JP2014189520A - Polyhydroxy compound having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyhydroxy compound having a new fluorene skeleton (9,9-bisaryl fluorene skeleton) useful as a resin raw material or the like.SOLUTION: A polyhydroxy compound is added to the following compound (1) so as to be a composition including the following compound (2)[in the formula, a ring Z denotes an aromatic hydrocarbon ring; Rdenotes a substituent group; k denotes an integer of 0 to 4; X denotes a group-[O-RO)-H] (in the formula, Rdenotes an alkylene; and m denotes an integer or 0 or more); n denotes an integer of 2 or more; Rdenotes a substituent; p denotes an integer of 0 or more; and q denotes an integer of 0 or more].

Description

  The present invention relates to a polyhydroxy compound having a fluorene skeleton (for example, a 9,9-bisarylfluorene skeleton).

  Polyhydroxy compounds having a fluorene skeleton such as bisphenol fluorene (BPF), biscresol fluorene (BCF), and bisphenoxyethanol fluorene (BPEF) are known to have excellent functions in terms of refractive index and heat resistance. Used as a raw material.

  As the polyhydroxy compound having such a fluorene skeleton, a bifunctional compound (dihydroxy compound) is generally used as described above, but a polyfunctional compound is also being developed. For example, in JP-A-2005-104935 (Patent Document 1), 9-fluorenone and catechol are reacted in the presence of β-mercaptopropionic acid and sulfuric acid to produce 9,9-bis (3,4-hydroxy). Phenyl) fluorene (biscatechol fluorene) was obtained, and this biscatechol fluorene was reacted with ethylene carbonate to obtain a polyhydric alcohol in which an ethoxy group was added to biscatechol fluorene. It is described that alcohol and acrylic acid were reacted to obtain a tetraacrylic acid ester having a purity of 98%.

  A polyhydroxy compound having a fluorene skeleton includes, for example, 9-fluorenone, corresponding phenols (eg, phenol, cresol, catechol, etc.) and phenoxyalkanols (eg, 2-phenoxyethanol) as described in Patent Document 1 above. Etc.) in the presence of an acid catalyst.

  In JP 2010-1000077 (Patent Document 2), when 2-phenoxyethanol or the like is used in such a reaction, the target product, bisphenoxyethanol fluorene [that is, 9,9-bis (4- In addition to (2-hydroxyethoxy) phenyl) fluorene] and the like, it is disclosed that a compound represented by the following formula can be obtained as a minor by-product.

(In the formula, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group; X ¹¹ and X ¹² each independently represent a C _{2 to} C ₄ alkylene group.)
On the other hand, JP-A-2011-219465 (Patent Document 3) discloses 9-fluorenone and 9,9-bis (6-hydroxy-2-naphthyl) fluorene in the presence of 3-mercaptopropionic acid and sulfuric acid. It is described that a polynuclear compound represented by the following formula was obtained by reaction.

JP-A-2005-104935 (Claims, Examples) JP 2010-1000077 (claims, paragraph [0012], examples) JP 2011-219465 A (Claims, Examples)

  An object of the present invention is to provide a novel polyhydroxy compound (mixture or composition of polyhydroxy compounds) having a fluorene skeleton (9,9-bisarylfluorene skeleton).

  Another object of the present invention is to provide a polyhydroxy compound having a novel fluorene skeleton useful as a resin raw material.

  Still another object of the present invention is to provide a polyhydroxy compound having a fluorene skeleton useful for improving or improving curability.

  Another object of the present invention is to provide a polyhydroxy compound having a fluorene skeleton that can improve or improve the curability without impairing the properties (eg, high refractive index) derived from the fluorene skeleton.

  As is clear from Patent Document 3, 9,9-bis (6-hydroxy-2-naphthyl) fluorene itself, which is a polyhydroxy compound, is used as a raw material in order to obtain a polynuclear body (or multimer). In a polyhydroxy compound having a fluorene skeleton, although a trace amount of a polynuclear compound may be obtained as an impurity in the production process of Patent Document 2, the polynuclear compound is used under limited conditions such as when 2-phenoxyethanol is used. In addition, the polynuclear body is used as it is as in Patent Document 3, or as a raw material for a thermoplastic resin such as a polyester resin as in Patent Document 2, and the dihydroxy compound [9, 9 as a product] -Bis (4- (2-hydroxyethoxy) phenyl) fluorene etc.] It was limited to be recognized that there is a case.

  Under these circumstances, the present inventors have intensively studied to achieve the above object, and as a result, among the polyhydroxy compounds having a fluorene skeleton, the polyhydroxy compounds having a fluorene skeleton having four or more hydroxyl groups are also used. The presence of a polynuclear body having a specific structure, and the use of a polyhydroxy compound containing such a polynuclear body (particularly, a relatively large amount) as a raw material for a heat or photocurable resin (for example, an acrylic resin) Surprisingly, it can be found that the curability can be improved or improved as compared with the case where no polynuclear substance is contained, and further, such curability can be improved without impairing the excellent properties derived from the fluorene skeleton, The present invention has been completed.

  That is, the polyhydroxy compound (polyhydroxy composition) of the present invention includes a compound represented by the following formula (1) and a compound represented by the following formula (2).

