JP5951286B2 - Thermoplastic (meth) acrylic resin with fluorene skeleton - Google Patents

Description

  The present invention relates to a novel thermoplastic (meth) acrylic resin having excellent properties such as a high refractive index, a method for producing the resin, and a composition for obtaining the resin.

  A polymer obtained by chain polymerization is obtained by polymerizing a polymerizable unsaturated monomer (radical polymerization, ionic polymerization, etc.). Such a polymer has various excellent properties depending on the type of monomer as a polymerization component, and is used as various resin materials. For example, polymethyl methacrylate resin (PMMA resin) is used in various fields such as optical materials, household electrical appliances, and parts of automobiles, taking advantage of its transparency and dimensional stability. In recent years, PMMA resins have been widely used in optical materials such as optical lenses, prisms, liquid crystal display sheets and films, and light guide plates.

  And the performance (for example, heat resistance, optical characteristics, etc.) required for such a polymer has become higher with the enhancement of the functionality of resin materials. For example, the PMMA resin having transparency as described above tends to be required to be thin and light (for example, lamp lens unit use) with design and power saving. In order to reduce the distance between the lens and the light source, excellent heat resistance is required. However, although the PMMA resin has excellent transparency, it has problems such as a low refractive index and low heat resistance.

  On the other hand, compounds having a fluorene skeleton are known to have excellent heat resistance, and attempts have been made to introduce a fluorene skeleton derived from such a compound into a resin.

  JP-A-2009-79013 (Patent Document 1) discloses 9-fluorenyl (meth) acryloyloxyfluorenes and 9-fluorenyl (meth) acryloyloxymethylfluorenes as disclosed in JP-A-2009-13096 (Patent Document 2). ) Describes that 9- (meth) acryloyloxyphenyl-9-phenylfluorene or the like can be used as a diluent for a heat or photocurable (meth) acrylic resin, respectively. In these documents, 9-fluorenyl (meth) acryloyloxyfluorenes can be used as resin modifiers (diluents, copolymerizable monomers (or resin modifiers), etc.). It is not assumed to be a thermoplastic polymer raw material.

  JP-A-2004-346125 (Patent Document 3) describes (A) (meth) acrylate monomer represented by the general formula (1) or (2):

(Wherein R ₁ and R ₂ are alkylene groups having 1 to 3 carbon atoms, m is 0 or 1, and X represents a (meth) acryloyloxy group); (B) Aliphatic, alicyclic One or more polyvalent (meth) acrylate monomers selected from the group of polyvalent and aralkyl polyvalent (meth) acrylate monomers; and (C) a photopolymerization initiator or / and a thermal polymerization initiator as essential components A curable resin composition is disclosed.

  Furthermore, JP 2000-319336 A (Patent Document 4) discloses a resin composition containing 9- (meth) acryloyloxymethylfluorene (A) and an unsaturated group-containing compound (B) other than the component (A). Is disclosed. As the unsaturated group-containing compound (B), reactive monomers (for example, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy -3-phenyloxypropyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, o-phenylphenyloxyethyloxyethyl (meth) acrylate, 2 -Hydroxy-3- (dibromophenyl) oxypropyl (meth) acrylate, dicyclopentanyl (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, tetrabromobisphenol A (Meth) such as reethoxy di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate Acrylate-based reactive monomers, N-vinylcaprolactam, etc.), reactive oligomers (for example, epoxy (meth) acrylates, which are a reaction product of epoxy resins and (meth) acrylic acid, polyols and organic polyisocyanates) And (meth) acrylate-based reactive oligomers such as urethane (meth) acrylate, which is a reaction product of hydroxyl group-containing (meth) acrylates, and the like. In this document, it is assumed that the resin composition is cured by ultraviolet rays or the like, and similarly to Patent Document 3, the production of a thermoplastic polymer is not assumed.

  JP 2006-193708 (Patent Document 5) discloses a (meth) acrylic polymer containing one or more groups selected from a carboxylic acid group, a carboxylic anhydride group, and a carboxylic acid t-butyl ester group; A method of obtaining a fluorene skeleton-containing (meth) acrylic polymer by reacting a fluorene compound having a functional group capable of reacting with these groups (such as 9-fluorenylmethanol) is disclosed. However, although the method of this document can introduce a fluorene unit into a methacrylic polymer, it requires a two-step reaction to react with a fluorene compound after polymerization. In addition, carboxylic acid groups and the like may remain without reacting with the fluorene compound, and there is a possibility that a (meth) acrylic polymer having desired characteristics cannot be obtained efficiently.

  In JP-A-2006-312709 (Patent Document 6), 9-fluorenylmethanol is reacted with a (meth) acrylic acid ester polymer (polymethyl methacrylate, etc.) to contain a polycyclic aromatic group. A method for producing a (meth) acrylic acid ester polymer is disclosed. However, this method also requires a two-step reaction, and the reaction with alcohol uses transesterification with an ester group having poor reactivity, so that a substantially special transesterification catalyst is required. . Further, since transesterification occurs randomly, it is difficult to obtain a polymer having a structural regularity such as a block structure. Furthermore, alcohol (such as methanol) by-produced by transesterification and 9-fluorenylmethanol become a competitive reaction, and there is a possibility that the 9-fluorenylmethyl group cannot be efficiently introduced.

JP 2009-79013 A (Claims) JP 2009-13096 A (Claims) JP 2004-346125 A (Claims) JP 2000-319336 A (claims, paragraphs [0004], [0008] to [0010], examples) JP 2006-193708 A (Claims) Japanese Patent Laying-Open No. 2006-312709 (Claims)

  Accordingly, an object of the present invention is to provide a composition (polymerization) useful for obtaining a novel (meth) acrylic resin (thermoplastic (meth) acrylic resin) having a fluorene skeleton and having excellent properties such as a high refractive index. Composition), a fluorene skeleton-containing (meth) acrylic resin obtained from the composition, and a method for producing the (meth) acrylic resin.

  Another object of the present invention is to provide a composition capable of efficiently introducing a fluorene skeleton into a (meth) acrylic resin, and a fluorene skeleton-containing (meth) acrylic resin obtained from this composition.

