, 75 to 100% by weight).

[Polyisocyanate compound]
The polyisocyanate compound is not particularly limited as long as it is a compound that can react with a polyol compound to form a bond (urethane bond). For example, polyisocyanate (aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic aliphatic polyisocyanate). Isocyanates, aromatic polyisocyanates, etc.), polyisocyanates having a polyol skeleton, modified polyisocyanates [or derivatives such as multimers (dimers, trimers, etc.), carbodiimides, biurets, allophanates, uretdiones Body, polyamine modified body, etc.].

Examples of the aliphatic polyisocyanate include aliphatic diisocyanate {eg, alkane diisocyanate [eg, hexamethylene diisocyanate (HDI) (1,6-hexane diisocyanate, etc.), 2,2,4, or 2,4,4-trimethylhexa C _2-20 alkane-diisocyanate such as methylene diisocyanate, lysine diisocyanate, etc., preferably C _4-12 alkane-diisocyanate, etc.] etc.} Aliphatic polyisocyanate having 3 or more isocyanate groups (for example, 1, 3, 6 -Hexamethylene triisocyanate, triisocyanates such as 1,4,8-triisocyanatooctane) and the like.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanate {cycloalkane diisocyanate (for example, C _5-8 cycloalkane-diisocyanate such as methyl-2,4- or 2,6-cyclohexanediisocyanate), isocyanatoalkyl, and the like. cycloalkanes isocyanate [e.g., 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI) isocyanato _{C 1-6} alkyl _{-C 5-10} cycloalkane such as - isocyanates, preferably isocyanato _{C 1 -4} alkyl _{-C 5-8} cycloalkane - isocyanate, di (isocyanatomethyl) cycloalkanes [e.g., di and hydrogenated xylylene diisocyanate (isocyanato _{C 1-6} a _{Kill) C 5-10} cycloalkane, di (isocyanatomethyl cycloalkyl) alkanes [e.g., hydrogenated diphenylmethane-4,4'-diisocyanate (4,4'-methylene-bis-cyclohexyl isocyanate) bis (such as isocyanato _{C 5- 10} cycloalkyl) C _1-10 alkane etc.], polycycloalkane diisocyanate (eg norbornane diisocyanate etc.)}, alicyclic polyisocyanate having 3 or more isocyanate groups (eg 1,3,5-triisocyanatocyclohexane etc.) And the like.).

Examples of the araliphatic polyisocyanate include di (isocyanatoalkyl) arene [for example, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) (1,3- or 1,4-bis (1-isocyanato). Bis (isocyanato C _1-6 alkyl) C _6-12 arene, preferably bis (isocyanato C _1-4 alkyl) C _6-10 arene etc.] and the like] such as -1-methylethyl) benzene) Can be mentioned.

Aromatic polyisocyanates include aromatic diisocyanates {eg, arene diisocyanates [eg, C _6-12 arenes such as o-, m- or p-phenylene diisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate (NDI)]. Diisocyanate etc.], di (isocyanatoaryl) alkanes [for example, diphenylmethane diisocyanate (MDI) (2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate etc.), bis (isocyanato C _6-10 aryl such as tolidine diisocyanate, etc. ) C _1-10 alkane, preferably bis (isocyanato C _6-8 aryl) C _1-6 alkane etc.], heteroatom (oxygen atom, sulfur atom etc. Etc.] [for example, di (isocyanatophenyl) ether, di (isocyanatophenyl) sulfone, etc.]} aromatic polyisocyanates having three or more isocyanate groups (for example, 4,4′-diphenylmethane) -2,2 ', 5,5'-triisocyanate, etc.) and the like.

  The polyisocyanate compound also includes a polyisocyanate having a polyol skeleton. As the polyisocyanate compound having such a polyol skeleton, the structure is not particularly limited as long as it is a compound having a polyol skeleton (or a skeleton derived from a polyol compound) in the molecule and having a plurality of isocyanate groups. Usually, a polyisocyanate having a polyol skeleton and a terminal isocyanate group [or a reaction product (or urethane prepolymer) obtained by reacting a polyol compound (particularly a diol compound) and a polyisocyanate compound (particularly a diisocyanate compound)]. That is, the polyisocyanate having a polyol skeleton is usually a reaction product obtained by reacting a diol compound and a diisocyanate compound, and may be a compound having an isocyanate group at both ends (or a urethane prepolymer).

  In the polyisocyanate having a polyol skeleton, examples of the polyol compound include those exemplified in the above-mentioned other polyols, for example, low molecular weight polyols (for example, alkane diol, polyalkane diol), high molecular weight polyols (for example, polyether polyol, Polyester polyol and the like). In the polyisocyanate having a polyol skeleton, examples of the polyisocyanate compound include the polyisocyanates exemplified above (for example, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, etc.). It is done.

  Polyisocyanate compounds may be used alone or in combination of two or more.

  Preferred polyisocyanate compounds include aliphatic polyisocyanates [especially aliphatic diisocyanates (eg HDI)], alicyclic polyisocyanates [especially alicyclic diisocyanates (eg IPDI)], araliphatic polyisocyanates [especially , Araliphatic diisocyanates (eg XDI, TMXDI etc.)], aromatic polyisocyanates [especially aromatic diisocyanates (eg MDI, TDI, NDI)], in particular araliphatic polyisocyanates, aromatic polyisocyanates. Polyisocyanates having an aromatic skeleton such as isocyanate are preferred. Therefore, the polyisocyanate compound may be composed of at least these compounds.

