JP4514491B2 - Compatibilizer - Google Patents

Description

  The present invention relates to a compatibilizing agent composed of a compound having a fluorene skeleton, a plastic material using the compatibilizing agent, and a molded article.

  In recent years, the reuse or reuse of waste plastics has become an important issue from the viewpoints of protection of the global environment, effective use of resources (recycling), waste disposal problems, and the like. However, the reuse of plastic products has a very large technical problem, and at present, the reuse is hardly performed except for the recycling of polyethylene terephthalate (PET) bottles (pet bottles).

  In other words, the conventional technology is made of a transparent single resin that does not contain additives such as PET bottles, and even when the contents in use are extremely clean plastic products, viscosity reduction, coloring, and various physical properties during reuse A decline is inevitable. As a result, a recycled product with sufficient performance as a product cannot be obtained. Considering the collection cost of used products and the appearance, quality, etc. of recycled products, even a plastic bottle is still a sufficiently practical recycling system. It is not.

  Therefore, since plastic products other than PET bottles contain a large amount of additives or are composed of various resins, coloring and deterioration of physical properties are inevitable when reused. That is, for plastic products other than PET bottles, the safety, productivity, and quality of recycled products are insufficient for practical use, and there is also a recycling cost, and a recycling system has not yet been established.

  In addition, it is difficult to completely separate and collect the waste plastic, and usually a plurality of types of polymers are mixed in the regeneration process. Therefore, the physical properties of the recycled plastic are reduced. A large amount of plasticizer such as oil is blended during plastic regeneration to prevent deterioration of physical properties, but it is difficult to restore the original physical properties. Furthermore, if the plural types of polymers mixed at the time of regeneration are different polymers that are incompatible with each other, uniform dispersion cannot be obtained, and the polymer properties of the recycled plastic are greatly reduced.

  A method of mixing different types of polymers using a compatibilizer is known. For example, JP-A-3-273056 (Patent Document 1) proposes a method of alloying an aromatic polysulfone and a polyamide resin using a compatibilizing agent. In this document, a compound having a functional group such as a carboxylic acid group, an acid anhydride group, an ester group, an amino group, an acid amide group, an imide group, or a hydroxyl group is used as a compatibilizing agent. JP-A-8-302217 (Patent Document 2) proposes a compatibilizing agent composition containing a bisoxazoline compound, a compound having a hydrophobic main chain and an active hydrogen atom, and a method for producing the compatibilizer composition. Japanese Patent Application Laid-Open No. 9-51965 (Patent Document 3) proposes a method for improving the properties of a golf ball by alloying an ionomer resin and a diene rubber using a compatibilizing agent. In this document, a polymer having maleic anhydride, an oxazoline group, a glycidyl group and the like is used as a compatibilizing agent. However, even in these methods, there is no known method for effectively recycling the plastic molded body without any deterioration in physical properties.

  Thus, since the recycled plastic polymer has low physical properties, it can be used only for limited applications where low physical properties can be used. Under such circumstances, recycling of plastic waste remains at a very low level, which is a major cause of environmental and resource problems.

  On the other hand, various plastic products often require flame retardancy. Therefore, in order to impart flame retardancy to a plastic molded body, generally, a flame retardant is blended with a plastic material. However, when a flame retardant is added to a plastic material, the physical properties of the plastic are likely to deteriorate. In particular, when a plastic material contains a plurality of types of polymers that are incompatible with each other, a uniform dispersion of these polymers cannot be obtained, and the physical properties of the plastic are further greatly reduced by the addition of a flame retardant. That is, the problem of deterioration in physical properties due to the blending of the flame retardant becomes greater when the plastic material is recycled from the waste plastic than in the case of an unused plastic material.

  Various plastic products are often required to improve various performances and functions such as strength, heat resistance, water resistance, warm water resistance, and moisture resistance. In such a case, various inorganic fillers are blended in the plastic material according to various performances and functions. However, when an inorganic filler is added to the plastic material, the physical properties of the plastic are likely to be lowered as in the case of the flame retardant.