  Yet another object of the present invention is to refraction without impairing the excellent properties of thermoplastic (meth) acrylic resins (for example, (meth) acrylic resins based on methyl methacrylate such as polymethyl methacrylate). It is in providing the composition which can improve characteristics, such as a rate and heat stability, and the fluorene skeleton containing (meth) acrylic resin obtained by this composition.

  As described above, monofunctional (meth) acrylic monomers having a fluorene skeleton such as 9-fluorenyl (meth) acryloyloxymethylfluorenes are used as diluents and constituent monomers of thermosetting resins (that is, polyfunctional monomers and Monomer used in combination) was known to be used, but it was not recognized that it could be used as a thermoplastic resin raw material, particularly as a thermoplastic (meth) acrylic resin raw material, and there was no report of it. It was.

  In such a situation, the present inventors have intensively studied to achieve the above-mentioned problem, and as a result, the monofunctional (meth) acrylic monomer having a fluorene skeleton is polymerized alone, resulting in excellent optical properties and It is possible to form a thermoplastic (meth) acrylic resin having heat resistance stability (such as a high thermal decomposition temperature), and such monofunctional (meth) acrylic monomers can be used for other monofunctional (meth). Compared to other monofunctional (meth) acrylic polymers, thermoplastic (meth) acrylic resins that can be copolymerized with acrylic monomers and that have a fluorene skeleton introduced by such copolymerization. The present inventors have found that the optical characteristics and heat stability are remarkably improved, and the present invention has been completed.

  That is, the polymerizable composition of the present invention contains a monofunctional (meth) acrylic monomer (A) having a fluorene skeleton. Such a polymerizable composition may usually be a polymerizable composition for producing a thermoplastic resin (particularly, a thermoplastic (meth) acrylic resin).

  The monofunctional (meth) acrylic monomer (A) may be, for example, a compound represented by the following formula (A1).

(In the formula, R ¹ represents a cyano group, a halogen atom or an alkyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group, and R ⁴ represents a direct bond, an alkylidene group or an alkylene group. R ⁵ represents a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and n is 0 or 1.)
Typically, the monofunctional (meth) acrylic monomer (A) may be a compound in which R ⁴ is a direct bond or a methylene group, m is 0, and n is 0 in the formula (A1). .

  The polymerizable composition of the present invention may further contain a monofunctional non-fluorene (meth) acrylic monomer (B). Such a non-fluorene type (meth) acrylic monomer (B) may typically contain methyl methacrylate. Such a non-fluorene (meth) acrylic monomer (B) preferably contains methyl methacrylate alone or as a main component. For example, the non-fluorene (meth) acrylic monomer (B) is methacrylic acid. Methyl may be contained in a proportion of 50 mol% or more.

  In such a composition, the proportion of the monofunctional (meth) acrylic monomer (A) is based on the total amount of the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer (B). It may be 10 mol% or more.

  The present invention also includes a method for producing a resin (particularly, a thermoplastic (meth) acrylic resin) by polymerizing the polymerizable composition.

  Further, the present invention is a heat stability improver for improving the heat stability of a thermoplastic (meth) acrylic resin comprising a monofunctional non-fluorene (meth) acrylic monomer (B) as a polymerization component. In addition, a heat-resistant stability improver composed of a monofunctional (meth) acrylic monomer (A) having a fluorene skeleton is also included.

  Furthermore, the present invention includes a resin (particularly, a thermoplastic (meth) acrylic resin) obtained by polymerization of the polymerizable composition. Such a resin typically has a ratio of methyl methacrylate units in units derived from the non-fluorene-based (meth) acrylic monomer (B) of 50 mol% or more, and a monofunctional (meth) acrylate ( A thermoplastic having a proportion of the unit derived from A) of 10 mol% or more based on the total amount of the unit derived from the monofunctional (meth) acrylate (A) and the unit derived from the non-fluorene-based (meth) acrylate (B) ( It may be a (meth) acrylic resin.

  The resin has a high refractive index and excellent heat stability (or heat resistance). For example, the refractive index at 25 ° C. and 589 nm is 1.5 or more and the 5% weight loss temperature is 200 ° C. or more. May be.

  In the present specification, “non-fluorene-based” means “not having a fluorene skeleton”. In the present specification, “class” such as “fluorenes” means that it may have a substituent.

  The polymerizable composition of the present invention is useful for obtaining a novel (meth) acrylic resin (thermoplastic (meth) acrylic resin) having excellent properties such as a high refractive index. Then, by subjecting such a composition to polymerization, the (meth) acrylic resin has excellent properties [for example, optical properties (high refractive index, high transparency, etc.) and heat resistance (or heat stability, for example, (Meth) acrylic resin having a high thermal decomposition temperature, etc.].

  In the polymerizable composition of the present invention, a monofunctional (meth) acrylic monomer having a fluorene skeleton can be copolymerized with another monofunctional (meth) acrylic monomer, so that the fluorene skeleton is converted into a (meth) acrylic resin. Can be introduced efficiently. The (meth) acrylic resin having such a fluorene skeleton introduced is a polymer of other monofunctional (meth) acrylic monomers [that is, a thermoplastic (meth) acrylic resin (for example, methacrylic acid such as polymethyl methacrylate). The properties such as refractive index and heat stability can be improved without impairing the excellent properties of the (meth) acrylic resin containing methyl as a main component. In particular, in the present invention, characteristics such as refractive index and heat stability can be sufficiently improved or improved by using a small amount of a monofunctional (meth) acrylic monomer having a fluorene skeleton as a polymerization component.

[Polymerizable composition]
The polymerizable composition of the present invention contains a monofunctional (meth) acrylic monomer (A) having at least a fluorene skeleton as a polymerization component (particularly a polymerization component of a thermoplastic resin).

(Monofunctional (meth) acrylic monomer (A))
The monofunctional (meth) acrylic monomer (A) (sometimes referred to as a fluorene monomer) has a fluorene skeleton and has a monofunctional (that is, one (meth) acryloyl group which is an addition polymerizable group). If it is a compound, it will not specifically limit, For example, the compound represented by a following formula (A1), the compound represented by a following formula (A2), etc. are mentioned.