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 2 or more, R ³ represents a substituent, p represents an integer of 0 or more, and q represents an integer of 0 or more. ]
In the above formulas (1) and (2), the ring Z may be a benzene ring or a naphthalene ring, R ² may be a C _2-4 alkylene group, and m may be about 0 to 10. In addition, n may be about 2 to 4, R ³ may be an alkyl group or an aryl group, and p may be about 0 to 3. In particular, in the formulas (1) and (2), the ring Z may be a benzene ring, R ² may be a C _2-4 alkylene group, m may be 0 to 2, n may be 2 or 3, and p may be 0.

  In the formulas (1) and (2), the following formula (a)

(In the formula, Z, X, R ³ , n, and p are the same as described above.)
A group (unit) represented by the following formula (a1):

(In the formula, p1 represents an integer of 0 to 3, and X and R ³ are the same as described above.)
The group (unit) represented by these may be sufficient.

  In the polyhydroxy compound of the present invention, the ratio of the compound represented by the formula (2) may be, for example, 10 mol or more with respect to 100 mol of the compound represented by the formula (1).

  Further, the compound represented by the formula (2) may include at least the compound (2A) in which q is 0 in the formula (2) and the compound (2B) in which q is 1 in the formula (2). Good. In such a case, the ratio of the compound (2A) to the compound (2B) may be, for example, the former / the latter (molar ratio) = 99/1 to 50/50.

  Typically, the ratio of the compound represented by the formula (2) is 20 moles or more with respect to 100 moles of the compound represented by the formula (1), and the ratio of the compound (2A) and the compound (2B). However, the former / the latter (molar ratio) may be about 90/10 to 50/50.

  The present invention includes a resin having the polyhydroxy compound as a polymerization component (for example, a polyol component). Such resins are particularly heat or photo-curing resins having a polyhydroxy compound as a polyol component [for example, poly (meth) acrylate of a polyhydroxy compound (a hydroxyl group of a polyhydroxy compound is substituted with a (meth) acryloyloxy group) Compound)]]. Moreover, the hardened | cured material of the said resin (heat | fever or photocurable resin) is also contained in this invention.

  In the present invention, a novel polyhydroxy compound (mixture or composition of polyhydroxy compounds) having a fluorene skeleton (9,9-bisarylfluorene skeleton) is obtained. Such a polyhydroxy compound, in addition to a polyhydroxy compound having a specific fluorene skeleton having 4 or more hydroxyl groups, includes a multimeric compound of this polyhydroxy compound, which is generally recognized as an impurity. Surprisingly, it is highly useful and useful as a resin raw material. In particular, when the polyhydroxy compound of the present invention is used as a heat or photocurable resin or its raw material, the curability is improved as compared to the case of a polyhydroxy compound having a specific fluorene skeleton having four or more hydroxyl groups. Or it can be improved. For example, when used as a raw material for an acrylic resin, curability (or crosslinkability) is improved, and a cured product with higher hardness can be obtained.

  In addition, as described above, the polyhydroxy compound of the present invention unexpectedly impairs properties derived from a fluorene skeleton (for example, a high refractive index, etc.), despite the fact that it contains a multimeric compound that can be generally recognized as an impurity. There is nothing. Therefore, for example, the curability and the like can be improved or improved without impairing the properties derived from the fluorene skeleton, which is extremely useful.

[Polyhydroxy compounds]
The novel polyhydroxy compound of the present invention includes a compound represented by the following formula (1) (sometimes referred to as compound (1)) and a compound represented by the following formula (2) (compound (2)). Included).

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 2 or more, R ³ represents a substituent, p represents an integer of 0 or more, and q represents an integer of 0 or more. ]
In the above formulas (1) and (2), examples of the aromatic hydrocarbon ring Z 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 hydrocarbon 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. In the formula (1) or the formula (2), the plurality of Z may be the same or different aromatic hydrocarbon rings, and may usually be the same. In the formulas (1) and (2), Z may be the same or different aromatic hydrocarbon rings, but may usually be the same.

In the formula (1) or (2), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a carboxyl group, a hydrocarbon group [for example, an alkyl group, an aryl group. (Hydrocarbon groups described later such as a C _6-10 aryl group such as a phenyl group)] and the like, 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 k is plural (2 to 4), plural groups R ¹ may be different from each other or the same. Moreover, in Formula (1) or (2), several R < ¹ > may be the same and may differ. Furthermore, in Formula (1) and Formula (2), R ¹ may be the same or different groups, and may usually be the same.

In addition, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The number k of substitutions may be the same or different in formula (1) or (2), and may be the same or different in formula (1) and formula (2).

In the formula (1) or (2), examples of the alkylene group represented by the group R ² include C _2-6 such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. An alkylene group, preferably a _C2-4 alkylene group, more preferably a _C2-3 alkylene group is mentioned.

In the formula (1) or (2), when m is 2 or more, the groups R ² may be the same or may be composed of different alkylene groups (for example, an ethylene group and a propylene group). . In addition, m which is the substitution number of the oxyalkylene group corresponding to these alkylene groups may be the same or different in the formula (1) or (2).

