JP5350923B2 - β crystal nucleating agent and crystalline resin composition with β crystal structure formed - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a &beta; crystal nucleating agent that forms a crystal &beta; structure in a crystalline resin. <P>SOLUTION: The &beta; crystal nucleating agent is configured to include a phenolic compound, particularly a phenolic compound having a fluorene skeleton [for example, 9,9-bis(mono- to tri-hydroxyphenyl)fluorene, 9,9-bis(mono- or di-(1-4C alkyl)-hydroxyphenyl)fluorene, or the like]. Such a &beta; crystal nucleating agent and a crystalline resin (particularly an aliphatic polyester resin such as polylactic acid) are melt-mixed to form a &beta; crystal structure in the crystalline resin. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a crystal nucleating agent capable of forming a β crystal structure in a crystalline resin (β crystal nucleating agent), a method for producing a crystalline resin having a β crystal structure formed using the β crystal nucleating agent, the β The present invention relates to a crystalline resin composition containing a crystal nucleating agent and a molded product thereof.

  Of the crystalline resins, aliphatic polyester resins are often highly biodegradable, and because they are derived from plants and microorganisms, they protect the global environment, effectively use resources (recycle), and dispose of waste. It is a resin that is attracting attention in terms of the above problems. In particular, among the aliphatic polyester resins, polylactic acid is excellent in heat resistance and has high utility value in terms of cost. Such aliphatic polyester resins are required to be further improved in properties such as strength and elasticity.

As a method for improving the properties of such polylactic acid, for example, Japanese Patent 2003-293221 (Patent Document 1), forming a L-form or D-form 3 ₁ helical structure polylactic acid molecular chain in a single Polylactic acid fibers having a Worcester plaque of 2% or less are disclosed. This document, typically, alpha polylactic acid molecules having a crystal structure, beta since the crystal similar pattern was observed, 3 ₁ It was confirmed that the helical structure is formed, and this 3 ₁ helical It is described that since it has a structure, it exhibits a strong resistance to tension and exhibits sufficient mechanical properties not only at room temperature but also at a high temperature of 90 ° C. or higher. And in this document, the specific polylactic acid fiber is a homo PLLA having a weight average molecular weight of 100,000 to 300,000 is discharged from a die at a spinning temperature of 210 to 250 ° C., and the yarn is cooled and solidified by cooling air. When a fiber oil agent is applied and taken up at a high speed and wound as it is, the wound polylactic acid fiber has a crystal size in the (200) plane direction of 6 nm or more and / or a crystal orientation of 0.90 or more and U% of 2 It is also described that it can be obtained by determining the spinning conditions such as the take-up speed (spinning speed) so as to be 0.0% or less.

  Polylactic acid is known to have α, β, and γ crystal systems, but α crystal polylactic acid has been mainly studied in the past, and reports on β crystal polylactic acid have been made. These are just a few examples including the aforementioned Patent Document 1. The polylactic acid having a β crystal structure has a 3/1 helix structure, and has a more compact structure than the polylactic acid having an α crystal structure, as described in Patent Document 1 described above. Although known to be superior in terms of strength and the like as compared with α-crystal polylactic acid, it can be obtained unless special processes such as spinning at high speed and high stretching are performed as in Patent Document 1. The current situation is not possible.

  JP-A-2005-290258 (Patent Document 2) is a composition containing a resin component and a resin additive, and the resin component contains at least an aliphatic polyester resin, and the resin An aliphatic polyester resin composition in which the additive is composed of a compound having a fluorene skeleton is disclosed. In this document, a compound having a fluorene skeleton includes 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof [alkylene oxide adducts, 9,9-bis (hydroxyphenyl) fluorenes or alkylene oxide adducts thereof. Glycidyl ether, 9,9-bis (hydroxyphenyl) fluorenes or (meth) acrylates of alkylene oxide adducts thereof], 9,9-bis (aminophenyl) fluorenes or derivatives thereof, It is described that a resin (for example, a polyester-based resin) or the like included as a monomer component can be used. And this document describes that by adding the resin additive to an aliphatic polyester resin, an aliphatic polyester resin composition and a molded body having high flame retardancy, heat resistance and moldability can be obtained. ing.

  However, this document does not disclose any relationship between the compound having a fluorene skeleton and the crystal structure of the aliphatic polyester resin. In Examples, 9,9-bis (hydroxyphenyl) fluorenes and the like are not disclosed. There is no disclosure of an example in which a fluorene compound itself having a phenolic hydroxy group is added to an aliphatic polyester resin.

JP 2003-293221 A (claims, paragraph numbers [0012] to [0014], [0026]) JP-A-2005-290258 (claims, paragraph numbers [0026], [0033], [0041], [0048], Examples)

  Accordingly, an object of the present invention is to provide a nucleating agent (β crystal nucleating agent) capable of forming a β crystal structure in a crystalline resin (for example, an aliphatic polyester resin such as polylactic acid), and a resin containing the β crystal nucleating agent. It is in providing the composition (crystalline resin composition) and its manufacturing method.

  Another object of the present invention is to provide a nucleating agent (β crystal) that can easily form (or transfer or convert to β crystal structure) a β crystal structure even with a crystalline resin having another crystal structure such as α crystal structure. (Nucleating agent), a resin composition (crystalline resin composition) containing the β crystal nucleating agent, and a method for producing the same.

  Still another object of the present invention is to provide a nucleating agent capable of forming a β crystal structure in a crystalline resin and improving or improving the flame retardancy, heat resistance, and moldability of the crystalline resin. It is in providing the resin composition (crystalline resin composition) containing a nucleating agent, and its manufacturing method.

  Another object of the present invention is to provide a method capable of easily producing a crystalline resin having a β crystal structure.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have unexpectedly found that phenolic compounds [particularly, phenolic compounds having a fluorene skeleton such as 9,9-bis (hydroxyaryl) fluorenes] are crystalline. It is possible to form a β crystal structure in a resin (especially an aliphatic polyester resin such as polylactic acid), and a crystalline resin having such a β crystal structure is obtained by melt-mixing a crystalline resin and the phenol compound. The present invention has been completed by finding that it can be obtained by a simple method.

  That is, the β crystal nucleating agent of the present invention forms a β crystal structure in the crystalline resin [or converts the crystal structure (part or all) of the crystalline resin into a β crystal structure, or constitutes a crystalline resin. The β crystal nucleating agent for increasing the ratio of the β crystal structure in the crystal structure to be formed, which is composed of a phenol compound.

  Such a phenol compound may particularly have a fluorene skeleton, and the phenol compound having such a fluorene skeleton may be, for example, a compound represented by the following formula (1).