(Wherein R ¹ represents a substituent, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkylene group, R ⁴ represents a direct bond or a divalent non-aromatic hydrocarbon group, R ⁵ represents a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and n is 0 or 1.)

(In the formula, Z represents an aromatic hydrocarbon ring, p represents an integer of 0 or more, and R ¹ , R ² , R ³ , R ⁵ , k, and m are the same as described above.)
In the formulas (A1) and (A2), examples of the substituent represented by the group R ¹ include non-reactive substituents such as a cyano group, a halogen atom (chlorine atom, bromine atom, etc.), a hydrocarbon group [for example, An alkyl group, an aryl group (C _6-10 aryl group such as a phenyl group) and the like], and is often a cyano group, a halogen atom or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

In the formulas (A1) and (A2), examples of the alkylene group represented by the group R ³ include a C _2-10 alkylene group (eg, ethylene group, trimethylene group, propylene group, butane-1,2-diyl group). C _2-6 alkylene group such as hexylene group) and the like, and C _2-4 alkylene groups (particularly, C _2-3 alkylene groups such as ethylene group and propylene group) are particularly preferable. R ³ may be the same or different alkylene group when m is plural, and may usually be the same alkylene group. The number (addition mole number) m of oxyalkylene groups (OR ³ ) can be selected, for example, from a range of about 0 to 15 (eg, 0 to 10), for example, 0 to 8 (eg, 1 to 8), preferably May be 0-6 (eg, 1-6), more preferably 0-4 (eg, 1-4). In particular, from the viewpoint of a high refractive index, m may be about 0 to 2.

In the formula (A1), examples of the divalent non-aromatic hydrocarbon group R ⁴ include alkylidene groups (for example, C _{1- 1} such as methylene group, ethylidene group, propylidene group, propane-2,2-diyl group, etc.). ₁₀ alkylidene group, preferably C _1-6 alkylidene group, more preferably C _1-4 alkylidene group), alkylene group (for example, C _2-10 alkylene group such as ethylene group, propylene group, trimethylene group, tetramethylene group) , Preferably a C _2-6 alkylene group, more preferably a C _2-4 alkylene group), a cycloalkylene group (eg, a C _5-10 cycloalkylene group such as a cyclohexylene group, preferably a C _5-8 cycloalkylene group). And cycloalkanedimethylene groups (for example, 1,4-cyclohexanedimethylene group) It is. Representative divalent non-aromatic hydrocarbon groups include alkylidene groups and alkylene groups. Preferred groups R ⁴ are a direct bond, an alkylidene group (for example, a C _1-4 alkylidene group, particularly a methylene group), and an alkylene group (for example, a C _2-4 alkylene group such as an ethylene group).

In the formulas (A1) and (A2), as the substituent R ⁵ , for example, usually a non-reactive substituent such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.) C _1-12 alkyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group, etc., preferably C _{5 -6} cycloalkyl groups, etc.), aryl groups (eg C _6-14 aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc., preferably C _6-10 aryl groups, more preferably C _6-8 aryl) group, etc.), a hydrocarbon group such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group); alkoxy (Methoxy group, _{C 1-8} alkoxy group such as ethoxy group, etc. Preferably the _{C 1-6} alkoxy group), (such as _{C 5-10} cycloalkyl group such as a hexyloxy group cyclohexylene) cycloalkoxy group, an aryloxy group -OR such as (C _6-10 aryloxy group such as phenoxy group), aralkyloxy group (for example, C _6-10 aryl-C _1-4 alkyloxy group such as benzyloxy group) wherein R is A hydrocarbon group (such as the hydrocarbon group exemplified above) is shown. An alkylthio group (a C _1-8 alkylthio group such as a methylthio group or an ethylthio group, preferably a C _1-6 alkylthio group), a cycloalkylthio group (such as a C _5-10 cycloalkylthio group such as a cyclohexylthio group), -SR (wherein R is a C _6-10 arylthio group such as a thiophenoxy group), an aralkylthio group (eg, a C _6-10 aryl-C _1-4 alkylthio group such as a benzylthio group) Same as the above); acyl group (C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom) Nitro group; cyano group; substituted amino group (for example, dimethylamino) And the like, such as dialkylamino group), such as.

The preferred substituent R ⁵ is, 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, the group R ⁵ is preferably an alkyl group [C _1-4 alkyl group (particularly methyl group)], an aryl group [eg C _6-10 aryl group (particularly phenyl group)], or the like.

In the formula (A2), the substitution number p of the substituent R ⁵ can be appropriately selected depending on the kind of the ring Z and the like, and is not particularly limited, and is, for example, 0 to 8, preferably 0 to 6 (for example, 1 ~ 5), more preferably 0-4, in particular 0-2. In particular, when the ring Z is a benzene ring, the substitution number p is, for example, 0 to 3, preferably 0 to 2, and more preferably 0 or 1 (particularly 1). The number of substitutions p may be the same or different. In addition, the substitution position of the substituent R ⁵ is not particularly limited. For example, when the ring Z is a benzene ring, an appropriate 2-6 position (for example, the 3rd, 3,5-position, etc.) of the phenyl group. Can be replaced with a position.

Specific examples of the compound represented by the formula (A1) include compounds in which R ⁴ is a direct bond in the formula (A1) [for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy -9-alkylfluorene, 9- (meth) acryloyloxy-9-arylfluorene, etc.], a compound in which R ⁴ is a methylene group in the formula (A1) [for example, 9- (meth) acryloyloxymethylfluorene, etc.], etc. Is included.