In the formula (1) or (2), the number m of the oxyalkylene group (OR ² ) can be selected from a range of about 0 to 30 (for example, 0 to 25), for example, 0 to 20 (for example, 0 to 0). 10), preferably 0-8 (eg 1-8), more preferably 0-6 (eg 1-6), especially 0-4 (eg 1-4), particularly preferably 0-3 (eg 1 to 3) or 0 to 2 (for example, 1 to 2). In particular, from the viewpoint of high carbon density and the like, m is preferably 0 to 2, preferably about 0 to 1, and from the viewpoint of curability and handling properties, 1 or more (for example, 1 to 4), preferably 1 or 2 may be sufficient. Therefore, in the formula (1) or (2), the compound in which m is 1 to 2 (particularly 1) has sufficient properties such as high carbon density and sufficient curability and handling properties in a well-balanced manner. It is suitable. In the formula (1) or (2), m may be the same or different numbers. In the formulas (1) and (2), m may be the same or different numbers.

In the formula (1) or (2), the number n of the group X (that is, the group — [O— (R ² O) _m —H]) may be 2 or more, depending on the type of the ring Z and the like. For example, it may be 2 to 6 (for example, 2 to 4), preferably 2 to 3, and more preferably 2. In the formula (1) or (2), n may be the same or different numbers, and may usually be the same. Moreover, also in Formula (1) and Formula (2), n may be the same or different numbers, and may usually be the same.

  In addition, the substitution position of group X is not specifically limited, What is necessary is just to substitute to a suitable substitution position according to the kind etc. of Z. For example, when Z is a benzene ring, the group X is in an appropriate position at positions 2-6 of the benzene ring substituted at the 9-position of fluorene (especially at least 4-position such as 2,4-position, 3,4-position). May be substituted.

In the formula (1) or (2), examples of the substituent R ³ include an alkyl group (eg, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably C _1-8 alkyl group), cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (for example, C _6-10 such as phenyl group, tolyl group, xylyl group, naphthyl group, etc.) Hydrocarbon groups such as aryl groups (eg C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups); alkoxy groups (C _1-8 alkoxy such as methoxy groups and ethoxy groups) group, etc.), etc. C _5-10 cycloalkyl group such as a cycloalkoxy group (hexyloxy group cyclohexylene), an aryloxy group (phenoxy group Which _{C 6-10} 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 a hydrocarbon group ( The above-exemplified hydrocarbon groups and the like). 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 group R ³ includes, 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, C _{6 -10} aryl group), an aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group) and the like, and an alkoxy group (C _1-4 alkoxy group etc.). In particular, R ³ may be an alkyl group [C _1-4 alkyl group (particularly a methyl group)], an aryl group [eg C _6-10 aryl group (particularly a phenyl group)], or the like.

When p is plural, the plural groups R ³ may be different from each other or the same. In the ring Z of the formula (1) or the formula (2), the groups R ³ may be the same or different. Further, in the formulas (1) and (2), the groups R ³ may be the same or different groups, and may be particularly the same.

  In the formula (1) or (2), the preferred substitution number p may be, for example, 0 to 4 (for example, 0 to 3), preferably 0 to 2, more preferably 0 to 1, particularly 0. In the formula (1) or (2), the substitution number p may be the same or different, and may usually be the same. Moreover, also in Formula (1) and Formula (2), the substitution number p may be the same or different, and may be the same normally.

  Typically, in the formulas (1) and (2), the following formula (a)

(In the formula, Z, X, R ³ , n, and p are the same as described above.)
The group (unit) represented by the following formula (a1)

(In the formula, p1 represents an integer of 0 to 3, and X and R ³ are the same as described above.)
The group (unit) represented by these may be sufficient.

  Among the units (a1), in particular, the compound (2) having a unit represented by the following formula (a1-1) is easily obtained as an impurity in the synthesis process of the corresponding compound (1). This is advantageous in efficiently obtaining the polyhydroxy compound.

(Wherein, X, R ³ and p1 are the same as described above.)
The polyhydroxy compound of the present invention is characterized by containing the compound (2) in addition to the compound (1). Such a compound (2) has a structure corresponding to a multimer (oligomer) of the compound (1).

  In the formula (2), q is not particularly limited as long as q is an integer of 0 or more, and can be selected from a range of about 0 to 30 (for example, 0 to 20), for example, 0 to 10, preferably 0 to 5, and further Preferably it may be 0-4, especially 0-3.

  The compound represented by the formula (2) may be a single compound in q, and in particular, may be a mixture with a plurality of compounds (2) different in the value of q. Usually, the compound (2) often contains at least a compound in which q is 0 in the formula (2) (that is, a compound represented by the following formula (2A), sometimes referred to as the compound (2A)), In particular, it often includes at least the compound (2A) and a compound in which q is 1 in the formula (2) (that is, a compound represented by the following formula (2B) or a compound (2B)). .

(In the formula, Z, R ¹ , k, X, n, R ³ and p are the same as above.)
The ratio of the compound (2A) can be selected, for example, from the range of about 1 mol% or more (for example, 3 to 100 mol%) with respect to the entire compound (2), for example, 5 mol% or more (for example, 7 to 90 mol%), preferably 10 mol% or more (for example, 15 to 80 mol%), more preferably 20 mol% or more (for example, 25 to 75 mol%), particularly 30 mol% or more (for example, 35 to 70 mol%). %).