Under such circumstances, in order to impart various performances such as flame retardancy, there is a demand for the development of a technique that does not cause deterioration in the physical properties of the plastic even if a flame retardant or an inorganic filler is blended in the plastic material. In particular, when recycling and recycling waste plastics, when multiple types of polymers are mixed, especially when multiple types of polymers that are incompatible with each other are mixed, the physical properties of the polymer do not deteriorate. In addition, there is a demand for the development of technology that can impart functions such as flame retardancy.
JP-A-3-273056 (Claim 1) JP-A-8-302217 (Claim 1) JP-A-9-51965 (Claims 1, 3 to 5)

  Accordingly, an object of the present invention is to provide a compatibilizing agent capable of ensuring practical physical properties even when a plastic material is regenerated using a plurality of types of polymers including at least one used polymer, and a recycled plastic material using the same. And providing a molded body.

  Another object of the present invention is to provide a compatibilizing agent capable of ensuring practical physical properties even when a plastic material is regenerated using a plurality of types of polymers including a flame retardant and an inorganic filler, and a recycled plastic material and molding using the same. To provide a body.

  Still another object of the present invention is to provide a compatibilizing agent capable of improving flame retardancy, mechanical properties, heat resistance, and various resistances, a recycled plastic material and a molded body using the compatibilizer.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have regenerated a plastic material using a plurality of types of polymers including at least one type of used polymer when a compound having a fluorene skeleton is used as a compatibilizing agent. Even so, it was found that practical plastic properties could be secured, and the present invention was completed.

  That is, the compatibilizing agent of the present invention is composed of a compound having a fluorene skeleton. The compound may be a compound represented by the following formula (1).

(Wherein R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or a reactive group, n1 and n2 are the same or different and represent 0 or an integer of 1 to 5, and m1 and m2 are the same or Differently 0 or an integer of 1 to 4)
In the formula (1), the non-reactive group is, for example, an alkyl group, an aryl group, an aralkyl group, and the reactive group is, for example, a hydroxyl group, an amino group, or a group derived from these active hydrogens. It may be. The compound having a fluorene skeleton may be a thermoplastic resin, a thermosetting resin, or the like. For example, a resin obtained by polymerizing the compound represented by the formula (1) as a monomer component (for example, a polyester resin, Polyurethane resin, polycarbonate resin, acrylic resin, polyimide resin, etc.). The compatibilizer may further contain a compatibilizer such as an ionomer compound, a compound containing a reactive group or a functional group, or an elastomer compound.

  The present invention also includes a plastic material containing a plurality of types of polymers including at least one used polymer and the compatibilizer. The plastic material may further contain at least one selected from a flame retardant and an inorganic filler. Further, the present invention includes a molded body formed of this plastic material.

  According to the present invention, even if a plastic material containing a plurality of types of polymers including at least one type of used polymer is recycled, practical physical properties can be secured. Moreover, even if a flame retardant or an inorganic filler is further contained in the polymer, practical physical properties can be secured. Furthermore, flame retardancy, mechanical properties (strength, etc.) and various resistances (heat resistance, water resistance, warm water resistance, moisture resistance, etc.) can be improved.

[Compound having a fluorene skeleton]
The compatibilizing agent of the present invention is composed of a compound having a fluorene skeleton. The compound having a fluorene skeleton is not particularly limited as long as it has a fluorene skeleton. Usually, a compound having a 9,9-bisphenylfluorene skeleton is used. For example, the compound represented by the formula (1) or a derivative thereof is Used.

In the formula (1), the non-reactive group is not particularly limited, but examples thereof include alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group and the like). C _1-10 alkyl group, preferably C _1-7 alkyl group, more preferably C _1-6 alkyl group etc.), alkenyl group (C _2-6 alkenyl group such as vinyl group, allyl group etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group), aryl group [phenyl group, alkylphenyl group (Methylphenyl group (tolyl group), dimethylphenyl group (xylyl group, etc.)), C _6-20 aryl group such as naphthyl group, preferably C _6-10 aryl group, especially phenyl group ), Hydrocarbon groups such as aralkyl groups (C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group); alkoxy groups (C _1-4 alkoxy groups such as methoxy group); acyl Group (C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl group); N, N-disubstituted amino group [for example, substituted with hydrocarbon group Amino group (N, N-diC _1-6 alkylamino group such as dimethylamino group)]; halogen atom (fluorine atom, chlorine atom etc.); nitro group; cyano group and the like. Of these non-reactive groups, an alkyl group, a cycloalkyl group, an aryl group and the like are usually used.

