WO2016139826A1 - Fluidity improver and polyamide resin composition containing same - Google Patents

Abstract

[Problem] To provide: a fluidity improver which is capable of improving the melt fluidity of a polyamide resin; and a polyamide resin composition which contains this fluidity improver. [Solution] A compound having a 9, 9-bisarylfluorene skeleton represented by formula (1) is added to a polyamide resin, so that the melt viscosity thereof is decreased and the fluidity thereof is improved. (In the formula, ring Z represents an aromatic hydrocarbon ring; each of R¹ and R² represents a substituent; X represents a -[(OR³)_n-Y] group (wherein Y represents a hydroxyl group, a mercapto group, a glycidyloxy group or a (meth)acryloyloxy group; R³ represents an alkylene group; and n represents 0 or an integer of 1 or more) or an amino group; k represents an integer of 0-4; m represents an integer of 0 or more; and p represents an integer of 1 or more.)

Description

Fluidity improver and polyamide resin composition containing the same

The present invention relates to a fluidity improver (or melt viscosity reducing agent) useful for improving the melt fluidity of a polyamide resin, a thermoplastic resin composition containing the melt fluidity improver, and the fluidity of a polyamide resin. On how to improve.

Using a compound having a 9,9-bisphenylfluorene skeleton (sometimes simply referred to as a fluorene compound) as a monomer for the polymerization reaction, a resin having an excellent function such as a high refractive index and high heat resistance is produced. Yes. In addition, a fluorene compound is added to a resin to improve the refractive index, heat resistance, mechanical strength, and the like.

For example, JP 2005-162785 A (Patent Document 1) describes that a fluorene compound is added to a thermoplastic resin to increase the refractive index of the thermoplastic resin. Japanese Patent Application Laid-Open No. 2011-8017 (Patent Document 2) describes that a fluorene compound is added to a transparent resin to reduce the birefringence of the transparent resin. Furthermore, JP-A-2011-21083 (Patent Document 3) discloses 9,9-bis (4-hydroxy-3-methylphenyl) fluorene with respect to poly-L-lactic acid having an α crystal (melting point: 168 ° C.). 1 to 5% by weight was added and melt-kneaded to prepare poly-L-lactic acid in which β crystals (melting point: 163 ° C.) were formed, and Tg changed from 56.5 ° C. to 60.9-62.1 ° C. It is described.

JP 2014-218659 A (Patent Document 4) describes that a fluorene compound is added to a thermoplastic resin such as a polyethylene terephthalate resin to improve the strength of the resin. This document exemplifies a number of resins such as polyamide resin as the thermoplastic resin.

On the other hand, polyamide resins have high melt viscosity due to strong hydrogen bonds between molecules, and low flowability and moldability. For example, a polyamide resin has a relatively high melting point, and it is necessary to heat at a temperature higher than the melting point for molding. Moreover, since the melt viscosity of the polyamide resin is highly temperature-dependent and the decomposition temperature is close to the melting point, strict temperature control is required. Therefore, it is conceivable that a plasticizer is added to alleviate intermolecular hydrogen bonding, the melt viscosity of the polyamide resin is lowered, and the moldability is improved. However, the addition of a plasticizer reduces the mechanical properties of the polyamide resin. For this reason, it is not possible to suppress a decrease in mechanical properties while improving moldability.

Japanese Patent Laying-Open No. 2005-162785 (Claims and Examples) JP 2011-8017 A (Claims, Examples) Japanese Patent Laying-Open No. 2011-21083 (Claims and Examples) JP 2014-218659 A (Claims, [0058], Examples)

Accordingly, an object of the present invention is to provide a fluidity improver capable of improving the melt fluidity (lowering the melt viscosity) of the polyamide resin and a polyamide resin composition containing the fluidity improver.

Another object of the present invention is to provide a fluidity improver capable of improving the melt fluidity of a polyamide resin with a small amount of addition, and a polyamide resin composition containing the fluidity improver.

Still another object of the present invention is to improve the melt fluidity of the polyamide resin, a fluidity improver that can improve the melt fluidity without impairing the properties of the polyamide resin, the polyamide resin composition containing the fluidity improver, and the polyamide resin. It is to provide a way to do.

As a result of intensive studies to solve the above problems, the present inventors have added a compound having a 9,9-bisarylfluorene skeleton to a polyamide resin and analyzed by a Fourier transform infrared spectrophotometer (FT-IR). Then, the absorption peak intensity in the vicinity of 3300 cm ⁻¹ derived from the NH group decreases, the fluorene compound relaxes the hydrogen bond of the amide bond, and the melt viscosity of the polyamide resin greatly decreases due to such relaxation of the hydrogen bond. As a result, the present invention was completed.

That is, the fluidity improving agent of the present invention is a fluidity improving agent (melting viscosity reducing agent) for improving the melt fluidity (or lowering the melt viscosity) of the polyamide resin, which is a 9,9-bisaryl. A compound having a fluorene skeleton is included.

The compound having a 9,9-bisarylfluorene skeleton may be, for example, a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) _n —Y] (where Y is a hydroxyl group, mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is 0 or an integer of 1 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 The above integers are shown. ]
The compound having a 9,9-bisarylfluorene skeleton may be a compound represented by the following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
In the above formula (1) or (1A), each ring Z may be a benzene ring or a naphthalene ring, each R ¹ may be an alkyl group, and each k may be 0 to 1. Each R ² may be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxy group, each m may be 0 to 2, and each R ³ is a C _2-4 alkylene group. Each n may be 0 to 20, and each p may be 1 to 3.