  The polyisocyanate compound is usually composed of at least diisocyanate (or diisocyanate compound such as aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate, aromatic diisocyanate, etc.).

  In the polyisocyanate compound, the content ratio of the isocyanate group (—NCO) can be appropriately selected according to the type of the polyisocyanate compound, and for example, 0.5 to 70% by weight (for example, 1 ~ 65 wt%), preferably 2 to 60 wt%, more preferably about 3 to 55 wt%.

  In particular, the isocyanate group content of the polyisocyanate compound (such as aromatic diisocyanate) is 7% by weight or more [for example, 10 to 70% by weight (for example, 13 to 65% by weight)], preferably 15% by weight or more [for example, 20 to 60% by weight (for example, 22 to 58% by weight)], more preferably 25% by weight or more [for example, 25 to 57% by weight (for example, 27 to 56% by weight)], particularly preferably 25 to 55% by weight. % (For example, 30 to 55% by weight).

  In the polyisocyanate having a polyol skeleton, the content ratio of the isocyanate group is, for example, 0.5 to 30% by weight (for example, 1 to 27% by weight), preferably 1.5 to 25% by weight (for example, 2 to 2%). 22 wt%), more preferably 3-20 wt% (eg 4-18 wt%), in particular 5-15 wt% (eg 6-12 wt%), usually 1-20 wt% It may be a degree.

[Polyurethane resin and method for producing the same]
The polyurethane resin of the present invention is obtained by reacting the polyol compound with a polyisocyanate compound. Specifically, it is obtained by reacting the hydroxyl group of the polyol compound with the isocyanate group of the polyisocyanate compound to form a urethane bond. In the formula (1), a polyurethane resin may be prepared using a polyol compound in which n1 and n2 each contain two or more fluorene compounds. As described above, the polyol compound and the polyisocyanate compound are typically Are respectively a diol compound and a diisocyanate compound. A polyurethane resin obtained by the reaction of such a diol compound and a diisocyanate compound is a structural unit represented by the following formula (2) (or a polymer skeleton, that is, fluorene in which n1 and n2 are 1 in the formula (1). It is a polyurethane resin having at least a structural unit obtained by reacting a compound and a diisocyanate compound.

(In the formula, A represents a residue of a ^{diisocyanate, Z 1, Z 2, R} 1a, R 1b, R 2a1, R 2a2, R 2b1, R 2b2, R 3a, R 3b, k1, k2, m11, m12 , M21, m22, p1, and p2 are the same as above.)
In the above formula (2), A means a diisocyanate residue, that is, a group obtained by removing two isocyanate groups (-NCO) from OCN-A-NCO (where A is a diisocyanate residue). .

  The weight average molecular weight of the polyurethane resin is, for example, 2000 or more (for example, 2500 to 300000), preferably 3000 or more (for example, 3500 to 200000), more preferably 4000 or more (for example, 4500 to 150,000), particularly 5000 or more (for example, 6000 to 120,000) or about 5,000 to 100,000 (for example, 5500 to 80,000, preferably 6,000 to 60,000).

  The content ratio of the isocyanate group in the polyurethane resin is, for example, 5% by weight or less (for example, 0.01 to 4% by weight), preferably 3.5% by weight or less (for example, 0.03 to 3% by weight), and more preferably. May be about 3% by weight or less (for example, 0.04 to 2.8% by weight), particularly about 2.5% by weight or less (for example, 0.05 to 2% by weight).

  Moreover, the hydroxyl value of a polyurethane resin is 60 or less (for example, 0.05-55), for example, Preferably it is 50 or less (for example, 0.3-40), More preferably, it is 35 or less (for example, 0.5-30). ), Especially about 30 or less (for example, 0.7 to 25).

  Such a polyurethane resin of the present invention is excellent in handling property or handling property, and has a good balance of properties such as high heat resistance, high refractive index and excellent flexibility. Moreover, it is possible to obtain a polyurethane resin that is excellent in film formability and adhesion to a substrate and has scratch resistance.

For example, in the present invention, the polyoxyalkylene units derived from the compound represented by the formula _{^{(1) (- (OR 2a2}} ) m12 - (OR 2a1) m11 - and ^{_{- (OR 2b2) m22 - (}} OR 2b1) m21 -) However, a polyurethane resin having relatively high heat resistance can be obtained. The glass transition temperature of such a polyurethane resin may be, for example, less than 0 ° C. (for example, about −30 ° C. to −5 ° C.), or may be 0 ° C. or more (for example, about 5 to 200 ° C.). Good. The glass transition temperature of the polyurethane resin is 25 ° C. or higher (for example, 25 to 180 ° C.), preferably 30 ° C. or higher (for example, 30 to 150 ° C.), more preferably 40 ° C. or higher (for example, 40 to 140 ° C.). The temperature may be about 50 ° C. to 130 ° C. or about 40 to 150 ° C. (for example, 45 to 130 ° C., preferably 50 to 120 ° C., more preferably 55 to 110 ° C.). In the present invention, a polyurethane resin having a low glass transition temperature (for example, liquid at normal temperature) can also be obtained depending on the application.