Examples of the reactive group include a group containing active hydrogen (active hydrogen-containing group), a group derived from this active hydrogen-containing group, and the like. Examples of the active hydrogen-containing group include a hydroxyl group, a mercapto group, an amino group, and an N-monosubstituted amino group [for example, an amino group substituted with a hydrocarbon group (an N-monoC _1-6 alkyl such as a methylamino group). Amino group, etc.)], carboxyl group and the like, and usually a hydroxyl group, an amino group, or an N-monosubstituted amino group (particularly a hydroxyl group, an amino group).

Examples of the group derived from an active hydrogen-containing group include a group obtained through an active hydrogen atom of the active hydrogen-containing group (particularly, a hydroxyl group or an amino group). Such a group is not particularly limited, but is a group derived from an active hydrogen of a hydroxyl group or an amino group, for example, a group — [X— (R ⁵ O) _k —Y] (wherein R ⁵ is An alkylene group, a group X is an oxygen atom (ether group) or an imino group, a group Y is a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and k is an integer of 0 or 1 or more. , When k is 0, Y is not a hydrogen atom).

The alkylene group represented by the group R ⁵ is not particularly limited, and examples thereof include C _2-4 alkylene groups (ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.) In particular, C _2-3 alkylene groups (particularly ethylene groups and propylene groups) are preferred. R ⁵ may be the same or different alkylene group in the corresponding active hydrogen-containing group R ¹ (or R ² ), but is usually the same.

  The substitution number (or addition number) k of the oxyalkylene unit is the same or different and can be selected from the range of 0 or about 1 to 15, for example, 0 or 1 to 12, preferably 0 or 1 to 8, more preferably It may be 0 or 1-6, especially 0 or about 1-4. When k is 2 or more, the polyalkoxy group (polyalkyleneoxy group) may be composed of the same alkylene group or a mixture of different alkylene groups (for example, ethylene group and propylene group). Usually, it is often composed of the same alkylene group.

The groups R ¹ and R ² are usually often at least reactive groups. For example, when n1 and n2 are 2, 1 or 2 groups of 2 groups R ¹ are reactive groups, and 1 or 2 groups of 2 groups R ² are reactive groups.

Preferred groups R ¹ (or R ² ) include an alkyl group (C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group), an aryl group (C _6-10 aryl group), an aralkyl group ( C _6-8 aryl-C _1-2 alkyl group), alkoxy group (C _1-4 alkoxy group), hydroxyl group, amino group, N-monosubstituted amino group (N—C _1-4 alkylamino group), group - include _{^{[X- (R 5 O) k}} -Y]. In particular, an alkyl group (C _1-4 alkyl group), an aryl group (C _6-8 aryl group), an aralkyl group (C _6-8 aryl-C _1-2 alkyl group), a hydroxyl group, an amino group, the group − [X— (R ⁵ O) _k —Y] and the groups R ¹ and R ² contain at least a hydroxyl group, an amino group, or the group — [X— (R ⁵ O) _k —Y]. Is preferred. The group R ¹ (or R ² ) may be substituted on the benzene ring alone or in combination of two or more. The groups R ¹ and R ² may be the same or different from each other, but are usually the same. Further, the groups R ¹ (or R ² ) may be different or the same in the same benzene ring.

Incidentally, the substitution position of group R ¹ (or R ²⁾ is not particularly limited, may be selected from 2 to 6-position of the phenyl group substituted at position 9 of the fluorene. Usually, one reactive group (hydroxyl group, amino group, said group-[X- (R) _k -Y] etc.) is substituted at the 9-position of fluorene at the 3- or 4-position (ie phenyl It may be substituted at the 3- or 4-position with respect to the group, in particular at the 4-position. The non-reactive group is, for example, the 2-position, 3-position or 4-position (for example, 3-methylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, etc.) of the phenyl group substituted at the 9-position of fluorene. ) May be substituted.

The preferable substitution numbers n1 and n2 are 1 to 4, more preferably 1 to 3 (particularly 1 to 2). The number of preferred reactive groups in each group R ^1, R ^2, 1 to 3, in particular 1 to 2. The substitution numbers n1 and n2 may be different but are usually the same in many cases.

The groups R ³ and R ⁴ are usually alkyl groups (C _1-4 alkyl groups, especially methyl groups). The groups R ³ and R ⁴ may be different from each other or the same. Further, the groups R ³ (or R ⁴ ) may be different or the same in the same benzene ring. In addition, the bonding position (substitution position) of the group R ³ (or R ⁴ ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers m1 and m2 are 0 or 1, in particular 0. The substitution numbers m1 and m2 may be different but are usually the same.