In addition, specific compounds represented by the formula (A2) include, for example, 9- (meth) acryloyloxyphenyl-9-phenylfluorene [for example, 9- (4- (meth) acryloyloxyphenyl) -9- Phenylfluorene etc.], 9- (alkyl- (meth) acryloyloxyphenyl) -9-phenylfluorene [e.g. 9- (4- (meth) acryloyloxy-3-methylphenyl) -9-phenylfluorene, 9- ( 9- (mono- or di-C _1-4 alkyl- (meth) acryloyloxyphenyl) -9-phenylfluorene] such as 4- (meth) acryloyloxy-3,5-dimethylphenyl) -9-phenylfluorene], 9- (Aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene [for example, 9- (4- (me 9) 9- (mono or di-C _6-10 aryl- (meth) acryloyloxyphenyl) -9-phenylfluorene] such as acryloyloxy-3-phenylphenyl) -9-phenylfluorene], 9- (meth) acryloyloxy (poly) alkoxy-phenyl-9-phenyl fluorene [e.g., 9- (4- (2- (meth) acryloyloxy ethoxy) phenyl) -9-phenyl-fluorene 9- (meth) acryloyloxy _{(poly) C 2 4-} alkoxyphenyl-9-phenylfluorene and the like], 9- (alkyl- (meth) acryloyloxy (poly) alkoxyphenyl) -9-phenylfluorene [for example, 9- (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl) -9-phenylfluorene, 9- ( - (2- (meth) acryloyloxy ethoxy) -3,5-dimethylphenyl) -9-phenyl-fluorene 9- (mono- or _{di-C 1-4} alkyl - (meth) acryloyloxy _{(poly) C 2-4} Alkoxyphenyl) -9-phenylfluorene], 9- (aryl- (meth) acryloyloxy (poly) alkoxyphenyl) -9-phenylfluorene [e.g. 9- (4- (2- (meth) acryloyloxyethoxy)- 9- (mono- or di-C _6-10 aryl- (meth) acryloyloxy (poly) C _2-4 alkoxyphenyl) -9-phenylfluorene] such as 3-phenylphenyl) -9-phenylfluorene.

A preferred monofunctional (meth) acrylic monomer (A) is a compound represented by the formula (A1). In particular, in the formula (A1), R ⁴ is a direct bond or a methylene group, m is 0, and n is 0 (for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxymethylfluorene, etc.) May be suitably used. The compound represented by the formula (A1) can be suitably used for reasons such as easy suppression of coloring, low viscosity, and easy synthesis.

The monofunctional (meth) acrylic monomer (B) usually contains methyl methacrylate, but the monofunctional (meth) acrylic monomer (A) is a methacrylic monomer (for example, the formula (A1) or the formula In (A2), R ² may be a methyl group) or an acrylic monomer (for example, a compound in which R ² is a hydrogen atom in Formula (A1) or Formula (A2)). . In the present invention, even an acrylic monomer can be copolymerized with methyl methacrylate.

  The monofunctional (meth) acrylic monomer (A) may be used alone or in combination of two or more.

  The monofunctional (meth) acrylate monomer (A) can be homopolymerized (including copolymerization of different monofunctional (meth) acrylic monomers (A)), and by such polymerization, optical properties and heat resistance can be obtained. A thermoplastic (meth) acrylic resin having excellent properties and the like can be obtained.

  The monofunctional (meth) acrylic monomer (A) is not a monofunctional (meth) acrylic monomer (A) but a monofunctional (meth) acrylic monomer (that is, a monofunctional non-fluorene (meth) acrylic). It is also possible to copolymerize with a monomer. By copolymerization, the polymerizability may be improved as compared with the case where the monofunctional (meth) acrylic monomer (A) is used alone. Therefore, the polymerization component constituting the composition of the present invention can be composed only of the monofunctional (meth) acrylic monomer (A), but the monofunctional (meth) acrylic monomer (A) and the non-fluorene monomer You may comprise.

(Monofunctional non-fluorene (meth) acrylic monomer (B))
The non-fluorene-based (meth) acrylic monomer (B) is particularly a monofunctional (meth) acrylic monomer having no fluorene skeleton (that is, a compound having one (meth) acryloyl group which is an addition polymerizable group). Without limitation, for example, alkyl (meth) acrylate [methyl (meth) acrylate, (meth) acrylic acid ethyl, (meth) acrylic acid C _1-20 alkyl such as butyl (meth) acrylate, preferably (meth ) _C1-10 alkyl acrylate, more preferably _C1-4 alkyl (meth) acrylate], cycloalkyl (meth) acrylate [for example, (meth) acrylic acid C ₅ such as cyclohexyl (meth) acrylate. _-8 cycloalkyl; (meth) acrylates such as bornyl (meth) acrylate and isobornyl (meth) acrylate Polycyclic cycloalkylylyl], aryl (meth) acrylate [phenyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [(2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate) , Hydroxy C _2-10 alkyl (meth) acrylates such as 2-hydroxybutyl (meth) acrylate, etc.], (poly) oxyalkylene glycol mono (meth) acrylate [for example, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meta) ), etc. (poly) _{oxy-C 2-6} alkylene glycol mono (meth) acrylates such as acrylates, alkoxyalkyl (meth) acrylates [e.g., 2-methoxyethyl (meth) acrylate, (meth) acrylic Such as 3-methoxybutyl (meth) acrylic acid C _1-4 alkoxyalkyl, haloalkyl (meth) acrylates [for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) Halo C _1-10 alkyl (meth) acrylates such as acrylate], aryloxyalkyl (meth) acrylates [for example, phenoxy C _1-10 alkyl (meth) acrylates such as phenoxyethyl (meth) acrylate], aminoalkyl ( Meth) acrylate [for example, N-substituted aminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl acrylate, etc.], glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate (Meth) acrylic acid esters (or (meth) acrylates); (meth) acrylic acid; (meth) acrylamide, N-substituted (meth) acrylamide (N, N-dimethyl (meth) acrylamide, etc. (Meth) acrylamides such as N-diC _1-4 alkyl (meth) acrylamide, N-hydroxy C _1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide) and the like. The (meth) acrylic monomer (B) may be used alone or in combination of two or more.