Compounds having a 9,9-bisarylfluorene skeleton typically include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl- Hydroxyphenyl) fluorene, 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-) Hydroxyalkoxyphenyl) fluorene, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, 9,9-bis (hydroxyalkoxynaphthyl) fluorene, and alkylene oxide adducts of these compounds (eg, C _2-4 alkylene oxide) (Adjunct) It may be at least one selected.

The polyamide resin may be at least one selected from an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin.

The addition amount of the fluidity improver may be about 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin.

The fluidity improver (melt viscosity reducing agent) of the present invention reduces the melt viscosity of the polyamide resin and improves the melt fluidity without reducing the mechanical properties of the polyamide resin. Therefore, the present invention includes a thermoplastic resin composition containing a polyamide resin and the fluidity improver (melt viscosity reducing agent), and further a molded body formed from the resin composition.

Furthermore, the present invention provides a method for adding (or mixing) the fluidity improver (melt viscosity reducing agent) to the polyamide thermoplastic resin to reduce the melt viscosity of the polyamide resin (method for improving melt fluidity). Including.

In the present specification, “9,9-bis (hydroxyaryl) fluorenes” and “9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes” mean “9,9-bis (hydroxyaryl)”. As long as it has “) fluorene skeleton” or “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene skeleton”, it also includes compounds having substituents on aryl groups and fluorene skeletons (specifically, positions 2 to 7 of fluorene) Use for meaning. In the present specification, “9,9-bis (hydroxy (poly) alkoxyaryl) fluorene” means 9,9-bis (hydroxyalkoxyaryl) fluorene and 9,9-bis (hydroxypolyalkoxyaryl) fluorene. Used to mean both.

In the present invention, the melt fluidity and moldability of the polyamide resin can be improved by adding a predetermined fluorene compound. Moreover, the melt fluidity of the polyamide resin can be improved with a small amount of addition, and even if the fluorene compound is a low molecular compound, the properties of the polyamide resin are not impaired. Therefore, the melt fluidity can be improved and the molded product can be molded efficiently without impairing the properties of the polyamide resin.

FIG. 1 is a graph showing the results of a melt fluidity test of the resin compositions obtained in Comparative Example 1 and Examples 1 and 2. FIG. 2 is a graph showing the results of the melt fluidity test of the resin compositions obtained in Comparative Examples 2-4. FIG. 3 is a chart in which the absorption spectra of the resin compositions obtained in Comparative Example 1 and Example 1 using a Fourier transform infrared spectrophotometer are superimposed, the dotted line is the spectrum of Comparative Example 1, and the solid line is that of Example 1. The spectrum is shown. FIG. 4 is an enlarged view of the vicinity of the wave number of 3300 cm ^{−1 in} the chart of FIG. FIG. 5 is a graph showing the results of the melt fluidity test (injection speed: 20 mm / second) of the resin compositions obtained in Examples 5 to 6 and Comparative Example 5. FIG. 6 is a graph showing the results of the melt fluidity test (injection speed: 50 mm / sec) of the resin compositions obtained in Examples 5 to 6 and Comparative Example 5. FIG. 7 is a graph showing the results of the melt fluidity test (injection speed: 80 mm / sec) of the resin compositions obtained in Examples 5 to 6 and Comparative Example 5.

The fluidity improving agent of the present invention contains a compound having a 9,9-bisarylfluorene skeleton (hereinafter sometimes simply referred to as a fluorene compound).

[Fluorene compound]
The fluorene compound is a compound having no reactive group or functional group [a compound in which p is 0 in the following formula (1), for example, 9,9-bisarylfluorene such as 9,9-bisphenylfluorene, etc. However, it usually has a reactive group or a functional group.

Examples of reactive groups or functional groups include hydroxyl groups, mercapto groups, carboxyl groups, alkoxycarbonyl groups, amino groups, N-substituted amino groups, (meth) acryloyloxy groups, epoxy groups (eg, glycidyloxy groups), etc. Is mentioned. The fluorene compound may have these reactive groups singly or in combination of two or more.

The reactive group or functional group may be directly bonded to 9,9-bisarylfluorene, and 9,9-bisaryl may be bonded via an appropriate linking group (for example, (poly) oxyalkylene group). It may be bonded to fluorene. Specific examples of the fluorene compound include a compound represented by the following formula (1).

[Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) _n —Y] (where Y is a hydroxyl group, mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is 0 or an integer of 1 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 The above integers are shown. ]
In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon (for example, indene, naphthalene, etc. Condensed bicyclic to tetracyclic hydrocarbons such as C _8-20 condensed bicyclic hydrocarbons, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (eg anthracene, phenanthrene, etc.), etc. A ring assembly hydrocarbon ring (bi or ter C _6-10 arene ring such as biphenyl ring, terphenyl ring, binaphthyl ring). The two rings Z may be different rings, and may usually be the same ring. Preferred rings Z include a benzene ring, a naphthalene ring, and a biphenyl ring, and may be a benzene ring.