  Specific fluorene compounds include, for example, 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof, 9,9-bis (aminophenyl) fluorenes or derivatives thereof, and the like.

(1) 9,9-bis (hydroxyphenyl) fluorenes or derivatives thereof (1a) 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes, 9,9 -Bis (dihydroxyphenyl) fluorenes, 9,9-bis (trihydroxyphenyl) fluorenes and the like are included.

Examples of 9,9-bis (monohydroxyphenyl) fluorenes include 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene (bisphenolfluorene, BPF) and the like], substitution 9,9-bis (hydroxyphenyl) fluorene having a group {for example, 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene (biscresol fluorene, BCF), 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-butylphenyl) fluorene, 9,9-bis (3-hydroxy-2-methyl) Phenyl) fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) phenyl Oren such as 9,9-bis (C _1-4 alkyl - hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-2 , 6-Dimethylphenyl) fluorene, 9,9-bis (diC _1-4 alkyl-hydroxyphenyl) fluorene, such as 9,9-bis (4-hydroxy-3,5-di-t-butylphenyl) fluorene, etc. 9,9-bis (C _5-8 cycloalkyl-monohydroxyphenyl) such as 9,9-bis (cycloalkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene] ) Fluorene, etc.], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxy-3) Such as phenyl) fluorene 9,9-bis (C _6-8 aryl - hydroxyphenyl) fluorene, etc.], 9,9-bis (aralkyl - hydroxyphenyl) fluorene [e.g., 9,9-bis (4-hydroxy - 9,9-bis (C _6-8 aryl C _1-2 alkyl-hydroxyphenyl) fluorene etc.] such as 3-benzylphenyl) fluorene] and the like.

As 9,9-bis (dihydroxyphenyl) fluorenes, fluorenes corresponding to the 9,9-bis (monohydroxyphenyl) fluorenes, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9- Bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene, etc.] 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (3,4-dihydroxy-6-methylphenyl) fluore 9,9-bis such (C _1-4 alkyl - dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis (di C _{1 -4} alkyl-dihydroxyphenyl) fluorene, etc.], 9,9-bis (alkoxy-dihydroxyphenyl) fluorene [e.g., 9,9- such as 9,9-bis (3,4-dihydroxy-5-methoxyphenyl) fluorene. Bis (C _1-4 alkoxy-dihydroxyphenyl) fluorene and the like], 9,9-bis (aryl-dihydroxyphenyl) fluorene [eg, 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene and the like 9,9-bis (C _6-8 aryl-dihydroxyphenyl) fluorene and the like] and the like}.

  The 9,9-bis (trihydroxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (mono or dihydroxyphenyl) fluorenes such as 9,9-bis (2,4,6-triene). 9,9-bis (trihydroxy) such as hydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene Phenyl) fluorene and the like.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), fluorenones and phenols are reacted to form hydrocarbons It can be produced by using a method of producing bisphenolfluorene by crystallization with a crystallization solvent composed of a kind and a polar solvent (Japanese Patent Laid-Open No. 2003-221352).

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols). Among these methods, in particular, when the method (c) using hydrochloric acid or the method (d) using a specific crystallization solvent is applied, a product with higher yield and purity may be obtained. Many.

  (1b) As derivatives of 9,9-bis (hydroxyphenyl) fluorenes, alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes, 9,9-bis (hydroxyphenyl) fluorenes or alkylenes thereof Examples thereof include glycidyl ethers of oxide adducts, 9,9-bis (hydroxyphenyl) fluorenes, and (meth) acrylates of alkylene oxide adducts thereof.

(Alkylene oxide adduct)
Examples of alkylene oxide adducts of 9,9-bis (hydroxyphenyl) fluorenes include bis (mono to trihydroxyphenyl) fluorenes exemplified above as alkylene oxides (C _2-4 alkylene oxides, particularly C _2-3 alkylene oxides). ) Is added. The number of alkylene oxide units added (k in the above formula) is the same as described above (for example, 1 to 12, preferably 1 to 8, more preferably 1 to 6, particularly about 1 to 4), and is not particularly limited. Hereinafter, as an example, a compound in which k is 1 or 2 is illustrated.