[Wherein Z is an aromatic hydrocarbon ring, E is an oxygen atom or sulfur atom, R ¹ is a hydrocarbon group, —OR ³ (wherein R ³ represents a hydrocarbon group), — (OR ⁴ ) _q -OH (wherein R ⁴ is a divalent hydrocarbon group, q represents an integer of 1 or more), -SR ³ (wherein R ³ is the same as above), an acyl group, an alkoxycarbonyl group, a halogen atom , A nitro group, a cyano group or a substituted amino group, R ² is a cyano group, a halogen atom or a hydrocarbon group, m is an integer of 0 or more, n is an integer of 0 to 4, and p is an integer of 1 or more. ]
In the above formula (1), the phenol compound is a benzene ring or a naphthalene ring, E is an oxygen atom, R ¹ is an alkyl group, R ² is an alkyl group or an aryl group, and m is 0 The compound which is -2, n is 0-1, and p is 1-3 may be sufficient.

Typical examples of the phenol compound include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene, and 9,9-bis (mono or diC _{6). -10} aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene, 9,9-bis (trihydroxyphenyl) fluorene, and 9,9-bis (hydroxynaphthyl) fluorene It may be.

  The crystalline resin may be an aliphatic polyester resin (crystalline aliphatic polyester resin such as polylactic acid). Such an aliphatic polyester resin (particularly polylactic acid) is poor in a method for forming a β crystal structure, and is particularly useful as a crystalline resin to which the β crystal nucleating agent of the present invention is applied.

  The present invention also includes a resin composition composed of a crystalline resin and the β crystal nucleating agent. Such a resin composition may be a simple mixture (or dry blend) of a β crystal nucleating agent and a crystalline resin, or a molten mixture of a crystalline resin and a β crystal nucleating agent. In such a molten mixture, a β crystal structure is formed in the crystalline resin. In such a resin composition, the ratio of the β crystal nucleating agent may be, for example, about 0.05 to 30 parts by mass with respect to 100 parts by mass of the crystalline resin.

  As described above, a β crystal structure is formed in the crystalline resin by melt mixing of the crystalline resin with the β crystal nucleating agent. Therefore, the present invention includes a method for producing a crystalline resin having a β crystal structure by melting and mixing a crystalline resin and the β crystal nucleating agent (or a method for forming a β crystal structure in the crystalline resin or β Also included is a method of producing a resin composition comprising a crystalline resin having a crystal structure formed and the β crystal nucleating agent. In such a method, a β crystal structure can be easily formed in the crystalline resin. In order to reliably form the β crystal structure, the melt mixture after melt mixing (the melt mixture after cooling) may be further heat-treated (and / or stretched).

  Furthermore, the present invention also includes a molded body (fiber or the like) formed from the resin composition.

  In the present specification, “phenol” may be used to mean including thiophenol.

  The nucleating agent of the present invention is useful as a crystal nucleating agent (β crystal nucleating agent) capable of forming a β crystal structure in a crystalline resin. In particular, such a β-crystal nucleating agent of the present invention easily forms a β-crystal structure (or is transferred or converted into a β-crystal structure) even if it is a crystalline resin having another crystal structure such as an α-crystal structure. it can. That is, a crystalline resin having a β crystal structure can be easily produced by a simple method in which the β crystal nucleating agent of the present invention is added to a crystalline resin and melt mixed. Therefore, such a β-crystal nucleating agent is particularly useful as a nucleating agent for forming a β-crystal in a crystalline resin such as polylactic acid that could not form a β-crystal structure without going through a special process. Useful.

  In addition, since the β crystal nucleating agent of the present invention is composed of a compound having a fluorene skeleton, the β crystal structure can be formed in the crystalline resin, and the flame retardancy, heat resistance and moldability of the crystalline resin can be formed. Such characteristics can be improved or improved. In addition, when composed of a compound having a fluorene skeleton, the pigment and the like can be dispersed in the crystalline resin with high dispersibility, and the incorporation ability of the pigment and the like can be improved. Further, the β crystal nucleating agent of the present invention can improve the reactivity of the crystalline resin and the crosslinkability by the reaction, and the improvement of the strength of the crystalline resin can be expected.

[Β crystal nucleating agent]
The β crystal nucleating agent (sometimes simply referred to as a nucleating agent) of the present invention is composed of a phenol compound. Examples of phenol compounds (including thiophenol compounds) include phenols [eg, phenol, alkylphenol (eg, C _1-4 alkylphenol such as cresol, xylenol), etc.], naphthols [eg, naphthol (1-naphthol, 2-naphthol, etc.) Monophenol compounds (compounds having one phenolic hydroxyl group) such as naphthol and alkyl naphthol (C _1-4 alkyl naphthol such as methyl naphthol), etc., but usually two or more phenol groups A compound (phenol compound) having (phenolic hydroxyl group and / or thiophenolic mercapto group) can be preferably used. Moreover, as the phenol compound, a phenol compound having a fluorene skeleton is also preferable.

Examples of the compound having two or more phenol groups include arenediols {for example, dihydroxybenzenes [for example, dihydroxybenzene (1,3-dihydroxybenzene, 1,4-dihydroxybenzene, etc.), alkyldihydroxybenzene [dihydroxytoluene] (Such as 4-methylcatechol), dihydroxyxylene (mono or diC _1-6 alkyl-dihydroxybenzene such as 2,6-dihydroxy-p-xylene)], naphthalenediols [eg, dihydroxynaphthalene (eg, 1 , 4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, dihydroxynaphthalene such as 2,6-dihydroxynaphthalene), etc.], bisphenols {for example, biphenol (for example, 4,4′-dihi Roxybiphenyl, etc.), bis (hydroxyphenyl) alkanes [for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1 Bis (hydroxyphenyl) C _1-4 alkanes such as phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane; Bis (mono-C _1-4 alkyl-hydroxyphenyl) C _1-4 alkane] such as bis (4-hydroxy-3-methylphenyl) propane], bis (hydroxyphenyl) ether (eg 4,4′-dihydroxydiphenyl ether) -Tell etc.), bis (hydroxyphenyl) sulfone, bis (hydroxyphenyl) sulfoxy Compounds having two phenolic hydroxyl groups, such as bis (hydroxyphenyl) sulfide, etc.]; arenetriols {eg trihydroxybenzenes [eg trihydroxybenzene (1,2,4-trihydroxybenzene) , 1,3,5-trihydroxybenzene, etc.]], trihydroxynaphthalenes [e.g., trihydroxynaphthalene (e.g., 1,2,4-trihydroxynaphthalene, 1,3,8-trihydroxynaphthalene, etc.), etc. ], Trisphenols {e.g., tri (hydroxyaryl) alkanes [e.g., tri (hydroxy _C6-14 ) such as 4,4 '-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol). Aryl) alkanes, preferably tri (hydrides) Carboxymethyl _{C 6-12 aryl) C 1-8} alkane, more preferably tri (hydroxy _{C 6-10 aryl) C 1-4} alkane], etc.}, tetrakis phenols {e.g., di (hydroxy aralkyl - hydroxyaryl) alkane [ For example, di [(hydroxy C _6-14 aryl C _1-6 alkyl) hydroxy C _6-14 aryl] such as 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol]. Alkanes, preferably di [(hydroxy C _6-12 aryl C _1-4 alkyl) hydroxy C _6-12 aryl] C _1-8 alkane, more preferably di [(hydroxy C _6-10 aryl C _1-2 alkyl) - hydroxy _{C 6-10 aryl] C 1-4} 3 or more, such as alkanes (e.g., 3-8, good Is properly 3-6, further compounds having a phenolic hydroxyl group is preferably 3 to 4), thiophenol compounds corresponding to these (compounds obtained by substituting a hydroxyl group in the mercapto group in these compounds) and the like.