In the formula (1), examples of the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C ₆ such as a phenyl group). _-10 aryl group), etc.], acyl group (e.g., methyl group, an ethylcarbonyl group, and a non-reactive substituent such as an alkyl group), such as pentyl group, in particular, if that is a an alkyl group Many. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, such as _{C 1-8} alkyl group _{(e.g., C 1-6} alkyl groups, especially methyl groups, such as t- butyl group _{C 1- 4} alkyl group) and the like. When k is plural (2 to 4), the types of the plural groups R ¹ may be the same or different from each other. The types of the groups R ¹ substituted on different benzene rings may be the same or different from each other. Further, the bonding position (substitution position) of the group R ¹ is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. The two substitution numbers k may be the same or different.

The substituent R ² substituted on the ring Z is usually a non-reactive substituent, for example, an alkyl group (eg, a C _1-8 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Preferably a C _1-6 alkyl group), a cycloalkyl group (eg, a C _5-10 cycloalkyl group such as a cyclohexyl group), an aryl group (eg, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc.) an alkoxy group (e.g., methoxy group,; _{C 6-10} aryl group and the like), and an aralkyl group (e.g., benzyl group, a hydrocarbon group, such as such as _{C 6-10} aryl _{-C 1-4} alkyl group such as a phenethyl group) ethoxy and the like _{C 1-8} alkoxy group such group), cycloalkoxy groups (e.g., _{C 5-10} cycloalkyloxy such as cyclohexyloxy group cycloheteroalkyl Etc.), an aryloxy group (e.g., a _{C 6-10} aryloxy group such as phenoxy group), aralkyloxy group (e.g., _{C 6-10} aryl _{-C 1-4} alkyl group such as a benzyl group), etc. A group —OR [wherein R represents the hydrocarbon group exemplified above. A group —SR such as an alkylthio group (eg, a C _1-8 alkylthio group such as a methylthio group), etc. (wherein R is as defined above); an acyl group (eg, a C _1-6 acyl group such as an acetyl group) An alkoxycarbonyl group (eg, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a nitro group; a cyano group; Examples thereof include a substituted amino group (for example, a di-C _1-4 alkylamino group such as a dimethylamino group).

Preferred group R ² includes a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group etc.), cycloalkyl group (eg, C _5-8 cycloalkyl group etc.), aryl group (eg, C _{6 -10} aryl group, etc.), aralkyl groups (eg C _6-8 aryl-C _1-2 alkyl group etc.)], alkoxy groups (C _1-4 alkoxy group etc.) and the like. Further preferred groups R ² include an alkyl group [for example, a C _1-4 alkyl group (particularly a methyl group)], an aryl group [for example, a C _6-10 aryl group (particularly a phenyl group)] and the like. Incidentally, when the group R ² is an aryl group, a group R ^2, together with the ring Z, it may form the ring assembly hydrocarbon ring.

In the same ring Z, when m is plural (two or more), the types of the groups R ² may be the same or different from each other. In the two rings Z, the type of the group R ² may be the same or different. The number of substitutions m can be selected according to the type of the ring Z, and may be, for example, 0 to 8, preferably 0 to 4 (eg, 0 to 3), and more preferably 0 to 2. In different rings Z, the number of substitutions m may be the same or different from each other.

In the group X of the formula (1), examples of the alkylene group represented by the group R ³ include C _2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group. A group, preferably a C _2-4 alkylene group, and more preferably a C _2-3 alkylene group. When n is 2 or more, the type of alkylene group may be composed of different alkylene groups, and may be generally composed of the same alkylene group. In the two aromatic hydrocarbon rings Z, the type of the group R ³ may be the same or different.

The number (number of added moles) n of the oxyalkylene group (OR ³ ) may be 0 or 1 or more (for example, about 0 to 20), for example, 0 to 15 (for example, 1 to 12), preferably 0. It may be about 10 to 10 (for example, 1 to 8), more preferably about 0 to 7 (for example, 1 to 6), and particularly about 0 to 5 (for example, 0 to 2). When p is 2 or more, the number of substitutions n may be the same or different in two or more groups — [(OR ³ ) _n —Y] substituted on the same ring Z. The number of substitutions n may be the same or different in the group — [(OR ³ ) _n —Y] substituted on different rings Z.

The preferred group X is the group — [(OR ³ ) _n —Y], and the group Y is preferably a hydroxyl group. In addition, in Formula (1), the compound whose group Y is a hydroxyl group, and the alkylene oxide adduct of these compounds are represented by following formula (1A).

(In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
The substitution number p of the group X may be 1 or more (for example, 1 to 6), for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases.

In the formula (1) [or (1A)], the substitution position of the group X is not particularly limited, and it may be substituted at an appropriate substitution position on the ring Z. For example, when the ring Z is a benzene ring, the group X may be substituted at the 2-6 position of the phenyl group, and may preferably be substituted at the 4 position. In addition, when the ring Z is a condensed polycyclic hydrocarbon ring, the group X is a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring (for example, naphthalene In many cases, the ring is substituted at least on the 5-position, 6-position, etc. of the ring.

Specific fluorene compounds include 9,9-bis (hydroxyaryl) fluorenes [eg, 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxynaphthyl) fluorenes], 9,9 -Bis (hydroxy (poly) alkoxyaryl) fluorenes [eg, 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes], etc .; In the compound, a compound in which a hydroxyl group is substituted with a mercapto group, a glycidyloxy group, or a (meth) acryloyloxy group is 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 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], 9,9-bis ( Rehydroxyphenyl) fluorene [for example, 9,9-bis (di or trihydroxyphenyl) such as 9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene ) Fluorene].