Further, the polyurethane resin of the present invention, the polyoxyalkylene units as the _{^{(- (OR 2a2) m12 -}} (OR 2a1) m11 - and _{^{- (OR 2b2) m22 - (}} OR 2b1) m21 -) Includes Despite being a polymer that is relatively flexible, it has a relatively high refractive index. Such excellent flexibility and high refractive index (and high heat resistance) are incompatible characteristics, and are one of the major features of the polyurethane resin of the present invention. The refractive index of the polyurethane resin is, for example, at a wavelength of 589 nm, 1.50 or more (for example, 1.51 to 1.8), preferably 1.52 or more (for example, 1.53 to 1.75), more preferably It may be about 1.55 or more (for example, 1.56 to 1.7), 1.58 or more (for example, 1.59 to 1.75, preferably 1.6 to 1.7, more preferably 1.61 to 1.68).

  The polyurethane resin of this invention can be manufactured by making a polyol compound and a polyisocyanate compound react as mentioned above.

  In the reaction, the ratio of the polyol compound and the polyisocyanate compound is not particularly limited. For example, the isocyanate group of the polyisocyanate compound is 0.5 to 2 mol, preferably 0. The ratio is 7 to 1.5 mol, more preferably 0.8 to 1.3 mol, particularly 0.9 to 1.1 mol (1 mol or almost 1 mol).

  The reaction may be performed in the presence of a catalyst. Examples of the catalyst include organic tin compounds (for example, tin carboxylates such as tin octylate, dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate), metal naphthenates (copper naphthenate, zinc naphthenate, naphthene). Organometallic catalysts such as cobalt acid; tertiary amines [eg, trialkylamines such as triethylamine, chain tertiary amines such as benzyldimethylamine; pyridine, methylpyridine, N, N-dimethylpiperazine, tri Cyclic tertiary amines such as ethylenediamine] and the like. These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used is, for example, 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, and more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the total amount of the polyol compound and the polyisocyanate compound. It may be about 1 part by weight (for example, 0.02 to 0.5 part by weight).

  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, dioxolane and tetrahydrofuran), ketones (for example, acetone, methyl ethyl ketone, diisopropyl ketone, Dialkyl ketones such as isobutyl methyl ketone), esters (eg, acetates such as methyl acetate, ethyl acetate, and butyl acetate), hydrocarbons (eg, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene) Halogenated 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 may be performed at room temperature, may be performed under heating (for example, 40 to 150 ° C., preferably 50 to 120 ° C., more preferably about 60 to 100 ° C.), or may be performed under reflux. Good. Note that the reaction may be performed in an inert atmosphere (an atmosphere of nitrogen, helium, argon, or the like).

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

[Molded body]
The polyurethane resin of the present invention has excellent characteristics as described above. Therefore, in the present invention, a molded article (particularly, an optical molded article such as an optical film) composed of the polyurethane resin (or its resin composition, hereinafter sometimes referred to as a polyurethane resin including the resin composition). Is also included. The shape of the molded body is not particularly limited, and examples thereof include a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular shape, rod shape, tube shape, hollow shape, etc.), and the like.

  Such a molded body should just be comprised with the said polyurethane resin, and may be comprised 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.), release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming 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 manufactured 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, and the like.

  In particular, the polyurethane resin of the present invention is excellent in various optical properties and is useful for forming a film (particularly an optical film). Therefore, the present invention includes a film (optical film) formed of the polyurethane resin.

  The thickness of such a film can be selected from the range of about 0.01 to 1000 μm depending on the application, for example, 0.1 to 500 μm (for example, 0.5 to 300 μm), preferably 1 to 200 μm, more preferably. About 3-100 micrometers may be sufficient.

  Such a film can be produced by forming (or molding) the polyurethane resin (or a resin composition thereof) using a conventional film forming method, coating method, melt extrusion method, calender method, or the like.

  The coating method is not particularly limited, for example, spin coating method, dipping method, flow coating method, bar coating method, spray coating method, screen printing method, cast method, curtain coating method, roll coating method, gravure coating method, The slit method etc. can be mentioned.

  The film may be formed by forming a polyurethane resin or a composition thereof on a substrate (or a base material) (for example, forming a film by coating). In the present invention, as described above, a film (film) having excellent adhesion to a substrate can be formed.

  The base material or the substrate can be selected depending on the application, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polymethyl methacrylate or polycarbonate. The polyurethane resin of the present invention is excellent in adhesion to a substrate and has high transparency, and is therefore suitable for optical applications. Among these substrates, by coating on a transparent film, a transparent substrate or You may utilize as a laminated body with a transparent film. Examples of transparent films include cyclic olefin resins, styrene resins, (meth) acrylic resins (polymethyl methacrylate, etc.), acrylonitrile resins, polyester resins (for example, polyethylene terephthalate), polyamide resins, and cellulose esters. Examples thereof include a transparent film composed of (such as triacetyl cellulose).

  In the coating method or the like, the polyurethane resin may be dissolved in a solvent (or a diluent) and used as necessary. Since the polyurethane resin of the present invention is relatively excellent in solubility in various solvents and can form a uniform film with excellent film forming properties, a coating method using a solvent can be suitably applied.

  The solvent is not particularly limited, and examples thereof include ethers (for example, cyclic ethers such as 1,4-dioxane, dioxolane, and tetrahydrofuran), ketones (for example, dialkyl such as acetone, methyl ethyl ketone, diisopropyl ketone, and isobutyl methyl ketone). Ketone), halogenated 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.