  Representative (meth) acrylic monomers (B) include (meth) acrylic acid esters (monofunctional (meth) acrylic acid esters such as (meth) acrylic acid alkyl esters). In particular, the (meth) acrylic monomer (B) may comprise at least methyl methacrylate. Such a (meth) acrylic monomer (B) containing methyl methacrylate may be composed only of methyl methacrylate, and methyl methacrylate and other (meth) acrylic monomers (for example, not methyl methacrylate (meta ) Acrylic acid ester etc.). Typically, the non-fluorene (meth) acrylic monomer (B) often contains methyl methacrylate as a main component, for example, the ratio of methyl methacrylate in the non-fluorene (meth) acrylic monomer (B). Is 50 mol% or more (for example, 50 to 100 mol%), preferably 70 mol% or more (for example, 70 to 100 mol%), more preferably about 80 to 100 mol% (for example, 90 to 100 mol%). It may be.

  The ratio between the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) acrylic monomer (B) can be selected according to the desired properties, for example, the monofunctional (meth) acrylic monomer (A) Is 1 mol% or more (for example, 3 to 99 mol%), preferably 5 with respect to the total amount of the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) acrylic monomer (B). It may be about mol% or more (for example, 7 to 97 mol%), more preferably about 10 mol% or more (for example, 15 to 95 mol%), particularly about 20 mol% or more (for example, 25 to 90 mol%). .

  In particular, when the proportion of the monofunctional (meth) acrylic monomer (A) is relatively small, the total amount of the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer (B) 1 to 45 mol%, preferably 3 to 40 mol%, more preferably 5 to 40 mol%, and usually 7 to 35 mol% (for example, 10 to 30 mol%). With such a relatively small ratio, the amount of fluorene skeleton introduced into the resin (thermoplastic resin) described later is also correspondingly reduced. However, even with such a small amount of fluorene skeleton introduced, heat resistance is stable. Property and refractive index can be improved. Therefore, such characteristics can be improved or improved without reducing the characteristics derived from the monofunctional (meth) acrylic monomer (B) as much as possible.

  On the other hand, when the proportion of the monofunctional (meth) acrylic monomer (A) is relatively large, the total amount of the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer (B) 45 mol% or more (for example, 45 to 99 mol%), preferably 50 to 98 mol%, more preferably 55 to 97 mol%, particularly 60 to 95 mol% (for example, 70 to 90 mol%). May be. When the ratio is relatively large as described above, it is possible to efficiently obtain a resin (thermoplastic resin) having a large ratio of fluorene skeleton while increasing the polymerizability.

The polymerization component (or polymerizable composition) belongs to any category of the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) acrylic monomer (B) as long as there is no actual harm. May contain any monofunctional monomer. Examples of such monofunctional monomers include olefin monomers [eg, chain olefins (for example, α-C _2-6 olefins such as ethylene, propylene, 1-butene), cyclic olefins (such as norbornene)]. , Styrene monomers (for example, styrene, α-methylstyrene, vinyltoluene, etc.), vinyl ester monomers (for example, vinyl acetate), halogen-containing monomers (for example, vinyl halides such as vinyl chloride), vinyl cyanide Monomers (for example, (meth) acrylonitrile), vinyl ether monomers (for example, alkyl vinyl ethers such as methyl vinyl ether), unsaturated carboxylic acid monomers (for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, etc.), vinyl pyrrolidone, etc. Can be mentioned These monofunctional monomers may be used alone or in combination of two or more. The proportion of such a monofunctional monomer may be 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, based on the entire polymerization component. That is, the polymerizable composition of the present invention is usually a composition for obtaining a thermoplastic resin (that is, a thermoplastic (meth) acrylic resin) mainly composed of a (meth) acrylic monomer.

The polymerizable composition of the present invention is a composition mainly for obtaining a thermoplastic resin (particularly, a thermoplastic (meth) acrylic resin), but a polyfunctional monomer as long as the thermoplasticity is not impaired. May be included. Examples of the polyfunctional monomer include bifunctional (meth) acrylate {alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, hexanediol di (meth) acrylate, _C2-10 alkylene glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate], (poly) oxyalkylene glycol di (meth) acrylate [diethylene glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) ) (Poly) oxy C _2-6 alkylene glycol di (meth) acrylate etc.] such as acrylate], di (meth) acrylate of bisphenol A (or its C _2-3 alkylene oxide adduct), polyhydric alcohol (or C thereof) _2-3 alkylene oxide adduct) di (meth) acrylate [for example, diol of triol such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, etc. (Meth) acrylate, di (meth) acrylate of tetraol such as pentaerythritol di (meth) acrylate], bridged cyclic (meth) acrylate (for example, tricyclodecane dimethanol di (meth) acrylate)}, More than trifunctional officers Sex (meth) acrylate {e.g., (meth) acrylate of a polyhydric alcohol (or its C _2-3 alkylene oxide adduct), for example, glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane Such as tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Polyfunctional (meth) acrylic monomers such as polyol tri to hexa (meth) acrylate}; multifunctional non- (meth) acrylic such as divinylbenzene and triallyl isocyanurate Etc. system monomer. Polyfunctional monomers may be used alone or in combination of two or more. In addition, even when such a polyfunctional monomer is contained, the amount is very small. For example, even if it is 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less of the entire polymerization component. Good.

  The polymerizable composition of the present invention may contain a conventional additive in addition to the above polymerization components. Such additives can be selected according to the polymerization method, for example, polymerization initiator, catalyst (polymerization catalyst), emulsifier, dispersant, chain transfer agent (thiols, etc.), polymerization inhibitor (heat polymerization prohibited) Etc.). These additives may be used alone or in combination of two or more.

  Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Usually, in general radical polymerization, a thermal polymerization initiator can be preferably used. Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compound {2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyano) Azo compounds, etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime, etc.)]. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator is 100 mol of the polymerization component (for example, the total amount of the monofunctional (meth) acrylic monomer (A), the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) acrylic monomer)). On the other hand, it may be, for example, 0.01 to 20 mol (for example, 0.05 to 15 mol), preferably 0.1 to 10 mol, and more preferably about 0.3 to 5 mol.