The 9,9-bis (hydroxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyphenyl) fluorenes, and are compounds in which the phenyl group is substituted with a naphthyl group, for example, 9,9-bis ( Hydroxynaphthyl) fluorene [eg, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (5-hydroxy-1-naphthyl) fluorene] and the like.

9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene such as 9,9-bis (hydroxy _{C 2-4} alkoxyphenyl) fluorene}, 9,9-bis (alkyl - hydroxy alkoxyphenyl) Fluorene {eg, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, Such as 9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene 9,9-bis (mono or di C _1-4 alkyl-hydroxy C _2-4 alkoxyphenyl) fluorene}, 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene {eg, 9,9-bis [4- 9,9-bis (mono or di C _6-10 ) such as (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene 9,9-bis (hydroxyalkoxyphenyl) fluorenes such as aryl- _{hydroxyC 2-4} alkoxyphenyl) fluorene} (a compound in which n is 1 in the formula (1A)); 9,9-bis (hydroxydi) Alkoxyphenyl) fluorene {eg, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] 9,9-bis (hydroxydialkoxyphenyl) fluorenes such as 9,9-bis (hydroxydiC _2-4 alkoxyphenyl) fluorene} such as phenyl} fluorene (in the formula (1A), n is 2 or more) A certain compound) and the like.

Further, as 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes, wherein a phenyl group is substituted with a naphthyl group, For example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [6- (2-hydroxypropoxy) 9,9-bis (hydroxyalkoxynaphthyl) fluorenes such as 9,9-bis (hydroxyC _2-4 alkoxynaphthyl) fluorene} such as) -2-naphthyl] fluorene.

Among these fluorene compounds, in the formula (1A), when the group — [O— (R ³ O) _n —H] is represented by “A”, the two substitution numbers k are both shown in the table below. Compounds are preferred.

 

N in Table 1 may be an average value, and in a compound where n = 2 to 10, usually n = 2 to 8, preferably n = 2 to 7 (for example, 2 to 5) Also good.

Depending on the type of polyamide resin, a compound where n = 0 or a compound where n is 1 or more may significantly reduce the melt viscosity of the polyamide resin. Therefore, a compound in which n = 0 or a compound in which n is 1 or more can be selected as the fluorene compound. Compared with a compound with n = 0, a compound with n of 1 or more (for example, a compound with n = 1 to 10) does not impair the mechanical properties of the resin composition, and the ring Z is not only a benzene ring, Even a polycyclic aromatic hydrocarbon ring such as a biphenyl ring seems to effectively reduce the melt viscosity of the polyamide resin. Therefore, it seems that the fluorene compound preferably has an alcoholic hydroxyl group rather than a phenolic hydroxyl group.

Fluorene compounds may be used alone or in combination of two or more. The fluorene compound may be a commercially available product or may be synthesized by a conventional method.

[Flowability improver and resin composition]
The additive (fluorene compound) of the present invention reduces the melt viscosity of the polyamide resin and improves (or improves) the melt fluidity. That is, when a fluorene compound is added to or mixed with a polyamide resin, the absorption intensity in the vicinity of 3300 cm ⁻¹ derived from the NH group of the amide bond decreases in the FT-IR spectrum, and the intermolecular hydrogen bond due to the amide bond is relaxed. Or it can be reduced. Therefore, even if the addition amount of the fluorene compound is small, the melt viscosity of the polyamide resin can be lowered, the melt fluidity can be improved, and the moldability can be greatly improved.

The polyamide resin (PA) may be formed of an aliphatic, alicyclic and / or aromatic monomer.

Examples of aliphatic monomers include aliphatic diamines [eg, tetramethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, 2-methyloctamethylene diamine, trimethylhexamethylene diamine, decamethylene diamine, dodeca diamine. Linear or branched C _2-20 alkylene diamine such as methylene diamine (preferably linear or branched C _4-12 alkylene diamine, more preferably linear or branched C _6-9 alkylene diamine) ) Etc.]; aliphatic dicarboxylic acids [eg linear or branched C _2-18 alkanedicarboxylic acids such as adipic acid, sebacic acid, 1,10-decanedicarboxylic acid (preferably linear or branched) C _4-10 alkanedicarboxylic acid, more preferably Linear or branched C _4-8 alkanedicarboxylic acid)], etc.]; lactam [eg, 4- to 12-membered (preferably 7-12-membered) lactam such as ε-caprolactam, ω-laurolactam, etc.] Aliphatic aminocarboxylic acids [eg amino C _2-20 alkyl carboxylic acids such as 6-aminohexanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid (preferably amino C _4-16 alkyl carboxylic acids, more preferably Is an amino C _5-11 alkylcarboxylic acid).

The alicyclic monomer only needs to have an alicyclic skeleton (cycloalkane skeleton), for example, an alicyclic diamine [for example, diaminocycloalkane, di (aminoalkyl) cycloalkane (for example, diaminomethylcycloalkane, etc.) Etc.]; alicyclic dicarboxylic acids (for example, cycloalkane dicarboxylic acids); alicyclic aminocarboxylic acids (for example, aminocycloalkane carboxylic acids) and the like.

The aromatic monomer may have an aromatic ring skeleton, for example, an aromatic (or araliphatic) diamine [for example, diaminoarene such as m-phenylenediamine and p-phenylenediamine, m-xylylenediamine, etc. Di (aminoalkyl) arene etc.]; aromatic (or araliphatic) dicarboxylic acids [eg dicarboxyarenes such as terephthalic acid, isophthalic acid etc.]; aromatic aminocarboxylic acids (eg amino aminobenzoic acid etc. An aryl carboxylic acid etc.) can be illustrated.