Representative alkylene oxide adducts include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorene [eg, 9,9-bis [4- (2-hydroxyethoxy) -phenyl] fluorene (bisphenoxyethanol fluorene, BPEF). ), 9,9-bis [9,9-bis (2-hydroxyC _2-4 alkoxy) phenyl] fluorene such as 4- (3-hydroxypropoxy) -phenyl] fluorene], 9,9 having a substituent -Bis (hydroxyalkoxyphenyl) fluorene {for example, 9,9-bis (hydroxyC) such as 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (biscresol ethanolfluorene, BCEF) _2-4 alkoxy -C _1-4 alkylphenyl) fluorene, 9,9-bi [(2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene such as 9,9-bis (hydroxy C _2-4 alkoxy - di C _1-4 alkyl phenyl) fluorene, 9,9-bis [4- ( 9,9-bis [(2-hydroxyC _2-4 alkoxy) -C _6-8 arylphenyl] fluorene, such as 2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2 9,9- such as 9,9-bis [(2-hydroxyC _2-4 alkoxy) -C _6-8 aryl C _1-2 alkylphenyl] fluorene etc.} such as -hydroxyethoxy) -3-benzylphenyl] fluorene -Bis [mono (hydroxyalkoxy) phenyl] fluorenes, 9,9-bis [di or tri (hydroxyalkoxy) phenyl] fluorenes corresponding to these compounds {E.g., 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene such as 9,9-bis [di (2-hydroxy-C _2-4 alkoxy) phenyl] fluorene}, such as 9 , 9-bis [mono to tri (hydroxyalkoxy) phenyl] fluorenes; compounds corresponding to these compounds, wherein two alkylene oxide units are added to the hydroxyl group {for example, 9,9-bis {4- [2- 9,9-bis [2- (2- _{hydroxyC 2-4} alkoxy) C _2-4 alkoxyphenyl] fluorene, such as (2-hydroxyethoxy) ethoxy] phenyl} fluorene, 9,9-bis {3,4- di [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [2- (2-hydroxy-C _2-4 alkoxy) C _2-4 alkoxy 9,9-bis [mono to tri (hydroxypolyalkoxy) phenyl] fluorenes such as 9,9-bis [mono to tri (hydroxydialkoxy) phenyl] fluorenes, etc.}. .

In addition, although the manufacturing method of the alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorene is not specifically limited, For example, 9,9-bis (hydroxyphenyl) fluorene and corresponding alkylene oxide (C _2-4 alkylene oxide) or alkylene carbonate (C _2-4 alkylene carbonate), if necessary, in the presence of a catalyst (such as a base catalyst) or a phenoxy C _2-4 alcohol corresponding to fluorenone It may be produced by a method of reacting with (for example, JP-A-11-349657). Moreover, the alkylene oxide adduct of 9,9-bis (di or trihydroxyphenyl) fluorenes is replaced with 9,9-bis (hydroxyphenyl) fluorenes or phenoxy C _2-4 alcohols in the above production method. The corresponding alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes, di or tri (hydroxy C _2-4 alkoxy) benzenes, etc.] can be used.

(2) 9,9-bis (aminophenyl) fluorenes or derivatives thereof As 9,9-bis (aminophenyl) fluorenes, compounds corresponding to the 9,9-bis (hydroxyphenyl) fluorenes, Examples thereof include compounds in which the hydroxyl group of 9,9-bis (hydroxyphenyl) fluorenes is an amino group or an N-substituted amino group.

Typical 9,9-bis (aminophenyl) fluorenes include 9,9-bis (monoaminophenyl) fluorenes such as 9,9-bis (monoaminophenyl) fluorene [9,9-bis ( 4-aminophenyl) fluorene (bisaniline fluorene, etc.)], 9,9-bis (monoaminophenyl) fluorene having a substituent {for example, 9,9-bis (amino-alkylphenyl) fluorene [9,9-bis 9,9-bis (amino-C _1-4 alkylphenyl) fluorene such as (4-amino-3-methylphenyl) fluorene, 9,9-bis (3-amino-2-methylphenyl) fluorene, 9,9 -Bis (4-amino-3,5-dimethylphenyl) fluorene, 9,9-bis (4-amino-2,6-dimethylphenyl) fluorene, 9 9,9-bis (amino-diC _1-4 alkylphenyl) fluorene such as 9-bis (4-amino-3,5-di-t-butylphenyl) fluorene], these 9,9-bis (Amino-alkylphenyl) fluorene alkyl group is a cycloalkyl group (C _5-8 cycloalkyl group) or an aryl group (C _6-8 aryl group, etc.)}, corresponding to these compounds, amino 9,9-bis (monoaminophenyl) fluorenes whose group is an N-monosubstituted amino group (for example, N—C _1-4 alkylamino group).