  In the phenol compound having a fluorene skeleton, the fluorene skeleton is not limited and may be fluorene, but a 9,9-bisarylfluorene skeleton is preferable.

As such a phenol compound having a 9,9-bisarylfluorene skeleton (sometimes referred to as a 9,9-bisarylfluorene compound), a phenol compound having one phenol group {for example, 9-hydroxyaryl-9 -Aryl fluorenes [for example, 9-hydroxyphenyl-9-phenyl fluorene [for example, 9- (4-hydroxyphenyl) -9-phenyl fluorene, etc.], 9-hydroxyphenyl-9-alkylphenyl fluorene [for example, 9- (4-hydroxyphenyl) -9- (4-methylphenyl) 9-hydroxy-phenyl-9, such as fluorene _{(C 1-4} alkyl - phenyl) fluorene] compound described in 2009-13096 JP 2001-199175 etc. }, But two or more phenols Compounds having a group are preferred.

  Examples of the 9,9-bisarylfluorene compound having two or more phenol groups include a compound represented by the following formula (1).

(In the formula, Z is an aromatic hydrocarbon ring, E is an oxygen atom or sulfur atom, R ¹ and R ² are each a substituent, m is an integer of 0 or more, n is an integer of 0 to 4, and p is 1 or more. Indicates an integer.)
In the above formula (1), examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic aromatic hydrocarbon ring. As the condensed polycyclic aromatic hydrocarbon ring, a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed bicyclic hydrocarbon ring such as an indene ring or a naphthalene ring, preferably a C _10-16 condensed bicyclic ring) And condensed bicyclic hydrocarbon rings such as an anthracene ring and a phenanthrene ring. A preferable condensed polycyclic aromatic hydrocarbon ring includes a naphthalene ring. The two rings Z may be the same or different rings, and may usually be the same ring.

  Preferred ring Z includes a benzene ring and a naphthalene ring (particularly a benzene ring).

  In the formula (1), E is an oxygen atom or a sulfur atom, but in the same ring Z, when p is plural (two or more), E may be the same or different from each other, and usually the same. There may be. In the two rings Z, E may be the same or different, and may usually be the same. Preferred E is an oxygen atom (—O—). The preferred substitution number p may be 1 to 6, preferably 1 to 4 (for example, 1 to 3), more preferably 1 to 2, particularly 1. In different rings Z, the substitution numbers p may be the same or different from each other, and may be usually the same.

The substituent R ¹ substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Preferably a C _1-8 alkyl group, more preferably a C _1-6 alkyl group, etc., a cycloalkyl group (C _5-10 cycloalkyl group such as a cyclohexyl group, preferably a C _5-8 cycloalkyl group, Preferably a C _5-6 cycloalkyl group), an aryl group (eg, a C _6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, preferably a C _6-10 aryl group, more preferably C _6-8 such aryl groups), hydrocarbon such as an aralkyl group (a benzyl group and _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) Group; an alkoxy group (methoxy group, an ethoxy group, a propoxy group, _{C 1-12} alkoxy group such as butoxy, preferably _{C 1-8} alkoxy group, more preferably a _{C 1-6} alkoxy group), cycloalkoxy ( such as _{C 5-10} cycloalkyl group such as a hexyloxy group cyclohexylene), _{C 6-10} aryloxy groups such as an aryloxy group (phenoxy group), _{C 6-10} aryl -C such aralkyloxy group (a benzyloxy group Groups such as _1-4 alkyloxy group) —OR ³ [wherein R ³ represents a hydrocarbon group (such as the hydrocarbon group exemplified above). A group such as a hydroxyalkoxy group (a hydroxy C _1-12 alkoxy group such as a methylol group or 2-hydroxyethoxy group, preferably a hydroxy C _1-8 alkoxy group, more preferably a hydroxy C _1-6 alkoxy group, etc.) (OR ⁴ ) _q —OH [wherein R ⁴ is a divalent hydrocarbon group (for example, a divalent group corresponding to the above exemplified hydrocarbon group such as an alkylene group such as a C _2-4 alkylene group), q Represents an integer of 1 or more (for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2). An alkylthio group (a C _1-12 alkylthio group such as a methylthio group or an ethylthio group, preferably a C _1-8 alkylthio group, more preferably a C _1-6 alkylthio group), a cycloalkylthio group (C _5-10 cycloalkylthio). Groups), arylthio groups (C _6-10 arylthio groups), aralkylthio groups (C _6-10 aryl-C _1-4 alkylthio groups) and the like —SR ³ (wherein R ³ is the same as 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, bromine atom, iodine) Nitro group; cyano group; substituted amino group (for example, dialkylamino group such as dimethylamino group) ), And the like. In the group —OR ⁴ —OH, R ⁴ usually does not contain an aromatic hydrocarbon group in many cases.

Of these, typically, the group R ³ is a hydrocarbon group, —OR ³ (wherein R ³ represents a hydrocarbon group), — (OR ⁴ ) _q —OH (wherein R ⁴ Is a divalent hydrocarbon group, q represents an integer of 1 or more, -SR ³ (wherein R ³ is the same as above), an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, or It may be a substituted amino group.

Preferred group R ¹ includes 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), aralkyl group (for example, C _6-8 aryl-C _1-2 alkyl group and the like), alkoxy group (C _1-4 alkoxy group and the like) and the like. In particular, R ¹ is a hydrocarbon group such as an alkyl group [C _1-4 alkyl group (especially a methyl group)] or an aryl group [eg C _6-10 aryl group (especially a phenyl group)]. preferable.

In the same ring Z, when m is plural (2 or more), the groups R ¹ may be different from each other or the same. In the two rings Z, the groups R ¹ may be the same or different. The preferred substitution number m may be 0 to 8, preferably 0 to 4 (for example, 0 to 3), more preferably 0 to 2, particularly 0 to 1 (0 or 1). In different rings Z, the number of substitutions m may be the same or different from each other, and may usually be the same.

Examples of the group R ² include non-reactive substituents such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom and the like), a hydrocarbon group (such as the hydrocarbon group exemplified above), and the like. An alkyl group) in many cases. 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. When n is plural (2 or more), the groups R ² may be different from each other or the same. Further, the groups R ² 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 ² with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number n is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions n may be the same or different from each other.

  Specific compounds represented by the formula (1) (or 9,9-bisarylfluorene compounds having two or more phenol groups) include 9,9-bis (hydroxyphenyl) fluorenes, 9,9- Bis (mercaptophenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes, 9,9-bis (mercaptonaphthyl) fluorenes and the like are included.