  Moreover, the polymerizable composition may contain a solvent depending on the polymerization method and the like. Examples of the solvent (or dispersion medium) include alcohols (alkyl alcohols such as ethanol, propanol and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (depending on the type of raw materials used) Aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (such as methylene chloride and chloroform), ethers (dimethyl ether, Chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran), esters (such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and ethyl butyrate), ketones (acetone, ethyl methyl ketone, methyl) Isobutyl ketone Cyclohexanone, N-methyl-2-pyrrolidone, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (methylcarbitol, ethyl carbitol, butyl carbitol etc.), propylene glycol monoalkyl ethers ( Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate etc.), amides (N, N-dimethylformamide, N N-dimethylacetamide), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetonitrile, Nzonitoriru etc.), and organic solvents such as N- methylpyrrolidone. The solvent can be used alone or as a mixed solvent. Depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.), the polymerization can be carried out in the presence of water.

  The ratio of the polymerization component in the solvent (or dispersion medium) is, for example, about 0.01 to 10 mol / L, preferably about 0.1 to 5 mol / L, and more preferably about 0.3 to 3 mol / L. May be.

[Resin and its production (polymerization) method]
The composition (polymerizable composition) of the present invention is useful as a composition for obtaining a resin. Such a resin may be a heat or photocurable resin, but is usually a thermoplastic resin. Such a thermoplastic resin is usually a monofunctional (meth) acrylic monomer (A) or a monofunctional (meth) acrylic monomer (A) and a non-fluorene-based (meth) acrylic as described above. In many cases, it is a resin having the monomer (B) as a main component of the polymerization component, that is, a thermoplastic (meth) acrylic resin.

  Such a resin (in particular, a thermoplastic (meth) acrylic resin) can be obtained by polymerizing the polymerizable composition. The polymerization (method) is not particularly limited as long as it is addition polymerization (chain polymerization), and may be any of radical polymerization, ionic polymerization (such as anionic polymerization), and coordination polymerization. For this purpose, radical polymerization can be preferably used. The radical polymerization may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In the present invention, from the viewpoint of reaction control, solution polymerization may be particularly preferably used among radical polymerizations.

  The polymerization reaction may be performed under cooling or heating depending on the polymerization method. When heating (for example, when thermally polymerizing), the heating temperature may be, for example, 35 to 200 ° C, preferably 40 to 150 ° C, and more preferably about 45 to 100 ° C. The polymerization time (reaction time) may be, for example, about 20 minutes to 100 hours, preferably 1 to 50 hours, more preferably about 2 to 30 hours (for example, 3 to 20 hours).

  The reaction may be performed in air, but may be performed in an atmosphere or flow of an inert gas (such as helium, nitrogen, argon). Further, the reaction may be performed under normal pressure, increased pressure, or reduced pressure.

  The product is separated by a conventional method, for example, separation means (separation method) such as filtration, concentration, reprecipitation, extraction, crystallization (recrystallization, etc.), column chromatography, or a combination of these. It may be purified.

  The resin (thermoplastic (meth) acrylic resin) of the present invention is obtained as described above. The weight average molecular weight of such a resin (particularly, a thermoplastic (meth) acrylic resin) is, for example, 3000 to 1000000, preferably 5000 to 500000, more preferably 7000 to 200000 (for example, 10000 to 100000), particularly 15000. It may be about 80,000. In addition, a weight average molecular weight can be calculated | required in polystyrene conversion by gel permeation chromatography (GPC).

  In the resin, the proportion of units derived from the monofunctional (meth) acrylic monomer (A), the non-fluorene-based (meth) acrylic monomer (B), and the like generally corresponds to the proportion in the resin composition. For example, the proportion of methyl methacrylate units in the units derived from the non-fluorene (meth) acrylic monomer (B) constituting the resin is 50 mol% or more (for example, 50 to 100 mol%), preferably 70 mol%. It may be about (for example, 70 to 100 mol%), more preferably about 80 to 100 mol% (for example, 90 to 100 mol%).

  Moreover, the ratio of the unit derived from the monofunctional (meth) acrylic monomer (A) constituting the resin is the unit derived from the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer (B). 1 mol% or more (for example, 3-99 mol%), preferably 5 mol% or more (for example, 7-97 mol%), more preferably 10 mol% or more (for example, 15 mol%) with respect to the total amount of the derived unit. ˜95 mol%), particularly about 20 mol% or more (for example, 25 to 90 mol%).

  In particular, when the proportion derived from the monofunctional (meth) acrylic monomer (A) constituting the resin is relatively small, the unit derived from the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer 1 to 45 mol%, preferably 3 to 40 mol%, more preferably 5 to 40 mol%, usually 7 to 35 mol% (for example, 10 to 30 mol%) based on the total amount of the unit derived from (B). It may be a degree.

  On the other hand, when the proportion of the unit derived from the monofunctional (meth) acrylic monomer (A) constituting the resin is relatively large, the unit derived from the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) 45 mol% or more (for example, 45 to 99 mol%), preferably 50 to 98 mol%, more preferably 55 to 97 mol%, particularly 60 to 95 mol, based on the total amount of units derived from the acrylic monomer (B). % (For example, 70 to 90 mol%) may be sufficient.

  When the monofunctional (meth) acrylic monomer (A) and the non-fluorene (meth) acrylic monomer (B) are combined and polymerized, these copolymers are obtained. The form of such a copolymer is not particularly limited, and may be a random copolymer, a block copolymer, an alternating copolymer, or the like. In particular, in the present invention, even a block copolymer can be obtained. In such a block copolymer, characteristics such as refractive index and heat resistance are likely to be improved while maintaining characteristics derived from the polymer of the monomer (A) and characteristics derived from the polymer of the monomer (B). .

  The resin of the present invention is excellent in various properties such as optical properties and heat resistance (heat stability). For example, the refractive index of the resin of the present invention can be selected from a range of about 1.5 or more (for example, 1.51 to 1.75) at 25 ° C. and 589 nm, and 1.52 or more (for example, 1.525 to 2525). 1.7), preferably 1.53 or more (for example, 1.54 to 1.68), more preferably 1.55 or more (for example, 1.56 to 1.65), particularly 1.57 or more (for example, It may be about 1.58 to 1.64).