  When the compound (2) includes the compound (2B), the ratio of the compound (2B) is selected from a range of, for example, about 1 mol% or more (for example, 2 to 80 mol%) with respect to the entire compound (2). For example, 3 mol% or more (for example, 4 to 70 mol%), preferably 5 mol% or more (for example, 7 to 60 mol%), more preferably 10 mol% or more (for example, 12 to 50 mol%). In particular, it may be 15 mol% or more (for example, 18 to 40 mol%).

  When compound (2) includes compound (2A) and compound (2B), the ratio of the total amount of compound (2A) and compound (2B) is 5 mol% or more (for example, 10 to 100 mol%), for example, 20 mol% or more (for example, 25 to 100 mol%), preferably 30 mol% or more (for example, 35 to 95 mol%), more preferably 40 mol % Or more (for example, 45 to 90 mol%), particularly 50 mol% or more (for example, 55 to 85 mol%).

  When compound (2) includes compound (2A) and compound (2B), the ratio of compound (2A) to compound (2B) is the former / the latter (molar ratio) = 99/1 to 5/95 ( For example, it can be selected from the range of about 98/2 to 15/85), for example, 97/3 to 20/80 (for example, 96/4 to 30/70), preferably 95/5 to 40/60 (for example, 93/7 to 45/55), more preferably 90/10 to 50/50 (for example, 85/15 to 55/45), and usually 99/1 to 50/50 (for example, 95 / 5 to 55/45, preferably 90/10 to 60/40, more preferably 85/15 to 63/37, particularly 80/20 to 65/35).

  In the polyhydroxy compound of the present invention, the ratio of the compound (2) can be selected from the range of about 1 mol or more (for example, 5 to 1000 mol) with respect to 100 mol of the compound (1). For example, 15 to 800 mol), preferably 20 mol or more (for example, 25 to 500 mol), more preferably about 30 mol or more (for example, 35 to 300 mol), and usually 10 to 250 mol (for example, 15 to 200 mol, preferably 20 to 180 mol, more preferably 30 to 150 mol, particularly 40 to 130 mol).

  In particular, the ratio of the compound (2A) is, for example, 1 mol or more (for example, 3 to 500 mol), preferably 5 mol or more (for example, 8 to 300 mol), more preferably 100 mol of the compound (1). May be about 10 mol or more (for example, 15 to 100 mol), usually 5 to 80 mol (for example, 8 to 70 mol, preferably 10 to 65 mol, more preferably 15 to 65 mol, particularly 20 to 20 mol). About 60 mol).

  When the compound (2) includes the compound (2B), the ratio of the compound (2B) is, for example, 1 mol or more (for example, 2 to 300 mol), preferably 3 with respect to 100 mol of the compound (1). Mol or more (for example, 4 to 100 mol), more preferably about 5 mol or more (for example, 7 to 80 mol), and usually 3 to 70 mol (for example, 4 to 60 mol, preferably 5 to 50 mol). Mol, more preferably 7 to 40 mol, particularly 10 to 30 mol).

  Furthermore, when compound (2) includes compound (2A) and compound (2B), the ratio of the total amount of compound (2A) and compound (2B) is, for example, 5 mol or more with respect to 100 mol of compound (1) (For example, 7 to 500 mol), preferably 10 mol or more (for example, 15 to 300 mol), more preferably about 20 mol or more (for example, 25 to 200 mol), and usually 10 to 100 mol ( For example, it may be about 15 to 90 mol, preferably 20 to 85 mol, more preferably 30 to 80 mol, particularly 35 to 75 mol).

[Production method of polyhydroxy compound]
As described above, the polyhydroxy compound of the present invention is a mixture (composition) of the compound (1) and the compound (2), and its production method is not particularly limited. For example, (i) the compound (1) A method of producing (by-product) compound (2) in the synthesis process to obtain a mixture of compound (1) and compound (2), (ii) A method of synthesizing compound (2) and mixing with compound (1) , (Iii) a method of combining these, and the like.

  The method (i) is suitable in that the compound (2) can be produced as a by-product together with the synthesis of the compound (1), and it is not necessary to prepare the compound (2) separately.

  On the other hand, although the method (ii) needs to prepare the compound (2) separately, it is suitable depending on the type of the compound (1) when the compound (2) is difficult to obtain in the synthesis process.

  In addition, as a method for obtaining the compound (2), the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2011-219465), that is, the compound (1) and a fluorenone (represented by the formula (1a) described later) A method of reacting a compound) in the presence of an acid catalyst can be used.

  The method (iii) is useful when the compound (2) is produced as a by-product in the synthesis process of the compound (i), but it is difficult to obtain a desired polyhydroxy compound due to a small amount.

  Hereinafter, the method (i) will be described in detail.

In the method (i), although not particularly limited, a compound represented by the following formula (1a) (sometimes referred to as fluorenones) is reacted with a compound represented by the following formula (1b). Along with this reaction, compound (1) is produced, and compound (2) is produced (by-product), and a reactant is obtained in the form of a mixture of compound (1) and compound (2). In the formula (1) or (2), when m is 1 or more, a compound in which m is 0 or 1 is obtained, and a corresponding alkylene oxide (for example, ethylene oxide, propylene oxide) is obtained. C _2-4 alkylene oxide) and the like can also be reacted.