The polyamide resin can be obtained by polymerizing these monomers alone or in combination of two or more. The polyamide resin may be a homopolyamide formed of a single monomer (a single diamine and dicarboxylic acid, or a single lactam and / or aminocarboxylic acid), and a copolyamide obtained by copolymerizing a plurality of monomers. It may be. Representative polyamide resins include, for example, aliphatic polyamide resins, alicyclic polyamide resins, aromatic polyamide resins and the like.

The aliphatic polyamide resin may be formed of an aliphatic monomer unit. For example, a homopolyamide of an aliphatic diamine and an aliphatic dicarboxylic acid (for example, polyamide 46, polyamide 66, polyamide 610, polyamide 612, etc.); lactam And / or homopolyamides of aliphatic aminocarboxylic acids corresponding to lactams (eg polyamide 6, polyamide 11, polyamide 12 etc.); copolymers of a plurality of aliphatic monomers (eg copolyamide 6/66, copolyamide 6) / 11, copolyamide 66/12, etc.).

The alicyclic polyamide resin only needs to have at least an alicyclic monomer unit, and may be formed by combining an aliphatic monomer and an alicyclic monomer. For example, a homopolyamide (for example, a polymer of diaminomethylcyclohexane and adipic acid) of alicyclic diamine and aliphatic dicarboxylic acid can be exemplified.

The aromatic polyamide resin only needs to have at least an aromatic monomer unit, for example, a semi-aromatic polyamide resin formed from an aromatic monomer and an aliphatic (or alicyclic) monomer, and an aromatic monomer. And wholly aromatic polyamide resins that do not contain aliphatic and alicyclic monomer units.

Examples of the semi-aromatic polyamide resin include a homopolyamide of an aromatic (or araliphatic) diamine and an aliphatic dicarboxylic acid (for example, polyamide MXD6 (polymer of m-xylylenediamine and adipic acid)); Homopolyamides of aliphatic diamines and aromatic dicarboxylic acids [eg, polyamide 6T (polymer of hexamethylenediamine and terephthalic acid), polyamide 9T (polymer of nonamethylenediamine and terephthalic acid), polyamide 10T (decamethylene) Polymer of diamine and terephthalic acid), polyamide 12T (polymer of dodecamethylenediamine and terephthalic acid), polyamide M5T (polymer of 2-methylpentamethylenediamine and terephthalic acid), polyamide M8T (2-methylocta Between methylenediamine and terephthalic acid. Polymer), polyamide 6I (polymer of hexamethylenediamine and isophthalic acid), polymer of trimethylhexamethylenediamine and terephthalic acid, etc.]; copolymer containing at least aliphatic diamine and aromatic dicarboxylic acid (for example, Copolyamide 6T / 66, copolyamide 6T / M5T, copolyamide 6T / 6I, copolyamide 6T / 6I / 6, copolyamide 6T / 6I / 66, etc.).

Examples of wholly aromatic polyamide resins include homopolyamides of aromatic diamines and aromatic dicarboxylic acids (for example, polymers of m-phenylenediamine and isophthalic acid, polymers of p-phenylenediamine and terephthalic acid, etc.) Etc.

The polyamide resin may be a polyamide having an N-alkoxymethyl group, a polymerized fatty acid-based polyamide resin having a polymerization component of dimer acid which is a dimer of unsaturated higher fatty acid. These polyamide resins can be used alone or in combination of two or more.

The polyamide resin may be crystalline or amorphous, or may be a transparent polyamide resin (amorphous transparent polyamide resin). As the polyamide resin, from the viewpoint of the mechanical properties of the molded product, a crystalline resin is usually used in many cases.

In particular, since the melt viscosity of the polyamide resin greatly depends on the melting temperature and the decomposition temperature is close to the melting point, the present invention is applied to a polyamide resin having low melt fluidity (high melt viscosity) and poor moldability. Is advantageous. The melting point of such a polyamide resin may be about 200 to 300 ° C. (preferably 210 to 280 ° C., more preferably 220 to 260 ° C.), or 200 to 400 ° C. (preferably 220 to 350 ° C., more preferably 230 to 330 ° C.). In particular, among polyamide resins, for example, polyamide resins having relatively high melting points such as semi-aromatic polyamide resins and tending to have low melt fluidity, the fluidity improver of the present invention is effective in melt viscosity. Can be reduced to improve moldability. The number average molecular weight of the polyamide resin is about 0.7 × 10 ⁴ to 100 × 10 ⁴ (preferably 1 × 10 ⁴ to 75 × 10 ⁴ , more preferably 2 × 10 ⁴ to 50 × 10 ⁴ ). It may be about 3 × 10 ⁴ to 100 × 10 ⁴ (for example, 5 × 10 ⁴ to 50 × 10 ⁴ ). The molecular weight can be measured using a conventional method such as gel permeation chromatography (GPC), and may be evaluated as a molecular weight in terms of polystyrene.