  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 number average molecular weight for calculating the weight average molecular weight and the polydispersity was measured by gel permeation chromatography (GPC). For GPC, an analysis sample prepared by adjusting polyurethane to a 0.1% tetrahydrofuran solution and then filtered through a membrane filter (0.45 μm) is used, and an HLC-8320GPC type manufactured by Tosoh Corporation is used as the apparatus. Tetrahydrofuran (special grade reagent) is used as the eluent, a differential refractometer and UV-visible detector (254 nm) are used as the detector, the measurement flow rate is 1.00 mL / min, and the molecular weight standard is Tosoh Corporation. Polystyrene was used.

(Glass-transition temperature)
The glass transition temperature was measured with a differential scanning calorimeter (DSC). For DSC, an EXTAR DSC 6220 manufactured by Seiko Instruments Inc. was used as an apparatus, a sample was put in an aluminum pan, and the measurement temperature range was 30 to 250 ° C. In Example 9, the measurement was performed at a measurement temperature range of −30 to 150 ° C.

(Adhesion and film-forming properties)
Based on the description in JIS-K 5400 8.5.1, adhesion between the film (coat layer) and the substrate film was determined as follows. Using a cutter guide with a gap of 2 mm, 100 square cuts that penetrate the coating layer and reach the base film are made on the surface of the coating layer. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., No. 405; 24 mm width) was attached to the grid-shaped cut surface. Then, the cellophane adhesive tape was peeled off from the surface of the coating layer vertically, and the number of squares of the coating layer peeled off from the base film was visually counted, and the adhesion between the coating layer and the base film was determined from the following formula. . In addition, what peeled partially in the square was counted as the square which peeled off.

Adhesiveness (%) = (1−number of peeled squares / 100) × 100
And the said adhesiveness and film-forming property were evaluated on the following references | standards.

  (Double-circle): A film (film | membrane) is uniform and favorable film-forming property, and adhesiveness is 100%.

  Δ: Although a film can be formed, it is non-uniform and the film formability is poor.

  X: Formation of a film is difficult.

(Scratch resistance)
In accordance with the method of JIS K5400 (pencil hardness measurement method), the film was scratched with a pencil having a core hardness of 6B, and the recovery of the scratch was observed, and scratch resistance was evaluated according to the following criteria.

  A: More than 80% of the wounds recovered after 5 days.

  X: No recovery of scratches can be confirmed even after 5 days.

(Synthesis Example 1)
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 The reaction was carried out using 4 moles of ethylene oxide (EO) per mole. From the hydroxyl value of the obtained product, a compound in which 3.0 mol of EO is added to 1 mol of BPEF (in the above formula (1), the average value of m11 + m12 + m21 + m22 is 5.0, hereinafter BPEF-3 .0EO)).

(Synthesis Example 2)
In Synthesis Example 1, a compound obtained by adding 5.0 mol of EO to 1 mol of BPEF (in the above formula (1), except that the amount of EO used was changed to 6 mol, in the same manner as in Synthesis Example 1) A compound having an average value of m11 + m12 + m21 + m22 of 7.0, hereinafter referred to as BPEF-5.0EO) was obtained.

(Synthesis Example 3)
In Synthesis Example 1, except that the amount of EO used was changed to 10 mol, a compound in which 9.0 mol of EO was added to 1 mol of BPEF (in the formula (1), A compound having an average value of m11 + m12 + m21 + m22 of 11.0, hereinafter referred to as BPEF-9.0EO) was obtained.

(Synthesis Example 4)
In the same manner as in Example 1 of JP-A No. 2001-139651, a product was obtained by reacting 10.0 mol of propylene oxide (PO) with respect to 1 mol of BPEF. From the hydroxyl value of the obtained product, a compound in which 10.0 mol of PO is added to 1 mol of BPEF (in the above formula (1), the average value of m11 + m12 + m21 + m22 is 12.0, hereinafter BPEF− It was found to be 10.0PO.)

Example 1
45.65 g (0.08 mol) of BPEF-3.0EO obtained in Synthesis Example 1 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer. 2,2-dimethylolpropionic acid (DMPA) 10.73 g (0.08 mol) and 1.6 L of chlorobenzene were added and dissolved by vigorous stirring and heated to 75 ° C. Furthermore, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI, manufactured by Tokyo Chemical Industry Co., Ltd., NCO content ratio 33.6 wt%, the same shall apply hereinafter) was added and heated to 100 ° C. Stirring was stopped after 1.5 hours. A viscous material was deposited on the bottom of the flask.

  When the liquid portion in the flask was transferred to a beaker and allowed to stand overnight, a viscous material was deposited on the bottom of the beaker. After removing the supernatant in the beaker, the viscous material was dissolved in 80 mL of tetrahydrofuran to obtain Solution 1.

  On the other hand, the viscous material deposited on the bottom of the flask was dissolved in 20 mL of methanol and 200 mL of tetrahydrofuran (THF) to obtain a solution 2.

  Solution 1 and solution 2 were added to 1.2 L of methanol with stirring. The separated viscous material was collected, transferred to a bottle, and vacuum dried at room temperature to obtain a solid.

  In the obtained solid, the weight average molecular weight Mw was 6200, the molecular weight distribution Mw / Mn was 2.0, and the glass transition temperature was 103 ° C.

  Further, the obtained solid was dissolved in tetrahydrofuran (concentration 20% by weight). The obtained solution was applied to a substrate film (polyethylene terephthalate film, the same applies hereinafter), and heated at 80 ° C. for 5 minutes on a hot plate to form a 10 μm thick film. The film was uniform and the film forming property was good.