(In the formula, Z, R ¹ , k, X, n, R ³ and p are the same as above.)
In the above formulas (1a) and (1b), Z, R ¹ , k, X, n, R ³ and p are the same as described above, and preferred embodiments are also the same as described above. As a compound (fluorenones) represented by a typical formula (1a), for example, 9-fluorenone can be mentioned. The purity of the fluorenones is not particularly limited, but is usually 95% by weight or more, preferably 98% by weight or more, and more preferably 99% by weight or more.

  Further, as a typical compound represented by the formula (1b), a compound corresponding to the unit represented by the formula (a1), for example, dihydroxybenzene (for example, resorcinol, catechol, etc.), alkyldihydroxybenzene ( For example, a compound in which Z is a benzene ring, m is 0, and n is 2, such as 3,5-dihydroxytoluene, mono- or dialkyl-dihydroxybenzene such as 2,6-dihydroxy-p-xylene) : Corresponding to these compounds, m is 1 or more (for example 1 to 4), for example, di (hydroxyalkoxy) benzene [for example, 1,3-di (2-hydroxyethoxy) benzene, etc. 3-di (hydroxy (poly) alkoxy) benzene]: a compound corresponding to these compounds, wherein n is 3 or more For example, pyrogallol, etc.) and the like.

  Particularly, resorcinol, which is a compound corresponding to the unit represented by the formula (a1-1), a compound corresponding to resorcinol and m is 1 or more [1,3-di (2-hydroxyethoxy) benzene, etc. ] Is preferred because it tends to by-produce the compound (2).

  In the reaction, the amount of the compound represented by the formula (1b) is, for example, 2 mol or more (for example, 2.2 to 20 mol), preferably 2.5 mol or more (for example, for 1 mol of fluorenones). 2.7 to 15 mol), more preferably about 2.8 mol or more (for example, 3 to 10 mol). In addition, when there is much usage-amount of the compound represented by Formula (1b), it seems that a compound (2) is easy to byproduce.

Further, the reaction may be usually performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids {eg, sulfuric acid, hydrogen halide (hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), hydrohalic acid [eg, hydrochloric acid (eg, 5 to 36% by weight, preferably About 20 to 36% by weight of an aqueous solution of hydrogen chloride), hydrobromic acid, hydroiodic acid, etc.], phosphoric acid, etc.}, organic acid {eg, carboxylic acid, sulfonic acid [eg, alkane sulfonic acid (eg, C _1-4 alkane sulfonic acid such as methane sulfonic acid), arene sulfonic acid (for example, C _6-10 arene sulfonic acid such as benzene sulfonic acid, toluene sulfonic acid (p-toluene sulfonic acid)), haloalkane sulfonic acid (For example, halo C _1-4 alkane sulfonic acid such as trifluoromethane sulfonic acid etc.) and the like] and the like. The sulfuric acid includes dilute sulfuric acid (for example, sulfuric acid having a concentration of about 30 to 90% by weight), concentrated sulfuric acid (for example, sulfuric acid having a concentration of 90% by weight or more), fuming sulfuric acid, and the like, and can be converted into sulfuric acid in the reaction system. If present, sulfur trioxide may be used as the sulfuric acid precursor. In particular, as sulfuric acid, concentrated sulfuric acid may be preferably used. A solid acid (such as an inorganic solid acid or an organic solid acid such as an ion exchange resin) can be used as the acid catalyst. The acid catalyst may be used alone or in combination of two or more.

  The amount of the acid catalyst (for example, inorganic acid or organic acid) used depends on the type of the acid catalyst, the type of the compound (1b), etc. 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably about 0.2 to 10 parts by weight. In particular, when the acid catalyst is sulfuric acid, the amount of sulfuric acid used is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight with respect to 1 part by weight of the compound represented by formula (1). Parts (for example, 0.3 to 5 parts by weight), more preferably 0.5 to 4 parts by weight (for example, 0.7 to 3 parts by weight), especially about 0.8 to 2.5 parts by weight. Good.

  In addition, although the usage-amount of an acid catalyst is based also on the kind of acid catalyst and the kind of compound (1b), it is 0.1-100 mol with respect to 1 mol of compounds represented by Formula (1a), for example. , Preferably 0.5 to 50 mol, more preferably about 1 to 20 mol. In particular, when the acid catalyst is sulfuric acid, the amount of sulfuric acid used is, for example, 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of the compound represented by formula (1a), Preferably it may be about 1 to 8 moles.

The reaction may be performed in combination with a thiol as a co-catalyst in addition to the acid catalyst. When an acid catalyst and thiols are combined, the reaction can proceed efficiently. Examples of thiols include conventional thiols that function as promoters, such as mercaptocarboxylic acid (thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid. Etc.), alkyl mercaptans (for example, C _1-20 alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, preferably C _1-16 alkyl mercaptan), aralkyl mercaptans ( Benzyl mercaptan etc.).

Of these thiols, mercaptocarboxylic acids [for example, mercaptoalkanoic acids such as mercapto C _2-6 alkanoic acid (for example, β-mercaptopropionic acid)] and alkyl mercaptans (for example, C _1-16 alkyl mercaptan) are preferable. In particular, mercaptocarboxylic acid is preferred. Thiols can be used alone or in combination of two or more.