  The derivatives of 9,9-bis (aminophenyl) fluorenes include alkylene oxide adducts of the above 9,9-bis (aminophenyl) fluorenes.

  In addition, although the manufacturing method of 9,9-bis (aminophenyl) fluorene is not specifically limited, For example, in the manufacturing method of the said bis (hydroxyphenyl) fluorene, it replaces with phenol and uses corresponding aniline. Can be manufactured.

  The compatibilizer may be a resin having a fluorene skeleton (thermoplastic resin or thermosetting resin). For example, a compound having a fluorene skeleton represented by the formula (1) may be used as a monomer component of the resin. A resin (in particular, a resin obtained by polymerizing a compound having a fluorene skeleton as a monomer component of the resin) may be included.

  The resin having a fluorene skeleton is not particularly limited, and a conventional thermoplastic resin, thermoplastic elastomer, rubber, and thermosetting resin (or photocurable resin) can be used. These resins may be used alone or in combination of two or more.

  Examples of the thermoplastic resin include olefin resins (polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, polybutene, polymethylpentene, crosslinked polyolefin, amorphous polyolefin, etc.), vinyl-based resins, and the like. Resin (polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, etc.), halogen-containing vinyl resin (polyvinyl chloride, chlorinated polyether, chlorinated polyethylene, ethylene-vinyl acetate-vinyl chloride copolymer) Polymers, ethylene-vinyl chloride copolymers, acrylonitrile-chlorinated polyethylene-styrene copolymers (ACS resin), chlorine-containing resins such as polyvinylidene chloride, fluororesins, etc., acrylic resins (polymethyl methacrylate, etc.) , D Ryl resin (nitrile resin, polyether nitrile, etc.), styrene resin (polystyrene, acrylonitrile-styrene resin (SAN resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic ester-styrene copolymer Polymer (MS resin), acrylonitrile-acrylic ester-styrene copolymer (AAS resin), crosslinked polystyrene, etc., polycarbonate resin (bisphenol A type polycarbonate, etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate, poly Polyalkylene arylate resins such as cyclohexanedimethylene terephthalate and polyethylene naphthalate, polyarylate resins, allyl resins, alkyd resins, liquid crystal polyesters, etc.) Rear acetal resins (polyacetal, etc.), polyamide resins (polyamide 6, polyamide 66, polyamide 46, polyamide 6T, polyamide MXD, etc.), polyphenylene ether resins (polyphenylene ether, modified polyphenylene ether, etc.), polysulfone resins (polysulfone, Polyethersulfone, polyallylsulfone, etc.), polyphenylene sulfide resin (polyphenylene sulfide, etc.), polyimide resin (polyetherimide, polyamideimide, polyaminobismaleimide, etc.), polyketone resin, polyetherketone resin (polyetherketone) , Polyether ether ketone, etc.), imidazole resins (polybenzimidazole, etc.), xylene resins, petroleum resins, ionomer resins, etc. It is. The thermoplastic resins may be used alone or in combination of two or more.

  Examples of the thermoplastic elastomer include polyamide elastomers, polyester elastomers, polyurethane elastomers, polystyrene elastomers, polyolefin elastomers, polydiene elastomers, polyvinyl chloride elastomers, and fluorine thermoplastic elastomers. These thermoplastic elastomers can be used alone or in combination of two or more.

  Examples of the rubber include polybutadiene (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), natural rubber (NBR), acrylonitrile-butadiene rubber (nitrile rubber), and butyl rubber. These rubbers can be used alone or in combination of two or more.