The 9,9-bis (hydroxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl -Hydroxyphenyl) fluorene [e.g., 9,9-bis such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (Mono- or di-C _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, etc. , 9-bis (mono- or _{di-C 6-10} aryl - hydroxyphenyl) fluorene], such as the 9,9-bi (Monohydroxyphenyl) fluorenes; 9,9-bis (di- or trihydroxyphenyl) fluorenes {eg 9,9-bis (dihydroxyphenyl) fluorene [eg 9,9-bis (3,4-dihydroxyphenyl) And 9,9-bis (polyhydroxyphenyl) fluorenes] and the like. Moreover, as 9,9-bis (mercaptophenyl) fluorenes, in the 9,9-bis (hydroxyphenyl) fluorenes, a compound in which a hydroxyl group is substituted with a mercapto group, for example, 9,9-bis (mercaptophenyl) ) Fluorene [9,9-bis (4-mercaptophenyl) fluorene and the like]; 9,9-bis (alkyl-mercaptophenyl) fluorene [eg, 9,9-bis (3-methyl-4-mercaptophenyl) fluorene, 9,9-bis (mono- or C _1-4 dialkyl-mercaptophenyl) fluorene] such as 9,9-bis (3,5-dimethyl-4-mercaptophenyl) fluorene.

  The 9,9-bis (hydroxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyphenyl) fluorenes, for example, a compound in which a phenyl group is substituted with a naphthyl group, such as 9,9-bis (monohydroxy). Naphthyl) fluorenes {9,9-bis (hydroxynaphthyl) such as 9,9-bis [6- (2-hydroxynaphthyl)] fluorene, 9,9-bis [1- (5-hydroxynaphthyl)] fluorene ) Fluorene}, 9,9-bis (di- or trihydroxynaphthyl) fluorenes. The 9,9-bis (mercaptonaphthyl) fluorenes include compounds in which the hydroxyl group is substituted with a mercapto group in the 9,9-bis (hydroxynaphthyl) fluorenes.

Preferred phenolic compounds include arene polyols (eg, dihydroxybenzene, alkyldihydroxybenzene, dihydroxynaphthalene, trihydroxybenzene, trihydroxynaphthalene, etc.), compounds represented by the above formula (1), and the like. Among these, in the formula (1), Z is a benzene ring or a naphthalene ring, E is an oxygen atom, R ¹ is an alkyl group, R ² is an alkyl group or an aryl group, and m is 0 A compound in which n is 0 to 1 and p is 1 to 3, for example, 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (mono or di C _1-4 alkyl- Hydroxyphenyl) fluorene, 9,9-bis (mono or di-C _6-10 aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene, 9,9-bis (trihydroxyphenyl) fluorene, 9, 9-bis (hydroxynaphthyl) fluorene and the like] are preferable. When such a phenol compound having a fluorene skeleton is used, a β crystal structure can be reliably formed in the crystalline resin even in a small proportion.

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

  Note that the β crystal nucleating agent of the present invention may be composed only of the phenol compound (that is, it may be a β crystal nucleating agent consisting of only the phenol compound), depending on the type of crystalline resin to be applied. It may be configured in combination with other β crystal nucleating agents.

  Such other β crystal nucleating agents include, for example, carboxylates or esters (for example, aliphatic or aromatic carboxylic acids such as magnesium succinate, potassium 1,2-hydroxystearate, sodium benzoate, magnesium phthalate). Acid alkali or alkaline earth metal salts), sulfonates or esters (for example, sodium benzenesulfonate), amide compounds (for example, di- to tetraamides of aliphatic carboxylic acids such as adipic acid dianilide and aromatic amines; N , N′-dicyclohexyl-2,6-naphthalenedicarboxamide, N, N ′, N ″ -tricyclohexyl-1,3,5-benzenetricarboxamide and the like with dicyclic alicyclic amines To tetraamides), pigments (phthalocyanine pigments, quinacridone pigments) Fee, etc.), and the like. Such other β crystal nucleating agents are compounds known as polypropylene β crystal nucleating agents. Other β crystal nucleating agents may be used alone or in combination of two or more.

  In the β crystal nucleating agent of the present invention, when the phenol compound and another β crystal nucleating agent are combined, the ratio thereof is, for example, the former / the latter (mass ratio) = 99/1 to 10/90, preferably 95. / 5-30 / 70, more preferably about 90 / 10-50 / 50.

[Crystalline resin]
The β crystal nucleating agent of the present invention can be used as a component (additive) for forming a β crystal structure in a crystalline resin. Examples of the crystalline resin include olefin resins (for example, ethylene resins (polyethylene, etc.), propylene resins [polypropylene, copolymers having propylene as a main component (for example, 90 mol% or more) (propylene-ethylene copolymers) Etc.], halogen-based resins (vinylidene chloride resin, etc.), polyester resins {eg, aliphatic polyester resins, aromatic polyester resins [eg, poly C ₂ such as polyalkylene terephthalate (eg, polyethylene terephthalate, polybutylene terephthalate, etc.) _-4 alkylene terephthalates), polyalkylene naphthalate (e.g., poly C _2-4 alkylene naphthalate such as polyethylene naphthalate) polyalkylene arylate homopolyesters such as, alkylene arylate single Copolyester, liquid crystalline aromatic polyester, etc. with a content of 80 mol% or more)}, polyamide resins (for example, aliphatic polyamides such as polyamide 6 and polyamide 66), polyacetal resins, polyphenylene sulfide resins, polyethers, etc. Examples include ether ketone resins. These crystalline resins may be used alone or in combination of two or more.

  In addition, by adding a β crystal nucleating agent to the crystalline resin, the phenol group of the phenol compound constituting the β crystal nucleating agent is converted into a polar site [for example, a polar group (a carbonyl group, an ester group, etc.) of the crystalline resin. Or a polar site due to branching, etc.], a β crystal structure is formed. The formation of hydrogen bonds can be confirmed by an analysis means such as an absorption spectrum method [NIR (near infrared absorption) spectrum method or the like].

  Therefore, among these crystalline resins, polar groups (for example, groups containing carbonyl groups such as ester groups and amide groups), particularly crystalline resins having an ester group (for example, polyester resins) are preferable. Among these, aliphatic polyester resins can be preferably used.

  Examples of the aliphatic polyester resin include polyester obtained by polycondensation of an aliphatic dicarboxylic acid component and an aliphatic diol component, polyoxycarboxylic acid obtained by polycondensation of an aliphatic oxycarboxylic acid component, and ring-opening polymerization of a lactone. A polylactone obtained by combining these components and a polyester obtained by combining these components (for example, a polyester obtained by polycondensation of an aliphatic dicarboxylic acid component, an aliphatic diol component, and an aliphatic oxycarboxylic acid component, an aliphatic oxycarboxylic acid component, and Polyester obtained by polycondensation with lactone) and the like. These aliphatic polyester resins can be used alone or in combination of two or more.