  When the adhesion and film-forming property of the obtained film were evaluated, it was evaluated as “◎”.

(Example 2)
52.68 g (0.08 mol) of BPEF-5.0EO obtained in Synthesis Example 2 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer. 2,2-dimethylolpropionic acid (DMPA) 10.73 g (0.08 mol) and 1.6 L of chlorobenzene were added and dissolved by vigorous stirring and heated to 70 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. After 2 hours, stirring was stopped and the mixture was cooled to 50 ° C. A viscous material was deposited on the bottom of the flask.

  When the liquid portion in the flask was transferred to a beaker and allowed to stand overnight, a viscous material was deposited on the bottom of the beaker. After removing the supernatant in the beaker, the viscous material was dissolved in 30 mL of tetrahydrofuran to obtain Solution 1.

  On the other hand, the viscous material deposited on the bottom of the flask was dissolved in 20 mL of methanol and 200 mL of tetrahydrofuran (THF) to obtain a solution 2.

  Solution 1 and solution 2 were added to 1.2 L of methanol with stirring. The separated viscous material was collected, transferred to a bottle, and vacuum dried at room temperature to obtain a solid.

  In the obtained solid, the weight average molecular weight Mw was 18000, the molecular weight distribution Mw / Mn was 3.0, and the glass transition temperature was 88 ° C.

  Further, the obtained solid was dissolved in tetrahydrofuran (concentration 20% by weight). The obtained solution was applied to a substrate film and heated on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 10 μm. The film was uniform and the film forming property was good.

  When the adhesion and film-forming property of the obtained film were evaluated, it was evaluated as “◎”. Moreover, it was (double-circle) when the scratch resistance of the obtained film was evaluated.

(Example 3)
66.77 g (0.08 mol) of BPEF-9.0EO obtained in Synthesis Example 3 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer 2,2-dimethylolpropionic acid (DMPA) (10.73 g, 0.08 mol) and 1.6 L of chlorobenzene were dissolved by vigorous stirring and heated to 80 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. After 1.5 hours, stirring was stopped and the mixture was cooled to 50 ° C. A viscous material was deposited on the bottom of the flask.

  When the liquid portion in the flask was transferred to a beaker and allowed to stand overnight, a viscous material was deposited on the bottom of the beaker. After removing the supernatant in the beaker, the viscous material was dissolved in 30 mL of tetrahydrofuran to obtain Solution 1.

  On the other hand, the viscous material deposited on the bottom of the flask was dissolved in 20 mL of methanol and 200 mL of tetrahydrofuran (THF) to obtain a solution 2.

  Solution 1 and solution 2 were added to 1.2 L of methanol with stirring. The separated viscous material was collected, transferred to a bottle, and vacuum dried at room temperature to obtain a solid.

  In the obtained solid, the weight average molecular weight Mw was 9000, the molecular weight distribution Mw / Mn was 2.8, and the glass transition temperature was 57 ° C.

  Further, the obtained solid was dissolved in tetrahydrofuran (concentration 20% by weight). The obtained solution was applied to a substrate film and heated on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 10 μm. The film was uniform and the film forming property was good.

  When the adhesion and film-forming property of the obtained film were evaluated, it was evaluated as “◎”. Moreover, it was (double-circle) when the scratch resistance of the obtained film was evaluated.

(Comparative Example 1)
While blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube, and thermometer, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas) Chemical Co., Ltd. (hereinafter referred to as BPEF) 30.69 g (0.07 mol), 2,2-dimethylolpropionic acid (DMPA) 9.39 g (0.07 mol) and chlorobenzene 1.4 L were added and vigorously stirred. And dissolved and heated to 75 ° C. Further, 35.04 g (0.14 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. Since precipitation occurred in a relatively short time, stirring was stopped after 30 minutes. A solid was deposited at the bottom of the flask.

  When the liquid portion in the flask was analyzed by GPC, it was discarded because it was a low molecular weight component.

  On the other hand, the solid deposited on the bottom of the flask was mixed with 20 mL of methanol and 200 mL of tetrahydrofuran (THF) but did not dissolve, so it was dissolved by heating to 50 ° C.

  The obtained solution was added to 800 mL of methanol with stirring to precipitate a viscous product. Further, after stirring, it was separated and finely chopped, and again added to 400 mL of methanol, stirred, washed, further filtered, dried under reduced pressure at 60 ° C., and deaerated at room temperature under vacuum. Powdering was difficult.

  In the obtained solid, the weight average molecular weight Mw was over 100,000, the molecular weight distribution Mw / Mn was 17.1, and the glass transition temperature could not be measured.

  The obtained solid was mixed with tetrahydrofuran, but could not be completely dissolved (concentration: about 5% by weight). The obtained liquid mixture was apply | coated to the base film, and it heated at 80 degreeC with the hotplate for 5 minutes, and formed the film of thickness 10 micrometers. The film was non-uniform with whitening due to undissolved part of the film. Therefore, the film formability was extremely poor, and the evaluation of the adhesion and film formability of the obtained film was Δ. Moreover, it was x when the scratch resistance of the obtained film was evaluated.

Example 4
91.29 g (0.16 mol) of BPEF-3.0EO obtained in Synthesis Example 1 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer Then 1.6 L of chlorobenzene was added and dissolved by vigorous stirring and heated to 98 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. After 15 minutes, stirring was stopped and the reaction was terminated.