  The amount of thiols used is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 0.1 parts by weight with respect to 1 part by weight of the compound represented by the formula (1a). It may be about 5 parts by weight. Moreover, the ratio of thiols is 1-50 weight part (for example, 1.5-40 weight part) with respect to 100 weight part of acid catalysts, for example, Preferably it is 2-35 weight part (for example, 2.. 5 to 30 parts by weight), more preferably about 3 to 25 parts by weight (for example, 3.5 to 20 parts by weight).

The reaction may be performed in a solvent (or in the presence of a solvent). The solvent is not particularly limited. For example, alcohols (alkyl alcohols such as methanol, ethanol, isopropanol and butanol, cyclohexanol, etc.), ketones (alkyl ketones such as acetone, diisopropyl ketone, and methyl isobutyl ketone, cyclohexanone, etc.) , Ethers (chain ethers such as diethyl ether and diisopropyl ether; cyclic ethers such as tetrahydrofuran and dioxane), glycol ethers (ethylene glycol monomethyl ether, cellosolve, etc.), alkylene glycol monoalkyl ether acetates (methyl cellosolve acetate, Propylene glycol monomethyl ether acetate, etc.), esters (ethyl acetate, etc.), nitriles, amides (dimethyl) Formamide, dimethylacetamide, etc.), sulfoxides, hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene) C _6-12 arenes, preferably C _6-10 arenes, more preferably C _6-8 arenes), etc.], halogen solvents (for example, methylene chloride, chloroform, carbon tetrachloride, etc.). These solvents may be used alone or in combination of two or more.

  Although reaction temperature is not specifically limited, For example, 20-200 degreeC, Preferably it is 40-170 degreeC (for example, 45-150 degreeC), More preferably, it is about 50-120 degreeC (for example, 55-110 degreeC), Usually, it may be about 40 to 100 ° C. (for example, 50 to 90 ° C.). The reaction time may be, for example, 30 minutes to 48 hours, preferably 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 (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The reaction mixture contains unreacted components, catalysts and the like in addition to the target products (compound (1) and compound (2)), so that conventional methods such as filtration, concentration, extraction, crystallization, etc. You may refine | purify using separation means, such as precipitation, recrystallization, column chromatography, and the separation means which combined these.

  In this way, a polyhydroxy compound containing compound (1) and compound (2) is obtained as a reactant. In the reaction product, when the amount of the compound (2) is small in the desired application, the separately prepared compound (2) may be newly mixed as described above. In the reaction product, when the amount of compound (2) is large in the desired application, a part of compound (2) is separated (for example, using column chromatography) by a conventional method, and compound (2 The amount of 2) can also be adjusted.

[Uses of polyhydroxy compounds]
Since the polyhydroxy compound of the present invention has a specific fluorene skeleton in addition to a large number of hydroxyl groups, various properties (optical properties, heat resistance, water resistance, moisture resistance, chemical resistance, electrical properties, It has excellent mechanical properties, dimensional stability, etc.) and is useful for improving or improving these properties in various applications. Moreover, it has a high refractive index due to the skeleton. Therefore, the polyhydroxy compound of the present invention is a functional material [for example, additives (resist additives, resin additives, curing agents (resin curing agents), etc.), reagents (pharmaceuticals, agricultural chemicals, etc.) Or an intermediate thereof] (or a raw material or an intermediate thereof), a resin raw material, and the like, and can be used as a compound for efficiently imparting the excellent characteristics as described above.

  Among these uses, it is suitable as a resin raw material. That is, since a polyhydroxy compound has many hydroxyl groups, it can be used as a resin raw material. Such a resin may be any of a thermoplastic resin, a heat or a photocurable resin, and may be a heat or a photocurable resin in particular. When the polyhydroxy compound of the present invention is used as a heat or photocurable resin raw material, the curability of the cured product can be efficiently improved or improved.

  Specific resin raw materials include, for example, heat or photo-curing resins [for example, acrylic resins (for example, poly (meth) acrylates of polyhydroxy compounds (compounds obtained by (meth) acrylate converting hydroxyl groups of polyhydroxy compounds), etc.) Polyfunctional (meth) acrylates), vinyl ether resins, epoxy resins (for example, glycidyl ethers of polyhydroxy compounds), phenol resins, and the like]. In addition, when using as a polyol component (phenol component) of a phenol resin, in the said Formula (1) or (2), you may use suitably the compound whose m is 0.

  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 measurements were performed as follows.

(Refractive index)
Using a multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 <using circulating thermostatic bath 60-C3>), the refractive index before and after curing at 589 nm was measured while maintaining a temperature of 25 ° C.

(Pencil hardness)
It measured based on JIS5600-5-4. That is, the cured film was placed on a pencil hardness meter ("HEIDON-14" manufactured by Shinto Kagaku Co., Ltd.), and various pencils were pressed at a 45 degree angle while applying a load of 750 g, and cured at a speed of 1 mm / second. The pencil hardness was measured by moving on the film and visually confirming the presence or absence of scratches on the cured film.

(HPLC)
The LC purity was measured using a high-performance liquid chromatograph LaChrom Elite manufactured by Hitachi High-Technologies.