  Examples of the thermosetting resin include phenol resin, amino resin (urea resin, melamine resin, etc.), furan resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, silicone resin, thermosetting polyimide system. Resin (such as bismaleimide triazine resin), diallyl phthalate resin, vinyl ester resin (resin obtained by reaction of epoxy resin and (meth) acrylic acid or its derivatives, reaction of polyhydric phenols with glycidyl (meth) acrylate) Resin obtained), fiber reinforced plastic (FRP), and the like. In addition, the thermosetting resin (or photocurable resin) includes a polyfunctional (meth) acrylate [(meth) acrylate of the 9,9-bis (hydroxyphenyl) fluorenes, (poly) urethane (meth) acrylate]. , (Poly) ester (meth) acrylate, epoxy (meth) acrylate, etc.], vinyl ether (divinyl ether obtained by reaction of diol component and acetylene, etc.) and the like. Thermosetting resins may be used alone or in combination of two or more.

  Further, the thermosetting resin may contain an initiator, a reactive diluent, a curing agent, a curing accelerator, and the like depending on the type of the thermosetting resin (or photocurable resin). For example, the resin composition containing the epoxy resin or urethane resin may contain an amine-based curing agent or the like, and the resin composition containing the unsaturated polyester resin or vinyl ester resin may contain an initiator (peroxide resin). Oxides, etc.), polymerizable monomers (reactive diluents such as (meth) acrylic acid esters and styrene) and the like.

  A resin having a fluorene skeleton may be any resin as long as the resin skeleton is composed of a fluorene compound (for example, a polyol component such as a diol component, a polyamine component such as a diamine component, a polyamine component such as diglycidyl ether). You may prepare by using the compound which has a fluorene skeleton corresponding to this polymerization component (or monomer component) as glycidyl ether etc.). For example, a resin (polyester resin, polyurethane resin, epoxy resin, vinyl ester resin, (poly) urethane (meth) acrylate, (poly) ester (meth) acrylate), which uses a polyol component (particularly a diol component) as a polymerization component, In the vinyl ether, etc., a fluorene compound having a hydroxyl group [the 9,9-bis (hydroxyphenyl) fluorene or its alkylene oxide adduct, etc.] may be used for a part or all of the polyol component. In a resin (polyamide resin, polyimide resin, aniline resin, etc.) using a component (particularly a diamine component) as a polymerization component, a fluorene compound having an amino group in part or all of the polyamine component [9, 9- Bis (aminophenyl) full In the case of a resin (vinyl ester resin, epoxy (meth) acrylate, etc.) using an epoxy resin as a polymerization component (constituent component), an epoxy group may be added to a part or all of the epoxy resin. The fluorene compound (such as glycidyl ether of 9,9-bis (hydroxyphenyl) fluorene) may be used.

  Among these resins, polyester resins, polyurethane resins (thermoplastic or thermosetting polyurethane resins), polycarbonate resins, acrylic resins [polyfunctional (meth) acrylates (the 9,9-bis (hydroxyphenyl)) A thermosetting or photocurable resin such as (meth) acrylate of fluorenes], a polyimide resin (thermoplastic or thermosetting polyimide resin) and the like are preferable.

  Hereinafter, a resin containing a compound having a fluorene skeleton as a monomer component (polymerization component, constituent component, copolymerization component) will be described in detail.

(1) Polyester resin A polyester resin containing a compound having a fluorene skeleton as a polymerization component (particularly a polyester resin obtained by polymerizing a compound having a fluorene skeleton as a monomer component of the resin) is a fluorene compound having at least a hydroxyl group. (Polyol components such as the 9,9-bis (hydroxyphenyl) fluorenes or alkylene oxide adducts thereof, particularly diol components such as 9,9-bis (monohydroxyphenyl) fluorenes or alkylene oxide adducts thereof) and The polyester resin includes a saturated or unsaturated polyester resin and a polyarylate resin using an aromatic dicarboxylic acid as a polymerization component in addition to a saturated or unsaturated polyester resin.

The polyol component (particularly the diol component) of the polyester resin may be configured by combining the fluorene compound having a hydroxyl group and another diol component. Examples of such diol components (or diols) include alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decane. Linear or branched C _2-12 alkylene glycols such as diols), (poly) oxyalkylene glycols (eg di to tetra C _2-4 alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.) Alicyclic diols (for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adducts 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane etc.)), aromatic diols (eg, biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, Examples thereof include bisphenol F and their alkylene oxide ( _C2-3 alkylene oxide) adducts (such as 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane) and xylylene glycol). These diols may be used alone or in combination of two or more.