Typical examples of such polyamide resins include aliphatic polyamide resins such as polyamide 46, polyamide 6 and polyamide 66, alicyclic polyamide resins such as a polymer of diaminomethylcyclohexane and adipic acid, and polyamide 6T. And aromatic polyamide resins such as polyamide 9T and polyamide 6I. These polyamide resins may contain an aliphatic monomer having an alkylene group having a repeating unit having at least 4 to 12 carbon atoms (preferably about 6 to 11, more preferably 6 to 9, particularly at least 6). The aromatic monomer contained in the aromatic polyamide resin may have, for example, a phenylene group, preferably a p- or m-phenylene group, more preferably a p-phenylene group.

The fluorene compound has a high thermal decomposition temperature. For example, when measured by thermogravimetric differential thermal analysis (TG-DTA), the thermal decomposition temperature of 9,9-bis (4-hydroxyphenyl) fluorene (BPF) The decrease in temperature by 5 wt% is about 301 ° C., and the thermal decomposition temperature of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), which is a typical fluorene compound, is 5 wt%. Decrease temperature is about 342 ° C. Thus, it seems that the thermal decomposition temperature of an integer compound of n = 1 or higher is higher than that of a compound of n = 0. Furthermore, the thermal decomposition temperature of the compound in which the ring Z is a ring assembly hydrocarbon ring (such as a biphenyl ring) or a condensed polycyclic aromatic hydrocarbon ring (such as a naphthalene ring) is further increased. Therefore, the thermal decomposition temperature of the fluorene compound represented by the formula (1) or (1A) (for example, a compound having n = 0 to 2) is usually 300 to 400 ° C. (for example, 320 to 380 ° C.). ) Degree. Thus, the fluorene compound can improve the melt fluidity of the polyamide resin without being decomposed even at a high temperature.

Further, if necessary, olefin resin [ethylene resin, propylene resin, cyclic olefin resin, etc.], halogen-containing vinyl resin (polyvinyl chloride, fluorine resin, etc.), acrylic resin (polymethyl methacrylate (PMMA), etc.) Copolymers such as styrene resins (polystyrene (PS); styrene-methyl methacrylate copolymer (MS resin), styrene-acrylonitrile copolymer (AS resin)); high-impact polystyrene (HIPS), acrylonitrile-butadiene -Styrene copolymers (ABS resin), methyl methacrylate-butadiene-styrene copolymers (MBS resin) and other rubber graft styrene copolymers, etc., aromatic polyester resins (polyethylene terephthalate (PET), polybutylene terephthalate) (PBT), Lithylene naphthalate (PEN), polyarylate resin (PAR), etc.), polycarbonate resin (PC) (for example, aromatic polycarbonate resin, etc.), polyacetal resin (POM), polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS) , Polysulfone resin (PSF) (including polyethersulfone (PES), etc.), polyetherketone resin (PEK) (including polyetheretherketone resin (PEEK)), polyimide resin (polyetherimide (PEI), liquid crystalline) Polymers (including LCP) and thermoplastic resins such as thermoplastic elastomers may be used in combination. These thermoplastic resins may be used alone or in combination of two or more.

If necessary, the polyamide resin (PA) may form a polymer alloy with the thermoplastic resin. Examples of the polymer alloy include an alloy with the styrene resin (for example, ABS resin, MBS resin, etc.); an alloy with an aromatic polyester resin (for example, PET, PBT, PEN, PAR, etc.); an alloy with PPE; Examples include alloys with PC (for example, aromatic polycarbonate resin); alloys with PPS; alloys with LCP; alloys with PSF (including PES) and PEK (including PEEK). These polymer alloys may contain a compatibilizing agent.

The use ratio of the fluidity improver (fluorene compound) can be selected, for example, from a range of about 0.1 to 100 parts by weight (for example, 1 to 75 parts by weight) with respect to 100 parts by weight of the polyamide resin. 1 to 50 parts by weight (eg 1 to 40 parts by weight), preferably 2 to 30 parts by weight (eg 5 to 25 parts by weight), or 1 to 20 parts by weight (eg 2.5 May be about 15 to 15 parts by weight), particularly about 3 to 10 parts by weight (eg, 3 to 5 parts by weight).

Although the strength (mechanical strength) of the polyamide resin may be improved or improved by the fluidity improver of the present invention, the melt fluidity and moldability can be greatly improved. Therefore, the present invention also includes such a resin composition, that is, a thermoplastic resin composition containing a polyamide resin and a fluidity improver.

The resin composition may contain various additives [for example, fillers or reinforcing agents, colorants (dye pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet rays). Absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, low stress agents, carbon materials, etc.] Good. These additives may be used alone or in combination of two or more.

The polyamide resin composition is prepared by mixing a polyamide resin, a fluorene compound (fluidity improver) and other components (additives, etc.) as required by a conventional method such as dry mixing or melt kneading. The resin composition may be in the form of pellets.

The present invention also includes a molded body formed of the resin composition. The shape of the molded body is not particularly limited and can be selected according to the application. For example, a one-dimensional structure (such as a linear body), a two-dimensional structure (such as a film, sheet, or plate), or a three-dimensional structure. A structure (block shape, tubular shape, rod shape, tube shape, hollow shape, or the like) may be used.

The molded body can be produced by using a conventional molding method such as an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, or a casting molding method. .

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, various characteristics were measured as follows.

[Melting fluidity]
The resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were used at a temperature of 270 ° C. in accordance with JIS K7199 using a flow property tester (“Capillograph 1D” manufactured by Toyo Seiki Seisakusho Co., Ltd.). The melt viscosity was measured at extrusion speeds of 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000 (mm / min).