(Preparation method and molar ratio calculation method)
After separating each component from the obtained product in a preparative column, each component is measured by HPLC, and a calibration curve is created to determine the molar ratio of each component in the obtained product. Calculated.

Example 1
126 g (about 0.7 mol) of 9-fluorenone, 555 g (about 2.8 mol) of 1,3-di (2-hydroxyethoxy) benzene, 9.8 ml of β-mercaptopropionic acid, and 280 g of 1,4-dioxane It put into the reactor and 147 ml of 98% sulfuric acid was dripped in the heating state of 80 degreeC, and it reacted for 12 hours. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added for extraction. Excess sulfuric acid was removed by performing the same operation three times. After concentration of the solvent, 800 ml of toluene was added and then cooled to 10 ° C. to obtain 295 g of powder. When the obtained powder was analyzed by high performance liquid chromatography (HPLC), the compound represented by the following formula (1-1) (hereinafter referred to as the compound (1-1)), represented by the following formula (2A-1). It was found that the compound (hereinafter referred to as compound (2A-1)) and the compound represented by the following formula (2B-1) (hereinafter referred to as compound (2B-1)) were included. These compounds were identified by nuclear magnetic resonance (NMR) and electrolytic desorption mass spectrometry (FD-MS), and it was confirmed that each peak of HPLC had the following structure.

  In addition, in area% of HPLC, compound (1-1) is 66%, compound (2A-1) is 19%, compound (2B-1) is 9%, and most of the remainder is compound (2A-1) And Compound (2) other than Compound (2B-1). Moreover, the ratio of the total amount of the compound (2A-1) and the compound (2B-1) to 100 mol of the compound (1-1) is 43 mol, and the compound (2A-1) and the compound (2B-1) The ratio was the former / the latter (molar ratio) = 67/33, which was almost the same as the HPLC area ratio.

(Example 2)
40 g of the powder obtained in Example 1 (polyhydroxy compound containing compound (1-1), compound (2A-1) and compound (2B-1)), 43 g (0.6 mol) of acrylic acid, 70% by weight 1 g of an aqueous methanesulfonic acid solution, 0.01 g of hydroquinone and 100 mL of toluene were placed in a reactor equipped with a Dean-Stark trap and subjected to an esterification reaction under toluene reflux for 5 hours. Water generated during the esterification reaction was removed by a Dean Stark trap to obtain 45 g of a reaction product.

  The reaction product was analyzed in the same manner as in Example 1. As a result, polyacrylate of the polyhydroxy compound obtained in Example 1 (that is, Compound (1-1), Compound (2A-1), Compound (2B-1)) It was confirmed that the hydroxyl group was a compound in which the acryloyloxy group was substituted.

After adding 0.6 g of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) to 40 g of the obtained polyacrylate, ultraviolet rays are irradiated with an integrated light amount of 500 mJ / cm ^2. Thus, a cured product was obtained.

  The refractive index of the cured product was 1.59, and the pencil hardness (on the glass substrate, thickness 10 μm) was 3H.

(Example 3)
36 g (about 0.2 mol) of 9-fluorenone, 118 g (about 0.6 mol) of 1,3-di (2-hydroxyethoxy) benzene, 0.4 ml of β-mercaptopropionic acid, and 60 g of 1,4-dioxane It put into the reactor and 12 ml of 98% sulfuric acid was dripped in the heating state of 80 degreeC, and reaction was performed for 12 hours. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added for extraction. Excess sulfuric acid was removed by performing the same operation three times. After concentration of the solvent, 200 ml of toluene was added and then cooled to 10 ° C. to obtain 80 g of powder. When the obtained powder was analyzed by high performance liquid chromatography (HPLC), it was found to contain the compound (1-1), the compound (2A-1), and the compound (2B-1). These compounds were identified in the same manner as in Example 1.

  In addition, in area% of HPLC, compound (1-1) is 45%, compound (2A-1) is 21%, compound (2B-1) is 11%, and most of the remainder is compound (2A-1). And Compound (2) other than Compound (2B-1). Moreover, the ratio of the total amount of the compound (2A-1) and the compound (2B-1) with respect to 100 mol of the compound (1-1) is 71 mol, and the compound (2A-1) and the compound (2B-1) The ratio was the former / the latter (molar ratio) = 66/34, which was almost the same as the HPLC area ratio.

Example 4
In Example 2, 45 g of the reaction product was obtained in the same manner as in Example 2 except that 40 g of the powder obtained in Example 3 was used instead of the powder obtained in Example 1. It is confirmed that the polyacrylate of the polyhydroxy compound obtained in step (i.e., compound (1-1), compound (2A-1), compound in which hydroxyl group of compound (2B-1) is substituted with acryloyloxy group) did.

After adding 0.6 g of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) to 40 g of the obtained polyacrylate, ultraviolet rays are irradiated with an integrated light amount of 500 mJ / cm ^2. Thus, a cured product was obtained.

  The refractive index of the cured product was 1.59, and the pencil hardness (on the glass substrate, thickness 10 μm) was 3H.

(Comparative Example 1)
The powder obtained in Example 1 was further recrystallized using methyl isobutyl ketone (MIBK) and toluene to obtain a powder.