In the polyester, as the aliphatic dicarboxylic acid component (usually saturated aliphatic dicarboxylic acid component), for example, aliphatic dicarboxylic acid (for example, oxalic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin) C _2-12 aliphatic dicarboxylic acids such as acids and dodecanedioic acid, preferably C _2-8 aliphatic dicarboxylic acids, and reactive derivatives of aliphatic dicarboxylic acids (for example, C _{1- 3} alkyl esters, acid halides such as acid chloride, etc.). These dicarboxylic acid components can be used alone or in combination of two or more. Of these dicarboxylic acid components, C _2-6 alkane dicarboxylic acid components such as oxalic acid, succinic acid, and adipic acid are preferred.

Examples of the aliphatic diol component (usually saturated aliphatic diol component) include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, and octane. Examples thereof include C _2-12 aliphatic diols such as methylene glycol and dodecamethylene glycol, preferably C _2-8 aliphatic diols. These diol components can be used alone or in combination of two or more. Of these diol components, C _2-6 alkanediols such as ethylene glycol, 1,4-butanediol, and neopentyl glycol are preferred.

In the polyoxycarboxylic acid, the aliphatic oxycarboxylic acid component (usually a saturated aliphatic oxycarboxylic acid component) is, for example, an aliphatic oxycarboxylic acid (for example, glycolic acid, lactic acid, malic acid, oxypropionic acid, oxy C _2-10 aliphatic oxycarboxylic acids such as butyric acid, preferably C _2-8 aliphatic oxycarboxylic acids), reactive derivatives of aliphatic oxycarboxylic acids (for example, C _1-3 such as acid anhydrides and methyl esters) It may be an acid halide such as an alkyl ester or an acid chloride). These oxycarboxylic acids can be used alone or in combination of two or more. Of these oxycarboxylic acids, hydroxy C _2-6 alkanoic acids such as glycolic acid, lactic acid, malic acid, and oxybutyric acid are preferred.

In the lactone, examples of the lactone include C _3-12 lactone such as propiolactone, butyrolactone, valerolactone, and caprolactone. These lactones can be used alone or in combination of two or more. Among these lactones, C _3-10 lactones such as propiolactone and caprolactone (for example, ε-caprolactone, etc.) are preferable.

  These aliphatic polyester resins may usually be biodegradable. In addition, the aliphatic polyester resin may be a synthetic polyester-based resin, in particular, a natural polyester resin (for example, a microbially produced polyester such as polyoxybutyric acid) or a polyester produced from a raw material derived from a natural product (for example, Polyester obtained by polycondensation of lactic acid derived from plants such as corn may also be used. Further, the aliphatic polyester resin may be a resin regenerated by recycling.

Specific examples of the aliphatic polyester resin include polyalkylene succinates (for example, poly C _2-6 alkylene succinates such as polyethylene succinate, polybutylene succinate, polyneopentylene succinate), polyalkylene adipates ( For example, alkane diols (eg, C _2-6 alkane diols) such as polyethylene adipate, polybutylene adipate, poly C _2-6 alkylene adipate such as polyneopentylene adipate, polybutylene adipate succinate and alkane dicarboxylic acids (eg, , C _2-10 alkanedicarboxylic acid) and polyesters (including copolyesters), polyoxycarboxylic acids (eg, polyglycolic acid, polylactic acid, polyoxybutyric acid, polymalic acid, etc.) C _2-6 alkanoic acid), polylactones (eg, polypropiolactone, polycaprolactone, etc.).

  Among these aliphatic polyester resins, in particular, polylactic acid is difficult to form a β crystal structure, and therefore the β crystal nucleating agent of the present invention can be suitably applied. Examples of polylactic acid (polylactic acid-based resin) include D-lactic acid component [D-lactic acid and its reactive derivatives (in addition to the derivatives exemplified above, lactide and the like)] and L-lactic acid component [L-lactic acid and its reaction. Polymers having at least one selected from the functional derivatives (in addition to the above exemplified derivatives, complex tides, etc.) as polymerization components are included, for example, poly-D-lactic acid, poly-L-lactic acid and the like. In addition, polylactic acid with low optical purity (namely, the ratio of D-lactic acid component or L-lactic acid component is low) has low crystallinity.

  The poly D-lactic acid may be a polymer having a D-lactic acid component as a main component, and includes a homopolymer of D-lactic acid and a copolymer of a D-lactic acid component and a copolymer component. In such a copolymer, the proportion of the D-lactic acid component is, for example, 70 mol% or more (for example, about 75 to 99.5 mol%) of all the constituent monomers, preferably 80 mol% or more (for example, 85 to 85 mol%). About 99 mol%), more preferably 90 mol% or more (for example, about 92 to 98 mol%). As the copolymerizable component copolymerizable with the D-lactic acid component, in addition to the L-lactic acid component, a diol component (such as the aliphatic diol component illustrated above), a dicarboxylic acid component (such as the aliphatic dicarboxylic acid component illustrated above), Examples include lactones (such as the components exemplified above), cyclic ethers (such as tetrahydrofuran), and the like. These copolymer components may be used alone or in combination of two or more.

  In addition, poly L-lactic acid is the same as poly D-lactic acid, and poly L-lactic acid includes a homopolymer of L-lactic acid and a copolymer of an L-lactic acid component and a copolymer component. The proportion of the L-lactic acid component in the copolymer is the same as described above. Examples of the copolymerizable component that can be copolymerized with the L-lactic acid component include the D-lactic acid component and the exemplified copolymeric components (diol component, dicarboxylic acid component, lactone, cyclic ether) and the like. These copolymer components may be used alone or in combination of two or more.

  In addition, the weight average molecular weight of crystalline resin (especially aliphatic polyester resin, such as polylactic acid) is 100-1 million (for example, 500-700000), for example, Preferably it is 1000-500000 (for example, 3000-400000), Furthermore, Preferably, it may be about 5000 to 300000 (for example, 10000 to 250,000), and may generally be about 5000 to 5000000 (for example, 10000 to 400000, preferably 20000 to 300000, more preferably 30000 to 250,000).

  The crystallinity of the crystalline resin may be, for example, about 10 to 85%, preferably 20 to 80%, and more preferably about 30 to 70%. Further, although the crystal structure of the crystalline resin depends on the type, it is usually a crystalline resin having an α crystal structure (α crystal) as a main crystal structure.

  The ratio of the α crystal structure in the crystalline resin is, for example, 30% or more (for example, about 40 to 100%), preferably 50% or more (for example, about 60 to 99%) with respect to the entire crystal structure (crystal region). ), More preferably 70% or more (for example, about 80 to 95%). The crystalline resin may be a resin that can form a crystal (crystal region). If the resin forms a β crystal in combination with the β crystal nucleating agent of the present invention, the crystal region (crystal portion) is not necessarily used. [Or the crystal region may be small (for example, the crystallinity may be less than 10%)].