  The 5% weight reduction temperature (temperature at which 5% by weight decreases) of the resin of the present invention is, for example, 200 ° C. or higher (for example, 220 to 400 ° C.), preferably 230 ° C. or higher (for example, 240 to 370). ° C), more preferably 250 ° C or higher (eg, 260 to 350 ° C). In particular, in the present invention, a non-fluorene (meth) acrylic monomer (B) (for example, methyl methacrylate) is obtained by combining a monofunctional (meth) acrylic monomer (A) and a non-fluorene (meth) acrylic monomer. 5% weight loss temperature is 20 ° C. or higher (for example, 30 to 200 ° C.), preferably 40 ° C. or higher (for example 45 to 170 ° C.), more preferably 50 ° C. or higher (for example) 60 to 150 ° C.), particularly 70 ° C. or more (for example, 80 to 120 ° C.).

  Therefore, the monofunctional (meth) acrylic monomer (A) is a heat resistant stability (heat resistant) of a thermoplastic resin (thermoplastic (meth) acrylic resin) containing a non-fluorene (meth) acrylic monomer (B) as a polymerization component. (For example, as described above, the 5% weight loss temperature is increased by about 50 ° C. or more as compared with the case where only the non-fluorene (meth) acrylic monomer (B) is polymerized). Acts as a stability improver. That is, the monofunctional (meth) acrylic monomer (A) (or heat stability improver) is copolymerized with the non-fluorene-based (meth) acrylic monomer (B) to produce a non-fluorene-based (meth) acrylic monomer ( The heat resistance stability of the thermoplastic (meth) acrylic resin containing B) as a polymerization component is increased.

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

  In addition, the analysis or measurement method of various characteristics is as follows.

(Molecular weight)
Using “HLC-8120GPC” manufactured by Tosoh Corporation, the mobile phase was measured in terms of polystyrene at a flow rate of 1 mL / min with tetrahydrofuran (THF).

(Tg)
As a device, “Rigaku Thermo Plus series DSC8230” manufactured by Rigaku Corporation was used, and measurement was performed at room temperature to 150 ° C. (2nd run evaluation) at a temperature rising rate of 10 ° C./min.

(NMR)
Using “JSX-270” manufactured by JASCO Corporation, the measurement solvent was CDCl ₃ .

(5% weight loss temperature)
Using “SII TG / DTA6200” manufactured by SII Nanotechnology, Inc., measurement was performed under conditions of room temperature to 400 ° C. and a temperature increase rate of 10 ° C./min.

(Refractive index)
The refractive index at 25 ° C. and 589 nm was measured using “Abbe refractive index type DR-M2 / 1410” manufactured by Atago Co., Ltd.

  Further, 9-fluorenylmethyl acrylate (9-acryloyloxymethylfluorene) used for the polymerization was synthesized as follows.

  90.3-fluorenylmethanol 40.3 parts by weight, acrylic acid 87.6 parts by weight, toluene 151 parts by weight, paratoluenesulfonic acid 7.6 parts by weight, methoquinone 0.22 parts by weight, heated, the generated water is Distilled with solvent, condensed, and cooled the reaction mixture when 18 parts by weight of water were produced in the separator. The reaction temperature was 92-105 ° C. The reaction mixture was dissolved in 200 parts by weight of toluene, neutralized with a 10% aqueous NaOH solution, and then washed three times with 100 parts by weight of saturated brine. Metoquinone 0.22 part by weight was added, and the solvent was distilled off under reduced pressure to obtain 46.8 parts by weight of the product (9-fluorenylmethyl acrylate). Viscosity (25 ° C.) 404 cps, refractive index (25 ° C.) 1.606.

( Reference example )
Under a nitrogen stream, 9-fluorenylmethyl acrylate (5.059 g, 20.2 mmol), azobisisobutyronitrile (hereinafter referred to as AIBN, 33.2 mg, 0.202 mmol, 9-fluorenyl) was added to a Schlenk tube. 1 mol% relative to methyl acrylate) and toluene (20.2 mL) were added. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to give a white powder (1.88 g, yield 37.2%). The obtained powder was analyzed and confirmed to be a homopolymer of 9-fluorenylmethyl acrylate.

(Example 1 )
9-Fluorenylmethyl acrylate (3.020 g, 12.07 mmol), methyl methacrylate (hereinafter referred to as MMA, 2.820 g, 28.17 mmol, MMA / 9-fluorenylmethyl acrylate) in a Schlenk tube under a nitrogen stream = 70/30), AIBN (66.2 mg, 0.403 mmol, 1 mol% based on the total amount of monomers) and toluene (40.2 mL) were added. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to obtain a white powder (2.60 g, yield 44.5%). When the obtained powder was analyzed by NMR, a copolymer of 9-fluorenylmethyl acrylate and methyl methacrylate (units derived from 9-fluorenylmethyl acrylate / units derived from methyl methacrylate (molar ratio)). = 20/80).

(Example 2 )
In a Schlenk tube under a nitrogen stream, 9-fluorenylmethyl acrylate (5.013 g, 20.0 mmol), MMA (2.006 g, 20.0 mmol, MMA / 9-fluorenylmethyl acrylate = 50/50), AIBN (65.8 mg, 0.401 mmol, 1 mol% based on the total amount of monomers) and toluene (40.0 mL) were added. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to give a white powder (2.65 g, yield 37.8%). When the obtained powder was analyzed by NMR, a copolymer of 9-fluorenylmethyl acrylate and methyl methacrylate (units derived from 9-fluorenylmethyl acrylate / units derived from methyl methacrylate (molar ratio)). = 37/63).

(Example 3 )
In a Schlenk tube under a nitrogen stream, 9-fluorenylmethyl acrylate (2.530 g, 10.1 mmol), MMA (4.015 g, 40.4 mmol, MMA / 9-fluorenylmethyl acrylate = 20/80), AIBN (82.9 mg, 0.505 mmol, 1 mol% based on the total amount of monomers) and toluene (50.5 mL) were added. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to give a white powder (2.19 g, yield 33.4%). When the obtained powder was analyzed by NMR, a copolymer of 9-fluorenylmethyl acrylate and methyl methacrylate (units derived from 9-fluorenylmethyl acrylate / units derived from methyl methacrylate (molar ratio)). = 56/44).