  The obtained powder was analyzed by high performance liquid chromatography (HPLC). As a result, only the compound (1-1) was present, and the presence of a multimerized compound such as the compound (2A-1) or the compound (2B-1) was present. Could not be confirmed (that is, the compound multimerized by recrystallization was separated and removed).

  In Example 2, the reaction product was obtained in the same manner as in Example 2 except that 40 g of the powder obtained by repeating recrystallization as described above was used instead of the powder obtained in Example 1. 45 g was obtained and confirmed to be polyacrylate (tetraacrylate, ie, a compound in which the hydroxyl group of compound (1-1) was substituted with an acryloyloxy group).

After adding 0.6 g of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) to 40 g of the obtained polyacrylate, ultraviolet rays are irradiated with an integrated light amount of 500 mJ / cm ^2. Thus, a cured product was obtained.

  The refractive index of the cured product was 1.59, and the pencil hardness (on the glass substrate, thickness 10 μm) was H. From this result, it was found that the pencil hardness can be greatly improved without lowering the refractive index by including the multimerized compound.

(Comparative Example 2)
In Example 3, 88 g (0.8 mol) of catechol (1,2-dihydroxybenzene) was used instead of 118 g of 1,3-bis (2-hydroxyethoxy) benzene, and 5 mL was used instead of 12 mL of sulfuric acid. 65 g of powder was obtained in the same manner as in Example 3 except that.

  When the obtained powder was analyzed by high performance liquid chromatography (HPLC), it was a compound represented by the following formula (hereinafter referred to as compound (1-2)), and the compound (2A-1) or compound (2B- The presence of the multimerized compound as in 1) could not be confirmed. The compound was identified by NMR and FD-MS in the same manner as in Example 1 and confirmed that the HPLC peak had the following structure.

(Comparative Example 3)
In Example 2, 45 g of the reaction product was obtained in the same manner as in Example 2 except that 40 g of the powder obtained in Comparative Example 1 was used instead of the powder obtained in Example 1. Comparative Example 1 It was confirmed that the polyacrylate of the polyhydroxy compound (tetrahydroxy compound) obtained in (4) was a tetraacrylate (ie, a compound in which the hydroxyl group of the compound (1-2) was substituted with an acryloyloxy group).

After adding 0.6 g of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) to 40 g of the obtained polyacrylate, ultraviolet rays are irradiated with an integrated light amount of 500 mJ / cm ^2. Thus, a cured product was obtained.

  The refractive index of the cured product was 1.60, the pencil hardness (on the glass substrate, thickness 10 μm) was H, and almost the same results as Comparative Example 1 were obtained.

  The polyhydroxy compound of the present invention includes a resin material (for example, a heat or photocurable resin polyol component such as an acrylic resin) and a functional material [for example, an additive (resist additive, resin additive, Curing agents (curing agents for resins, etc.), raw materials or intermediates of reagents (pharmaceuticals, agricultural chemicals, etc.)] (or raw materials or intermediates thereof) and the like.

Claims (12)

A polyhydroxy compound comprising a compound represented by the following formula (1) and a compound represented by the following formula (2).

[Wherein, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, k is an integer of 0 to 4, X is a group — [O— (R ² O) _m —H] (wherein R ² is An alkylene group, m represents an integer of 0 or more), n represents an integer of 2 or more, R ³ represents a substituent, p represents an integer of 0 or more, and q represents an integer of 0 or more. ] In the formulas (1) and (2), ring Z is a benzene ring or naphthalene ring, R ² is a C _2-4 alkylene group, m is 0 to 10, n is 2 to 4, R ³ is an alkyl group or an aryl group, The polyhydroxy compound according to claim 1, wherein p is 0 to 3. The formula (1) or (2), wherein the ring Z is a benzene ring, R ² is a C _2-4 alkylene group, m is 0 to 2, n is 2 or 3, and p is 0. Polyhydroxy compound. In the formulas (1) and (2), the following formula (a)

(In the formula, Z, X, R ³ , n, and p are the same as described above.)
Is a group represented by the following formula (a1):

(In the formula, p1 represents an integer of 0 to 3, and X and R ³ are the same as described above.)
The polyhydroxy compound according to claim 1, which is a group represented by the formula:   The ratio of the compound represented by Formula (2) is 10 mol or more with respect to 100 mol of compounds represented by Formula (1), The polyhydroxy compound in any one of Claims 1-4.   The compound represented by formula (2) includes at least compound (2A) in which q is 0 in formula (2) and compound (2B) in which q is 1 in formula (2). A polyhydroxy compound according to any one of the above.   The polyhydroxy compound according to claim 6, wherein the ratio of the compound (2A) to the compound (2B) is the former / the latter (molar ratio) = 99/1 to 50/50.   The ratio of the compound represented by the formula (2) is 20 moles or more with respect to 100 moles of the compound represented by the formula (1), and the ratio of the compound (2A) and the compound (2B) is the former / The polyhydroxy compound according to claim 6 or 7, wherein the latter (molar ratio) = 90/10 to 50/50.   Resin which uses the polyhydroxy compound in any one of Claims 1-8 as a polymerization component.   The resin according to claim 9, which is a heat or photocurable resin having a polyhydroxy compound as a polyol component.   The resin according to claim 9 or 10, which is a poly (meth) acrylate of a polyhydroxy compound.   A cured product of the resin according to claim 10 or 11.