[Resin composition]
The β crystal nucleating agent of the present invention can form a β crystal structure in the crystalline resin. Therefore, the present invention also includes a composition (resin composition) containing the β crystal nucleating agent and the crystalline resin. In such a resin composition, the proportion of the β crystal nucleating agent is, for example, 0.05 to 30 parts by mass, preferably 0.1 to 25 parts by mass (for example, 0. 5 to 20 parts by mass), more preferably about 1 to 15 parts by mass (for example, 2 to 10 parts by mass). Particularly, in the β crystal nucleating agent of the present invention, 10 parts by mass or less (for example, 0.1 to 10 parts by mass, preferably 0.3 to 8 parts by mass, more preferably 0 to 100 parts by mass of the crystalline resin). .Beta. Crystal structure can be formed in the crystalline resin even with a small amount of about 5 to 7 parts by mass, particularly about 1 to 6 parts by mass. In addition, the ratio of the β crystal structure formed in the crystalline resin can also be adjusted by adjusting the ratio of the β crystal nucleating agent. In particular, although depending on the type of the crystalline resin, in order to obtain a crystalline resin containing a β crystal structure in a sufficient ratio, the ratio of the β crystal nucleating agent is 1 part by mass with respect to 100 parts by mass of the crystalline resin. It is good also as above [for example, 1-20 mass parts, preferably 1.5-15 mass parts (for example, 2-10 mass parts), especially 3-9 mass parts (for example, 4-8 mass parts)].

  The resin composition can be obtained by mixing a β crystal nucleating agent and a crystalline resin. In particular, since the β crystal structure is formed in the crystalline resin by melt mixing the β crystal nucleating agent and the crystalline resin, the resin composition is a molten mixture of the crystalline resin and the β crystal nucleating agent. (That is, a resin composition in which a β crystal structure is formed in a crystalline resin). The resin composition of the present invention includes a simple mixture (or dry blend) of a β crystal nucleating agent and a crystalline resin [that is, a resin composition (or a precursor in which a β crystal structure is not formed in the crystalline resin). Body)]. Such a simple mixture is obtained by mixing the crystalline resin and the β crystal nucleating agent without melting the crystalline resin (and the β crystal nucleating agent), thereby forming a β crystal structure in the crystalline resin. It can be used as a resin composition as a previous precursor.

  The melt mixing can be performed at a temperature equal to or higher than the melting point of the crystalline resin depending on the type of the crystalline resin. In the melt mixing, the mixing temperature (kneading temperature) is, for example, about T ° C. to T + 60 ° C., preferably T + 5 ° C. to T + 50 ° C., more preferably about T + 10 ° C. to T + 30 ° C. when the melting point of the crystalline resin is T ° C. There may be. The specific mixing temperature may be, for example, 100 to 400 ° C, preferably 120 to 350 ° C (for example, 130 to 300 ° C), and more preferably about 150 to 250 ° C. In particular, when the crystalline resin is an aliphatic polyester resin (such as polylactic acid), the mixing temperature may be 130 to 250 ° C, preferably 160 to 230 ° C, and more preferably about 180 to 220 ° C.

  In melt mixing, for example, a kneader (mixer) such as an extruder (single screw extruder, twin screw extruder, etc.), a roll kneader, a Banbury mixer, or the like can be used. These kneaders may be used in combination of two or more.

  And the said melt mixture is obtained by cooling the melt obtained by melt mixing. In addition, you may use for such heat processing and the extending | stretching process (stretching process more than glass transition point temperature) such a molten mixture (molten mixture after cooling) further. In the heat treatment, the temperature (heating temperature, heat treatment temperature) may be, for example, 90 to 150 ° C, preferably 100 to 140 ° C, and more preferably about 110 to 130 ° C. In the heat treatment, the time (heating time, heat treatment time) may be a time that allows sufficient crystallization, and is, for example, 1 minute or longer (for example, 1 minute to 3 hours), preferably 2 minutes or longer (for example, 2 minutes to 1 hour), preferably about 3 minutes or more (for example, 3 to 30 minutes). The heat treatment and stretching treatment may be performed alone or in combination. Usually, the β-crystal structure of the crystalline resin is not formed (or difficult to form) only by the melt mixing (and subsequent cooling), but the post-treatment after such melt-mixing ensures that the crystalline resin has a β-crystal structure. A crystal structure can be formed. In any case, such treatment is not an advanced or complicated treatment such as a high stretching treatment required for forming a β crystal structure when the β crystal nucleating agent of the present invention is not used. In the invention, the β crystal structure can be easily formed in the crystalline resin.

  That is, a crystalline resin and a β crystal nucleating agent can be melt-mixed to produce a crystalline resin having a β crystal structure (or a resin composition containing a crystalline resin having a β crystal structure and a β crystal nucleating agent). In the crystalline resin in which such a β crystal structure is formed, the proportion of the β crystal structure may be 100% of the entire crystal structure, and as described above, depending on the proportion of the β crystal nucleating agent used, It can be adjusted as appropriate (for example, with respect to the entire crystal structure, for example, 10 to 99%, preferably 30 to 95%, more preferably about 50 to 90%). In the crystalline resin in which such a β crystal structure is formed, the ratio between the β crystal structure and the α crystal structure is the former / the latter = 100/0 to 10/90, preferably 100/0 to 30/70. More preferably, it may be about 100/0 to 50/50. In the crystalline resin in which the β crystal structure is formed, the crystallinity may be, for example, about 10 to 85%, preferably about 20 to 80%, and more preferably about 30 to 70%.

  In addition, the β crystal structure of the crystalline resin is formed by using known parameters (melting point, crystallization temperature, predetermined peak in X-ray diffraction (wide-angle X-ray diffraction, etc.), predetermined peak in NMR, etc.) in the crystalline resin. It can be confirmed using it. For example, in poly L-lactic acid (homopolymer), it is known that the melting point of the β crystal structure differs from the melting point of the α crystal structure by several degrees C. to several tens of degrees C. (for example, Macromolecules, vol. 23, 642 (1990)). ) Etc.). Therefore, whether or not a β crystal structure is formed in the poly L-lactic acid can be confirmed based on whether or not the melting point of the original poly L-lactic acid is shifted to a low temperature side. The ratio of the β crystal structure can also be calculated from the peak intensity of the melting enthalpy corresponding to these melting points.

  In the present invention, the β crystal nucleating agent has some interaction with the crystalline resin (for example, an interaction between a carbonyl group constituting an aliphatic polyester such as polylactic acid and a phenol group of the β crystal nucleating agent). However, commercially available crystalline resins (for example, polylactic acid resins) are usually not pure crystalline resins in many cases. Therefore, such a crystalline resin varies to some extent between the crystalline portion and the non-crystalline portion, and may give a very fine change in the melting point value of the β crystal structure where such variation is obtained. Such a difference in values is negligible, and does not affect the level of whether or not a β crystal structure is formed.

  It should be noted that the resin composition of the present invention has additives such as stabilizers (anti-aging agents, antioxidants, ozone degradation inhibitors, ultraviolet absorbers, light stabilizers) as long as the effects of the present invention are not impaired. Agents, heat stabilizers, etc.), flame retardants, tackifiers, plasticizers, softeners, lubricants, mold release agents, antistatic agents, modifiers, colorants, coupling agents, antiseptics, antifungal agents, etc. It may be.