For the resin compositions obtained in Examples 5 to 6 and Comparative Example 5, electric injection molding machine [“SE18-DUZ” manufactured by Sumitomo Heavy Industries, Ltd., maximum mold clamping force: 18 tf, screw diameter: φ16 mm ( SL screw)] was used to evaluate the melt fluidity by spiral flow under the following conditions.
Mold spiral shape: width 5mm, thickness 3mm, maximum length 750mm (die according to EIMS T901)
Mold temperature: 80 ° C (actual value 79-82 ° C)
Resin drying: 100 ° C. × 24 hours (vacuum drying)
Molding temperature: 300-320 ° C
Injection speed: 20, 50, 80 mm / sec injection pressure; 50, 100, 150 MPa.

[Mechanical properties]
Test specimens obtained in Examples and Comparative Examples were subjected to predetermined test conditions (test speed) using a tensile tester (“5566 type” manufactured by Instron) in accordance with JIS K7161-1994 and JIS K7162-1994. Tensile strength, elongation, and tensile modulus were measured at 50 mm / min (the tensile modulus was measured at 1 mm / min), the distance between marked lines was 50 mm, the test temperature was 23 ± 1 ° C., and the humidity was 50 ± 5% RH. About each sample, it measured by N = 5 and computed the average value of the obtained measured value.

[Example 1]
90 parts by weight of polyamide 66 (“Amilan CM3001-N” manufactured by Toray Industries, Inc.) and fluorene compound 1 (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, manufactured by Osaka Gas Chemical Co., Ltd. BPEF ”) was dry blended with 10 parts by weight, then transferred to the hopper of a feeder (“ KS60 ”manufactured by K-Tron Co., Ltd., a gravimetric weighing single screw feeder), and a twin screw kneading extruder (manufactured by Parker Corporation) Using HK25D ", a co-rotating twin screw extruder), kneading was performed at 270 ° C, and injection molding was performed to prepare a flat plate test piece defined in JIS K7139 A1 type (multipurpose test piece).

Also, a melt-kneading was performed in the same manner as described above to prepare a pellet-shaped resin composition for measuring melt viscosity characteristics.

[Examples 2 to 4]
A flat plate test piece was prepared by injection molding in the same manner as in Example 1 except that the following fluorene compound was used in place of the fluorene compound 1, and a pellet-shaped resin composition was prepared.

Example 2: Fluorene Compound 2 (9,9-bis (4-hydroxy-3-methylphenyl) fluorene, “BCF” manufactured by Osaka Gas Chemical Co., Ltd.)
Example 3: Fluorene Compound 3 (9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, “BOPPEF” manufactured by Osaka Gas Chemical Co., Ltd.)
Example 4: Fluorene Compound 4 (Adduct obtained by adding 9 mol of ethylene oxide to 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, “BPEF-9EO” manufactured by Osaka Gas Chemical Co., Ltd.).

[Comparative Example 1]
Without adding the fluorene compound, polyamide 66 was injection molded in the same manner as in Example 1 to prepare a flat plate test piece, and a pellet-shaped resin composition was prepared.

[Comparative Example 2]
70 parts by weight of maleic acid-modified polypropylene PP (“Admer QF551” manufactured by Mitsui Chemicals, Inc.) was melt-kneaded in the same manner as in Example 1 and carbon black (“MA-100” manufactured by Mitsubishi Chemical Corporation) 30 Weight parts were charged by side feed of a biaxial kneading extruder and melt-kneaded, and injection molded in the same manner as in Example 1 to prepare a flat plate test piece and a pellet-shaped resin composition.

[Comparative Example 3]
63 parts by weight of maleic acid-modified polypropylene PP and 7 parts by weight of fluorene compound 1 are dry blended and melt-kneaded in the same manner as in Example 1, and 30 parts by weight of carbon black is fed into a twin-screw kneading extruder by side feed. The resulting mixture was melt-kneaded and injection molded in the same manner as in Example 1 to prepare a flat plate test piece and a pellet-shaped resin composition.

[Comparative Example 4]
A flat plate test piece was prepared by injection molding in the same manner as in Comparative Example 3 except that the fluorene compound 2 was used in place of the fluorene compound 1, and a pellet-shaped resin composition was prepared.

And when the melt fluidity of the pellet-shaped resin composition and the mechanical properties of the flat plate test piece were evaluated, the results shown in Table 2, FIG. 1 and FIG. 2 were obtained. FIG. 1 shows the results of the melt fluidity test of Comparative Example 1 and Examples 1 and 2, and FIG. 2 shows the results of the melt fluidity test of Comparative Examples 2 and 4.

 

As shown in FIG. 2, the modified propylene PP showed similar melt flow characteristics regardless of the addition of the fluorene compound. On the other hand, as shown in FIG. 1, in the polyamide resin, as apparent from the comparison with Comparative Example 1, the melt viscosity was greatly reduced by the addition of the fluorene compound 1 or 2.

Further, as shown in FIG. 3 and FIG. 4, the resin composition of Example 1 was analyzed by FT-IR and the spectrum of Comparative Example 1 (dotted line) and the spectrum of Example 1 (solid line) were superimposed. In comparison with Comparative Example 1, it was found that the absorption intensity in the vicinity of 3300 cm ⁻¹ due to the NH group of the amide bond was small. From this, it is considered that by adding the fluorene compound, the hydrogen bond of the polyamide resin is relaxed, the melt viscosity is lowered, and the melt fluidity is improved. In addition, as shown in Table 2, even if a fluorene compound is added, the mechanical properties are not improved so much.