(Comparative Example 1)
Under a nitrogen stream, MMA (5.06 g, 50.5 mmol), AIBN (82.9 mg, 0.505 mmol, 1 mol% with respect to MMA) and toluene (50.5 mL) were placed in a Schlenk tube. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to give a white powder (1.63 g, yield 32.3%).

(Comparative Example 2)
In a Schlenk tube under a nitrogen stream, methyl acrylate (hereinafter referred to as MA, 4.50 g, 52.3 mmol), AIBN (85.8 mg, 0.523 mmol, 1 mol% based on the total amount of monomers) and toluene (52.3 mL) Put. The mixture was bubbled with nitrogen for 30 minutes with vigorous stirring, and then reacted at 80 ° C. After 6 hours, a Schlenk tube was attached to ice water to stop the reaction, and the reaction solution was added dropwise to methanol (800 mL). The precipitated polymer was collected by filtration, washed with methanol (100 mL), and dried to give a white powder (1.29, yield 28.6%).

The table summarizes the properties of the polymers obtained in the reference examples, examples and comparative examples. In Table 1, “9-FMA” is 9-fluorenylmethyl acrylate, “MMA” is methyl methacrylate, “MA” is methyl acrylate, “Mn” is number average molecular weight, “ “Mw” represents the weight average molecular weight, and “Tg” represents the glass transition temperature.

  As can be seen from the table, 9-fluorenylmethyl acrylate can be homopolymerized, and by such homopolymerization, it has excellent heat resistance with a high refractive index and a high 5% by weight reduction temperature. An acrylic resin was obtained.

In addition, 9-fluorenylmethyl acrylate can be copolymerized with methyl methacrylate, and by such copolymerization, despite being an acrylate, it can be maintained at a high level without extremely reducing Tg, Compared with a homopolymer of methyl methacrylate (polymethyl methacrylate), the 5% weight loss temperature could be remarkably improved while improving the refractive index. In particular, in Example 1 , even when the introduction amount was as small as about 20 mol%, it was confirmed that the 5 wt% weight reduction temperature was significantly improved as compared with polymethyl methacrylate.

  The polymerizable composition of the present invention is useful for producing a thermoplastic (meth) acrylic resin having a high refractive index and high heat resistance. A thermoplastic (meth) acrylic resin (or a molded product thereof) obtained by polymerizing such a polymerizable composition is a resin material such as an ink material, a light emitting material, an organic semiconductor, a gas separation membrane, Coating agent (for example, optical overcoat agent such as a coating agent for LED (light emitting diode) elements or hard coating agent), lens [pickup lens (for example, pickup lens for DVD (digital versatile disc), etc.), Microlens (for example, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (for example, polarizing film for liquid crystal display), antireflection film (or antireflection film, for example, antireflection film for display device) , Film for touch panel, film for flexible substrate, for display Film [for example, PDP (plasma display), LCD (liquid crystal display), OLED (organic EL display), VFD (vacuum fluorescent display), SED (surface conduction electron-emitting device display), FED (field emission display), NED ( Nano-emissive displays), cathode ray tubes, films for displays (particularly thin displays) such as electronic paper (filters, protective films, etc.)], fuel cell membranes, optical fibers, optical waveguides, holograms and the like. In particular, the thermoplastic (meth) acrylic resin (or molded product thereof) of the present invention can be suitably used for optical material applications. Examples of the shape of such an optical material include a film or sheet, a plate, and a lens. Shape, tubular shape and the like.

Claims (8)

A polymerizable composition for producing a thermoplastic (meth) acrylic resin having the following formula (A1)

(Wherein R ¹ represents a cyano group, a halogen atom or an alkyl group, R ² represents a hydrogen atom or a methyl group, R ³ represents a C _2-4 alkylene group, R ⁴ represents a methylene group, R ⁵ represents a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and n is 0 or 1.)
A monofunctional (meth) acrylic monomer (A) having a fluorene skeleton represented by: and a monofunctional non-fluorene-based (meth) acrylic monomer (B),
The non-fluorene-based (meth) acrylic monomer (B) contains methyl methacrylate in a proportion of 70 to 100 mol%,
Polymeric composition containing the said monofunctional (meth) acryl monomer (A) in the ratio of 10-90 mol% with respect to the total amount of the said monofunctional (meth) acryl monomer (A) and methyl methacrylate . Prior following formula (A1), m is 0, n is Ru 0 der 請 Motomeko 1 Symbol placement of the polymerizable composition. Non fluorene-based (meth) acrylic monomer (B) is according to claim 1 or 2 polymerizable composition according methyl methacrylate. The ratio of the monofunctional (meth) acrylic monomer (A) is 15 to 90 mol% based on the total amount of the monofunctional (meth) acrylic monomer (A) and the non-fluorene-based (meth) acrylic monomer (B). the polymerizable composition according to any one of claims 1 to 3. Claim 1 to polymerize the polymerizable composition according to any one of 4, a method of making a thermoplastic (meth) acrylic resin. Claim 1 thermoplasticity polymerizable composition according is polymerized in any of 4 (meth) acrylic resin. Ratio of the non-fluorene-based (meth) acrylate makes the chromophore at the distal end Nomar (B) methyl methacrylate units in the unit derived is at least 50 mol%, the proportion of units derived from monofunctional (meth) acrylate Rumonoma (A) is a single functional (meth) acrylate Rumonoma (a) derived units and non-fluorene (meth) acrylate Rumonoma (B) is 10 to 90 mol% or more based on the total amount of units derived from claim 6 thermoplastic described (meth )acrylic resin. The thermoplastic (meth) acrylic resin according to claim 6 or 7 , wherein the refractive index at 25 ° C and 589 nm is 1.5 or more and the 5% weight loss temperature is 200 ° C or more.