  When the reaction solution was transferred to a beaker and 100 mL of methanol was added and allowed to stand overnight, a viscous material was deposited on the bottom of the beaker. Therefore, the solution was concentrated under reduced pressure at 85 ° C. and 15 to 20 mmHg to dryness.

  In the obtained solid, the weight average molecular weight Mw was 33000, the molecular weight distribution Mw / Mn was 4.0, and the glass transition temperature was 85 ° C.

  Further, the obtained solid was dissolved in tetrahydrofuran (concentration 20% by weight). The obtained solution was applied to a substrate film and heated on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 10 μm. The film was uniform and the film forming property was good.

  It was (double-circle) when the adhesiveness of the obtained film was evaluated.

(Example 5)
105.37 g (0.16 mol) of BPEF-5.0EO obtained in Synthesis Example 2 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer Then 1.6 L of chlorobenzene was added and dissolved by vigorous stirring and heated to 73 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. After 2.5 hours, stirring was stopped and the reaction was terminated.

  The reaction solution was transferred to a beaker and allowed to stand overnight to separate the emulsion portion and the deposited viscous material. 500 mL of methanol was poured into the deposited viscous material, and after stirring, separated from the methanol layer, concentrated under reduced pressure, dried, and further dried at 90 ° C. under vacuum to obtain a slightly viscous and elastic solid. It was.

  In the obtained solid, the weight average molecular weight Mw was 20000, and the molecular weight distribution Mw / Mn was 2.5.

  Further, the obtained solid was dissolved in tetrahydrofuran (concentration 20% by weight). The obtained solution was applied to a substrate film and heated on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 10 μm. The film was uniform and the film forming property was good.

  When the adhesion and film-forming property of the obtained film were evaluated, it was evaluated as “◎”.

(Example 6)
135.55 g (0.16 mol) of BPEF-9.0EO obtained in Synthesis Example 3 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer Then 1.6 L of chlorobenzene was added and dissolved by vigorous stirring and heated to 90 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. After 7.5 hours, stirring was stopped and the reaction was terminated.

  The reaction solution was concentrated under reduced pressure at 85 ° C. and 15-20 mmHg, and then washed with 300 mL of methanol. After removing the methanol layer, it was further dried under reduced pressure at 85 ° C. to obtain a viscous solid.

  In the obtained solid, the weight average molecular weight Mw / Mn was 19000, and the molecular weight distribution Mw was 4.5.

  The obtained solid was dissolved in tetrahydrofuran and methylene chloride, and swollen in toluene at a concentration of 10% by weight.

(Example 7)
135.55 g (0.16 mol) of BPEF-9.0EO obtained in Synthesis Example 3 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer Then 1.6 L of chlorobenzene was added and dissolved by vigorous stirring and heated to 90 ° C. Furthermore, isophorone diisocyanate (IPDI, manufactured by Tokyo Chemical Industry Co., Ltd., NCO content 37.8 wt%, the same applies hereinafter) 40.04 g (0.16 mol) and di-n-butyltin dilaurate 0.67 g (BPEF-9) (0.5 part by weight with respect to 100 parts by weight of 0.0EO) and reacted at 100 ° C. for 2 hours.

  The reaction solution was concentrated under reduced pressure at 85 ° C. and 15 to 20 mmHg, and then added with 400 mL of methanol and washed by heating and stirring at 50 ° C. for 6 hours. Since the upper layer and the lower layer were separated, the lower layer was separated, concentrated under reduced pressure at 90 ° C. and 15 to 20 mmHg, and further dried under vacuum at 90 ° C. to obtain a viscous solid.

  In the obtained solid, the weight average molecular weight Mw was 14000, and the molecular weight distribution Mw / Mn was 4.1.

  The obtained solid was dissolved in tetrahydrofuran and methylene chloride, and swollen in toluene at a concentration of 10% by weight.

(Example 8)
135.55 g (0.16 mol) of BPEF-9.0EO obtained in Synthesis Example 3 while blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer Then 1.6 L of chlorobenzene was added and dissolved by vigorous stirring and heated to 75 ° C. Furthermore, 26.91 g (0.16 mol) of hexamethylene diisocyanate (HDI, manufactured by Tokyo Chemical Industry Co., Ltd., NCO content ratio 50.0 wt%, the same shall apply hereinafter) and 0.67 g of di-n-butyltin dilaurate (BPEF- 9.0 EO (100 parts by weight) was added, and the mixture was reacted at 100 ° C. for 3 hours.

  The reaction solution was concentrated under reduced pressure at 85 ° C. and 15 to 20 mmHg, and then added with 400 mL of methanol and washed by heating and stirring at 50 ° C. for 6 hours. Since the upper layer and the lower layer were separated, the lower layer was separated, concentrated under reduced pressure at 90 ° C. and 15 to 20 mmHg, and further dried at 90 ° C. under vacuum to obtain a viscous solid.

  In the obtained solid, the weight average molecular weight Mw was 23000, and the molecular weight distribution Mw / Mn was 6.8.

  The obtained solid was dissolved in tetrahydrofuran and methylene chloride, and swollen in toluene at a concentration of 10% by weight (partially dissolved).