[Example 5]
100 parts by weight of polyamide 6T (“SOLDEL AT-1002” manufactured by SOLVAY) and 3 parts by weight of fluorene compound 1 were dry blended, and then a feeder (“KS60” manufactured by K-Tron, a gravimetric metering single-axis feeder. ), And kneaded at 320 ° C. using a twin-screw kneading extruder (“HK25D” manufactured by Parker Corporation, co-rotating twin-screw extruder), injection molded, and JIS K7139 A1 type (multipurpose) The flat plate test piece prescribed | regulated to a test piece) was prepared.

Also, a melt-kneading was performed in the same manner as described above to prepare a pellet-shaped resin composition for measuring melt viscosity characteristics.

[Example 6]
A flat plate test piece was prepared by injection molding in the same manner as in Example 5 except that the fluorene compound 1 was changed to 5 parts by weight, and a pellet-shaped resin composition was prepared.

[Comparative Example 5]
Without adding the fluorene compound 1, polyamide 6T was injection molded to prepare a flat plate test piece in the same manner as in Example 5, and a pellet-shaped resin composition was prepared.

The mechanical properties of the flat plate test piece thus obtained and the melt fluidity of the resin composition were evaluated, and the results shown in Tables 3 to 4 and FIGS. 5 to 7 were obtained. Table 3 shows the compositions of Examples 5 to 6 and Comparative Example 5, results of mechanical properties, and part of the results of melt flowability (spiral flow), and FIGS. 5 to 7 show Examples 5 to 6 and Comparative Examples. The result of the melt fluidity test (spiral flow) of Example 5 is shown.

 

As can be seen from Table 3 and FIGS. 5 to 7, Examples 5 to 6 in which the fluorene compound 1 was added to the polyamide 6T were compared with Comparative Example 5 in which the fluorene compound 1 was not added. Even under the injection conditions, the spiral flow length is increased and the melt fluidity is improved.

The fluidity improver (melt viscosity reducing agent) of the present invention can improve the melt fluidity of the polyamide resin without deteriorating the mechanical properties of the polyamide resin, and can greatly improve the moldability including the molding cycle. Therefore, the resin composition of the present invention is molded into various molded products to which polyamide resin is applied in the form of unreinforced polyamide, reinforced polyamide reinforced with reinforcing agent (glass fiber, carbon fiber, etc.), polymer alloy, and the like. It can be used as an engineering plastic. For example, using polyamide resin's excellent properties such as wear resistance, lubricity, heat resistance, and chemical resistance, fibers, films, daily necessities, automobile-related parts, electrical / electronic-related parts, machinery-related Can be used for a wide range of applications such as parts, construction-related parts, sports / leisure-related parts, such as ropes, tire cords, fishing nets, filter cloths, clothing core materials, packaging films, radiator tanks, manifolds, piping tubes and pipes , Hoses, air cleaners, clutch parts, connectors (including electrical circuit connectors, etc.), switches, gears, pulleys, cams, bushes, rollers, bearings, housings, casings, wire coverings, doors, rail parts, casters, shoes, shuttlecocks Can be used for a wide range of applications such as reels.

Claims (10)

1. A fluidity improver for improving the melt fluidity of polyamide resin, comprising a compound having a 9,9-bisarylfluorene skeleton.
2. The fluidity improver according to claim 1, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1).
   

   

   [Wherein ring Z is an aromatic hydrocarbon ring, R ¹ and R ² are substituents, X is a group — [(OR ³ ) _n —Y] (where Y is a hydroxyl group, mercapto group, glycidyl An oxy group or a (meth) acryloyloxy group, R ³ is an alkylene group, n is 0 or an integer of 1 or more) or an amino group, k is an integer of 0 to 4, m is an integer of 0 or more, and p is 1 The above integers are shown. ]
3. The fluidity improver according to claim 1 or 2, wherein the compound having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (1A).
   

   

   (In the formula, Z, R ¹ , R ² , k, m, R ³ , n, and p are the same as those in the formula (1).)
4. Ring Z is a benzene ring or naphthalene ring, R ¹ is an alkyl group, k is 0 to 1, R ² is an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkoxy group, m is 0 to 2, and R ³ is C The fluidity improver according to claim 2 or 3, wherein _2-4 alkylene group, n is 0 to 20, and p is 1 to 3.
5. Compounds having a 9,9-bisarylfluorene skeleton include 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene, 9,9-bis (di or trihydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) fluorene, 9,9-bis (hydroxyalkoxyphenyl) fluorene, 9,9-bis (alkyl-hydroxyalkoxyphenyl) fluorene , 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene, 9,9-bis (hydroxyalkoxynaphthyl) fluorene, and alkylene oxide adducts of these compounds. Described in any of Flow improvers.
6. 6. The fluidity improver according to claim 1, wherein the polyamide resin is at least one selected from an aliphatic polyamide resin, an alicyclic polyamide resin, and an aromatic polyamide resin.
7. The fluidity improver according to any one of claims 1 to 6, which is added at a ratio of 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin.
8. A thermoplastic resin composition comprising a polyamide resin and the fluidity improver according to any one of claims 1 to 7.
9. A molded body formed of the thermoplastic resin composition according to claim 8.
10. A method for improving the melt fluidity of the polyamide resin by adding the fluidity improver according to any one of claims 1 to 7 to the polyamide resin.

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