[Molded body]
The molded product of the present invention is formed of the resin composition. The shape of the molded body can be selected according to the application and is not particularly limited, and examples thereof include a fiber shape, a film shape, a sheet shape, a plate shape, a tubular shape, a rod shape, a tube shape, and a hollow shape. Such a molded body can be produced by molding the resin composition by a conventional method. As the molding method, depending on the type of the molded body, for example, extrusion molding method, injection molding method, thermoforming method (blow molding method, vacuum forming method, pressure forming method, vacuum pressure forming method, press forming method, etc.), Calendar processing, foam molding, compression molding, and the like can be used.

  In particular, since the resin composition of the present invention is composed of a crystalline resin having a β crystal structure, it has excellent properties such as strength and heat resistance, and is suitable for forming fibers (fibrous molded products). Yes. Examples of the fibrous molded body include multifilaments, monofilaments, flat yarns, staple fibers, and nonwoven fabrics. Such a fibrous shaped product can be obtained by, for example, a melt spinning method (such as an extruder melt spinning method).

  In the melt spinning method, the melt flow rate (MFR) of the resin composition is, for example, 0.1 to 10 g / 10 minutes, preferably 0.3 to 8 g / 10 minutes, more preferably 0.5 at the molding temperature. It may be about ˜7 g / 10 minutes. In the case of molding by melting as in the case of melt spinning, it is not always necessary to use the molten mixture (crystalline resin having a β crystal structure already formed) as described above. In order to form a β crystal structure, the molten mixture may be used as a resin composition for melt molding (such as melt spinning). As described above, when a β crystal structure is formed in a crystalline resin (for example, polylactic acid) without using a β crystal nucleating agent, a special treatment such as high-speed stretching or two-stage stretching is performed. Although necessary, when the β crystal nucleating agent of the present invention is used, a β crystal structure can be easily formed in the crystalline resin without requiring such treatment.

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

  In Examples and Reference Examples, the thermophysical properties of compounds or pellets were measured with a differential gravimetric thermal analyzer (manufactured by RIGAKU, DSC 8230). The amount of sample used in the measurement of thermophysical properties was 10 mg, and measurement was performed under conditions of a temperature of 25 to 250 ° C. and a temperature increase rate of 10 K / min.

  The physical properties of the fibers were measured with a universal testing machine (manufactured by Shimadzu Corp., EZGraph) using a tension jig, and the fiber diameter was measured with an optical microscope (OPTIPHOT manufactured by Nikon Corporation). It was measured.

Example 1
9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., melting point = 210 ° C., hereinafter referred to as BCF) as a phenol compound having a fluorene skeleton, and poly L-lactic acid ( Natureworks, “6400D”, melting point = 168 ° C., Mw = 18000) was dry blended with the former / the latter (mass ratio) = 1/99, and a twin screw extruder (Technobel, KZW15-30MG) ) And melt-kneaded at a temperature of 180 to 200 ° C., pelletized by air cooling, and further heat treated at a temperature of 120 ° C. for 5 minutes to obtain a compound. In addition, the obtained pellet was transparent.

(Example 2)
In Example 1, the compound was obtained by pelletizing in the same manner as in Example 1 except that the ratio of BCF and poly-L-lactic acid was changed to the former / the latter (mass ratio) = 3/97. In addition, the obtained pellet was transparent.

(Example 3)
In Example 1, the compound was obtained by pelletizing in the same manner as in Example 1 except that the ratio of BCF and poly-L-lactic acid was changed to the former / the latter (mass ratio) = 5/95. In addition, the obtained pellet was transparent.

Example 4
In Example 3, pelletized and compounded in the same manner as in Example 3 except that 2,2-bis (4-hydroxy-3-methylphenyl) propane (melting point = 139 ° C.) was used instead of BCF. Got. The obtained pellet was transparent.

(Example 5)
In Example 3, the same procedure as in Example 3 was used except that 4,4 ′-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol) (melting point = 206 ° C.) was used instead of BCF. And pelletized to obtain a compound. The obtained pellet was transparent.

(Example 6)
Example 3 is the same as Example 3 except that 2,2′-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol] (melting point = 195 ° C.) was used instead of BCF. Similarly, it was pelletized to obtain a compound. The obtained pellet was transparent.

(Reference Example 1)
In Example 1, instead of BCF, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene which is not a phenol compound (manufactured by Osaka Gas Chemical Co., Ltd., melting point 162 ° C., hereinafter referred to as “BPEF”) The compound was obtained by pelletizing in the same manner as in Example 1 except that was used. In addition, the obtained pellet was transparent.

(Reference Example 2)
In Example 2, a compound was obtained by pelletizing in the same manner as in Example 2 except that BPEF was used instead of BCF. In addition, the obtained pellet was transparent.

(Reference Example 3)
In Example 3, a compound was obtained by pelletizing in the same manner as in Example 3 except that BPEF was used instead of BCF. In addition, the obtained pellet was transparent.

(Comparative Example 1)
A compound was obtained by pelletizing in the same manner as in Example 1 except that BCF was not used in Example 1 (that is, melted and kneaded with poly-L lactic acid alone). In addition, the obtained pellet was transparent.

  And the thermophysical property (thermal characteristic) of the compound obtained in Examples 1-6, Reference Examples 1-3 and Comparative Example 1 was measured. The results are shown in Table 1. In Table 1, “PLLA” is poly L-lactic acid, “A1” is BCF, “A2” is 2,2-bis (4-hydroxy-3-methylphenyl) propane, and “A3” is 4,4 ′. -(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol), "A4" is 2,2'-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol], "B ”Indicates BPEF,“ Tg ”is the glass transition temperature,“ Tm1 ”is the melting point of the β crystal,“ Tm2 ”is the melting point of the α crystal,“ Tm3 ”is the melting point of the additives (A1 to A4, B), “ΔHm1” indicates the melting enthalpy at Tm1, and “ΔHm2” indicates the melting enthalpy at Tm2.

  As is clear from Table 1, in the poly L-lactic acid (Examples 1 to 3) to which BCF (A1) was added, not only the melting point of the α crystal (168 ° C.) but also the melting point of the β crystal different from this melting point ( 163 ° C.) and was found to have a β crystal structure. The ratio of the β crystal structure increases as the BCF addition ratio increases, and when it is added at a ratio of 5% by mass, the entire compound is poly L-lactic acid having a β crystal structure. There was found. Moreover, in Examples 1 to 3, the melting point (210 ° C.) of BCF was not confirmed, and BCF has a strong interaction with poly L-lactic acid, or the crystal structure of poly L lactic acid is effectively changed to β crystals. It turned out to be effective. Further, as is clear from comparison with Comparative Example 1, it was also confirmed that Tg was improved by addition of BCF.