Example 9
In a 2 L separable flask, under a stream of argon gas, 163.1 g (0.16 mol) of BPEF-10PO obtained in Synthesis Example 4 and 1500 ml of chlorobenzene were added, stirred and heated to dissolve. When the solution temperature reached 77 ° C., 40.0 g (0.16 mol) of diphenylmethane diisocyanate (MDI) and 100 ml of chlorobenzene were further added and heated to 100 ° C. After 25.5 hours, the heating was stopped, and after cooling, 100 ml of methanol was added to terminate the reaction. The reaction solution was concentrated to obtain 216.1 g of a viscous crude product.

  In order to remove the remaining BPEF-10PO, methanol washing was repeated once and isopropyl alcohol (IPA) washing was repeated three times to obtain 90.9 g of a viscous material.

  The viscous polyurethane resin thus obtained had a weight average molecular weight Mw of 9900, a molecular weight distribution Mw / Mn of 2.2, and a glass transition temperature of 29 ° C.

  Moreover, the obtained viscous body was melt | dissolved in tetrahydrofuran (concentration 20 weight%). The obtained solution was applied to a substrate film and heated on a hot plate at 80 ° C. for 5 minutes to form a film having a thickness of 10 μm. The film was uniform and the film forming property was good.

  When the adhesion and film-forming property of the obtained film were evaluated, it was evaluated as “◎”. Further, when the scratch resistance of the obtained film was evaluated, it was ◎ (recoverability was good, and 80% or more recovered after 1 day). Further, the obtained viscous material was dissolved in methylene chloride and toluene.

(Example 10)
At room temperature, under a stream of argon gas in a 2 L separable flask, 163.1 g (0.16 mol) of BPEF-10PO obtained in Synthesis Example 4 and 1550 ml of chlorobenzene were added, and the mixture was agitated and dissolved by heating. When the solution temperature was 50 ° C., 0.81 g of di-n-butyltin dilaurate (0.5 part by weight with respect to 100 parts by weight of BPEF-10PO) and 50 ml of chlorobenzene were added and heated to 100 ° C. The heating was stopped after 4.2 hours. After allowing to cool, 100 ml of methanol was added to terminate the reaction. The reaction solution was concentrated to obtain 223.5 g of a viscous product.

  In order to remove the remaining BPEF-10PO, methanol washing was repeated once and isopropyl alcohol washing was repeated twice to obtain 90.9 g of a viscous product.

  The obtained polyurethane resin had a weight average molecular weight Mw of 6300 and a molecular weight distribution Mw / Mn of 1.7. Moreover, the obtained viscous body was melt | dissolved in tetrahydrofuran, a methylene chloride, and toluene.

(Comparative Example 2)
While blowing argon gas into a 2 L three-necked round bottom flask, 70.16 g (0.16 mol) of BPEF and 1.6 L of chlorobenzene were added and dissolved by vigorous stirring and heated to 50 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. Stirring was stopped after 20 hours. A solid was deposited at the bottom of the flask.

  The deposited solid was taken out from the flask, but was hardly soluble in both tetrahydrofuran and methylene chloride. Therefore, the purification was abandoned, methanol was added, and it was cut into pieces, further washed with diethyl ether, and dried under reduced pressure at 90 ° C.

  Since the obtained solid was hardly soluble as described above, a very small amount of solid dissolved in tetrahydrofuran was subjected to GPC measurement. As a result, the weight average molecular weight Mw was over 100,000, the molecular weight distribution Mw / Mn was 6.9, glass The transition temperature was 166 ° C.

  Moreover, although dissolution of the obtained solid was tried, since it did not dissolve in tetrahydrofuran (and methylene chloride) as described above, a film could not be formed. Therefore, adhesiveness and film formability could not be evaluated (evaluation x). It was insoluble in toluene at a concentration of 10% by weight.

(Comparative Example 3)
While blowing argon gas into a 2 L four-necked separable flask equipped with a stirrer, argon gas blowing tube, cooling tube and thermometer, BPEF 35.08 g (0.08 mol), polyethylene glycol (molecular weight 1000, Wako Pure Chemical Industries, Ltd.) 80.00 g (0.08 mol) and 1.6 L of chlorobenzene were added and dissolved by vigorous stirring and heated to 75 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. Stirring was stopped at 5.5 hours, and the mixture was allowed to stand at room temperature for 14 hours.

  The reaction solution was transferred to a beaker, 100 mL of methanol was added, and the mixture was allowed to stand overnight, and then concentrated under reduced pressure at 85 ° C. and 15 to 20 mmHg, and further dried at 90 ° C. under vacuum to obtain a viscous solid.

  Since the obtained solid was hardly soluble in tetrahydrofuran, GPC measurement of a very small amount of solid dissolved in tetrahydrofuran revealed that the weight average molecular weight Mw was 13,000 and the molecular weight distribution Mw / Mn was 3.0. It was viscous and the glass transition temperature could not be measured.

  Further, the obtained solid was hardly soluble in tetrahydrofuran as described above, but was dissolved in methylene chloride. Therefore, the solution dissolved in methylene chloride was applied to the base film and heated at 80 ° C. on a hot plate. The film was heated for 5 minutes to form a 10 μm thick film. The film was viscous and could not be evaluated for adhesion and film formability (evaluation x).

(Comparative Example 4)
While argon gas was blown into a 2 L four-necked separable flask equipped with a stirrer, an argon gas blowing tube, a cooling tube, and a thermometer, 35.08 g (0.08 mol) of BPEF and an ethylene oxide 2 mol adduct of bisphenol A (2 , 2-bis [4- (2-hydroxyethoxy) phenyl] propane) (26.40 g, 0.08 mol) and 1.6 L of chlorobenzene were dissolved by vigorous stirring and heated to 75 ° C. Further, 40.04 g (0.16 mol) of diphenylmethane diisocyanate (MDI) was added and heated to 100 ° C. The reaction was completed in 20 hours and allowed to stand at room temperature for 14 hours. A viscous material was deposited on the bottom of the flask.

  The reaction solution was transferred to a beaker, 100 mL of methanol was added and allowed to stand overnight, and then the liquid part was removed. Dried to give a viscous solid.

  The obtained solid was difficult to dissolve in methylene chloride and was difficult to remove.

  Since the obtained solid was hardly soluble as described above, GPC measurement of a very small amount of solid dissolved in tetrahydrofuran revealed that the weight average molecular weight Mw was 53,000 and the molecular weight distribution Mw / Mn was 12.6. It was viscous and the glass transition temperature could not be measured.

  Further, the obtained solid was hardly soluble in tetrahydrofuran, and a film could not be formed. Therefore, adhesiveness and film formability could not be evaluated (evaluation x). It was insoluble in toluene at a concentration of 10% by weight.

The polyurethane resin (or composition thereof) of the present invention includes, for example, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a gas separation membrane (for example, a CO ₂ gas separation membrane), and a coating agent. (For example, an optical overcoat agent such as a coating agent for an LED (light emitting diode) element or a hard coat agent), a lens [a pickup lens (eg, a pickup lens for a DVD (digital versatile disk)), a microlens (For example, a microlens for a liquid crystal projector), a spectacle lens, etc.), a polarizing film (for example, a polarizing film for a liquid crystal display), a composite sheet, a brightness enhancement film, a prism sheet, an antireflection film (or an antireflection film, for example, Display device anti-reflection film, etc.), touch panel film, Film for flexible substrate, film for display [for example, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED ( Nano-emissive displays), cathode ray tubes, electronic paper and other displays (especially thin displays) films (protective films, etc.), retardation films, diffusion sheets, light guide plates, reflective sheet diffusers, barrier films, protective films, Overcoat, flexible film substrate, anisotropic conductive adhesive film (ACF), color filter [eg, lens filter, color filter for display, etc.], negative photoresist for liquid crystal display devices [eg, TFT array Etching photoresist, pigment dispersion type photoresist, dye type photoresist, protective film, etc.], interlayer insulating film, solder resist, photo spacer for liquid crystal display, fuel cell film, optical fiber, optical waveguide, hologram, various optical adhesives [For example, it can be suitably used for optical lenses, prisms, optical fibers, optical filters, optical waveguides], keypads, keyboards, touch panels, and the like.

Claims (13)

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

(Wherein, ^{Z 1} and ^{Z 2} are aromatic hydrocarbon ^{ring, R 1a} and ^{R 1b substituent, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} is an alkylene ^{group, R 3a} and ^{R 3b} are substituents, k1 And k2 are each an integer of 0 to 4, m11, m12, m21 and m22 are each an integer of 0 or more, n1 and n2 are each an integer of 1 or more, and p1 and p2 are each an integer of 0 or more, provided that m11 + m12 + m21 + m22 The average value of is 3 or more.)   The polyurethane resin according to claim 1, wherein an average value of m11 + m12 + m21 + m22 in the formula (1) is 3.5 to 17.   The polyurethane resin according to claim 1 or 2, wherein an average value of m11 + m12 + m21 + m22 is 4 to 15 in the formula (1). In the formula (1), a ^{Z 1} and ^{Z 2} is a benzene ring or a naphthalene ^{ring, R 2a1, R 2a2, R} 2b1 and ^{R 2b2} are _{C 2-4} alkylene group, the average value of m11 + m12 + m21 + m22 4.5~ The polyurethane resin according to claim 1, wherein n1 and n2 are each 1. In the formula (1), a ^{Z 1} and ^{Z 2} is a benzene ring or a naphthalene ^{ring, R 2a1 and, R 2b1} is ethylene ^{group, R 2a2} and ^{R 2b2} is ethylene group or propylene group, average of m11 + m12 + m21 + m22 The polyurethane resin according to any one of claims 1 to 4, wherein n is 4.5 to 13, and n1 and n2 are each 1.   The polyurethane resin according to any one of claims 1 to 5, wherein the polyol compound further contains a polyol other than the fluorene compound represented by the formula (1).   The polyurethane resin according to claim 6, wherein the other polyol includes a polyol having a carboxyl group.   The polyurethane resin according to claim 6 or 7, wherein the other polyol contains dimethylolalkanoic acid.   The polyurethane resin according to any one of claims 6 to 8, wherein the ratio of the fluorene compound and the other polyol is the former / the latter (molar ratio) = 95/5 to 20/80.   The polyurethane resin according to any one of claims 1 to 9, wherein the polyisocyanate compound contains at least one selected from an aromatic polyisocyanate and an araliphatic polyisocyanate.   The polyurethane resin according to any one of claims 1 to 10, wherein the polyisocyanate compound is a diisocyanate having an isocyanate group content of 20 to 60% by weight.   The polyurethane resin according to any one of claims 1 to 11, wherein the polyisocyanate compound contains an aromatic diisocyanate having an isocyanate group content of 25 to 55% by weight.   The film formed with the polyurethane resin in any one of Claims 1-12.