  The formation of such β crystals could also be confirmed by wide angle X-ray diffraction. In addition, from the NIR spectrum, hydrogen bonds that seem to be due to the formation of a β crystal structure were also confirmed.

  On the other hand, BPEF has a 9,9-bisphenylfluorene skeleton similar to BCF, but it has been found that the crystal structure of poly-L-lactic acid cannot be changed to β-crystal. That is, in Reference Examples 1 to 3, even when BPEF was added to poly L-lactic acid, the melting point of the β crystal was not confirmed, and only the melting point of the α crystal and the melting point of the BPEF itself were confirmed. Further, it has been found that even if BPEF is added, there is not much effect of improving Tg.

  It was also found that a β crystal structure can be formed even when phenol compounds (A2, A3 and A4) having no fluorene skeleton are added to poly L-lactic acid. Then, it was found that a phenol compound having a rigid structure seems to be able to form a β crystal structure more effectively than a structurally flexible phenol compound.

(Example 3-2)
Using the compound obtained in Example 3, monofilaments were spun. That is, the compound was melted at a temperature of 180 to 200 ° C. with a uniaxial melt extruder (manufactured by Technobel, SZW15-24MG), discharged from a die having a diameter of 1.2 mm, and then cooled at room temperature (natural cooling in the air). The monofilament cooled with a 1000 rpm winder was recovered. The collected filament was transparent, had sufficient hardness, and was flexible.

(Comparative Example 1-2)
In Example 3-2, monofilaments were collected in the same manner as in Example 3-2 except that the compound obtained in Comparative Example 1 was used instead of the compound obtained in Example 3. The collected filament was transparent, had sufficient hardness, and was flexible.

  The fiber properties [diameter, strength, elastic modulus, elongation (breaking elongation)] of the monofilaments obtained in Example 3-2 and Comparative Example 1-2 were measured. The results are shown in Table 2.

  As is apparent from Table 2, when polylactic acid added with BCF is used, a fiber superior in strength and elastic modulus to that of polylactic acid having an α crystal structure is obtained through a spinning process similar to that of polylactic acid having an α crystal structure. I found out that This also indicates that BCF effectively acts as a β-crystal nucleating agent for polylactic acid, and a high-strength fiber was obtained by the formation of β-crystal polylactic acid.

(Example 7)
In Example 1, the compound was obtained by pelletizing in the same manner as in Example 1 except that the ratio of BCF and poly-L-lactic acid was changed to the former / the latter (mass ratio) = 10/90. In addition, the obtained pellet was transparent.

(Example 8)
In Example 3, instead of BCF, 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., melting point = 229 ° C.) was used. The compound was obtained by pelletizing. The obtained pellet was transparent.

Example 9
In Example 3, Example 9 was used except that 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., melting point = 290 ° C.) was used instead of BCF. In the same manner as in Example 3, pelletization was performed to obtain a compound. The obtained pellet was transparent.

(Example 10)
In Example 3, Example 9 was used except that 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., melting point = 267 ° C.) was used instead of BCF. Similarly, it was pelletized to obtain a compound. The obtained pellet was transparent.

(Example 11)
In Example 3, 9,9-bis (6-hydroxy-2-naphthyl) fluorene (manufactured by Osaka Gas Chemical Co., Ltd., melting point = 264 ° C.) was used instead of BCF. And pelletized to obtain a compound. The obtained pellet was transparent.

(Example 12)
In Example 3, 9,9-biscatecholfluorene (or 9,9-bis (3,4-dihydroxyphenyl) fluorene, manufactured by Osaka Gas Chemical Co., Ltd., melting point = 240 ° C.) was used instead of BCF. Except for the above, pelletization was performed in the same manner as in Example 3 to obtain a compound. The obtained pellet was transparent.

(Example 13)
In Example 3, instead of BCF, bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd., melting point = 158 ° C.) was used, and the kneading temperature was changed to 150-170 ° C., in the same manner as in Example 3, The compound was obtained by pelletizing. The obtained pellet was transparent.

  The β crystal nucleating agent of the present invention is useful as an additive for forming a β crystal structure in a crystalline resin, in particular, a resin such as polylactic acid that could not form a β crystal without passing through a special process. The crystalline resin (the resin composition) having such a β crystal structure is derived from the β crystal structure and has excellent mechanical properties such as strength, heat resistance, and elongation. Molded articles, for example, injection molded articles (members and equipment constituting transportation vehicles such as automobiles, office automation (OA) equipment such as personal computers, displays, copiers, and printers, home appliances such as televisions and refrigerators, Building materials such as wall materials and floor materials, various appliances (housing, casing, parts, etc.), extrusion molded products (sheets, vacuum molded products, compressed air molded products, foam containers), blow molded products (drink containers, cosmetic containers, Medicine containers, etc.), inflation molded bodies (garbage bags, agricultural sheets, etc.) and fibrous molded bodies have excellent biodegradability and are useful as biodegradable molded bodies It is.

Claims (10)

A β-crystal nucleating agent for forming a β-crystal structure in polylactic acid , which is bis (hydroxyphenyl) alkane, tri (hydroxyaryl) alkane, di (hydroxyaralkyl-hydroxyaryl) alkane, 9,9-bis (hydroxy Phenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene, and 9,9-bis (hydroxynaphthyl) ) Β-crystal nucleating agent composed of at least one phenol compound selected from fluorene . The phenolic compound is 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene, 9,9-bis (mono or diC _6-10 aryl- hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene,及 beauty 9,9-bis (beta-crystal nucleating agent according to claim 1 Symbol placement is at least one selected from the hydroxy naphthyl) fluorene. A resin composition comprising polylactic acid and the β crystal nucleating agent according to claim 1 , wherein the β crystal nucleating agent is 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis. At least one selected from (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) fluorene, and 9,9-bis (hydroxynaphthyl) fluorene A resin composition comprising a phenol compound .   A resin composition comprising polylactic acid and the β crystal nucleating agent according to claim 1, wherein the proportion of the β crystal nucleating agent is 0.3 to 8 parts by mass with respect to 100 parts by mass of the polylactic acid. A resin composition. The resin composition according to claim 3 , wherein the ratio of the β crystal nucleating agent is 0.05 to 30 parts by mass with respect to 100 parts by mass of polylactic acid . The resin composition according to any one of claims 3 to 5, wherein the resin composition is a molten mixture of polylactic acid and a β crystal nucleating agent, and a β crystal structure is formed in the polylactic acid . Polylactic acid , 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (dihydroxyphenyl) A method for producing polylactic acid having a β crystal structure by melt-mixing fluorene and a β crystal nucleating agent composed of at least one phenol compound selected from 9,9-bis (hydroxynaphthyl) fluorene .   A method for producing polylactic acid having a β crystal structure by melt-mixing 0.3 to 8 parts by mass of the β crystal nucleating agent according to claim 1 or 2 with respect to 100 parts by mass of polylactic acid. The molded object formed with the resin composition in any one of Claims 3-6 . The molded article according to claim 9, which is a fiber.