Preferred diols are linear or branched C _2-10 alkylene glycols, particularly C _2-6 alkylene glycols (eg, linear or branched chain such as ethylene glycol, propylene glycol, 1,4-butanediol). C _2-4 alkylene glycol). As the diol, at least ethylene glycol is often used. When such diols (for example, ethylene glycol) are used, the polymerization reactivity can be enhanced and flexibility can be imparted to the resin.

  The ratio (molar ratio) between the fluorene compound having a hydroxyl group (particularly 9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct) and the diol is, for example, the former / the latter = 100 / 0 to 50/50, preferably 100/0 to 75/25 (for example, 100/0 to 70/30), more preferably about 100/0 to 90/10 (for example, 100/0 to 80/20). There may be.

  A polyol such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination with the diol component as necessary.

Examples of the dicarboxylic acid component constituting the polyester resin include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof [for example, acid anhydrides; acid halides (acid chlorides, etc.); Lower alkyl esters (such as C _1-2 alkyl esters)] and the like. These dicarboxylic acids can be used alone or in combination of two or more.

Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and other saturated C _3-20 aliphatic dicarboxylic acids. Acids (preferably saturated C _3-14 aliphatic dicarboxylic acids, etc.); unsaturated C _4-20 aliphatic dicarboxylic acids (preferably unsaturated C _4-14 aliphatics, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid) Dicarboxylic acid and the like); derivatives of these that can form esters. In the unsaturated polyester resin, the ratio of the aliphatic unsaturated dicarboxylic acid (maleic acid or its acid anhydride) is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, based on the entire dicarboxylic acid component. More preferably, it may be about 50 to 100 mol% (for example, 75 to 100 mol%).

Examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids (cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane dicarboxylic acid, etc. C _3-10 cycloalkane-dicarboxylic acid), unsaturated alicyclic dicarboxylic acid (C _3-10 cycloalkene-dicarboxylic acid such as 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid, etc.); Cyclic alkane dicarboxylic acids (di- or tricyclo C _7-10 alkane-dicarboxylic acids such as bornane dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid), polycyclic alkene dicarboxylic acids (bornene dicarboxylic acid, norbornene dicarboxylic acid, etc. di- or tricyclic C _7-10 A Ken - dicarboxylic acid), etc. These esters can form derivatives can be exemplified.

Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4'-diphenyldicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, 4 , 4′-diphenylmethane dicarboxylic acid, aromatic C _8-16 dicarboxylic acid such as 4,4′-diphenyl ketone dicarboxylic acid; and ester-forming derivatives thereof.

  The dicarboxylic acid may be used in combination with a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid, if necessary.

The dicarboxylic acid component is usually at least one selected from aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, in particular, aliphatic dicarboxylic acids (saturated aliphatic dicarboxylic acids or derivatives capable of forming esters thereof, particularly adipic acid, Saturated C _3-14 aliphatic dicarboxylic acids such as suberic acid and sebacic acid) and alicyclic dicarboxylic acids (C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid) are preferred.

  In the polyarylate-based resin, a dicarboxylic acid component containing at least an aromatic dicarboxylic acid is used, and the aromatic dicarboxylic acid may be used in combination with another dicarboxylic acid (aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid). Good. The ratio of the aromatic dicarboxylic acid to the other dicarboxylic acid is, for example, the former / the latter (molar ratio) = 100/0 to 10/90, preferably 100/0 to 30/70, more preferably 100/0 to 50. It may be about / 50.

  In the polyester resin, the ratio (molar ratio) between the dicarboxylic acid component and the polyol component (diol component, 9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct and diol) is usually the former. / The latter = 1.5 / 1 to 0.7 / 1, preferably 1.2 / 1 to 0.8 / 1 (particularly 1.1 / 1 to 0.9 / 1).

The weight average molecular weight Mw (polystyrene conversion) of the polyester resin is not particularly limited, and is, for example, 100 to 50 × 10 ⁴ , preferably 500 to 30 × 10 ⁴ (for example, 1000 to 20 × 10 ⁴ ), and more preferably 3000. About 30 × 10 ⁴ . In the case of an unsaturated polyester resin, the molecular weight per double bond may be 300 to 1000, preferably 350 to 800, and more preferably about 400 to 700. The terminal group of the polyester resin may be a hydroxyl group or a carboxyl group, and may be protected by a protecting group as necessary.

  The polyester resin is prepared by a conventional method, for example, a direct polymerization method (direct esterification method) or a transesterification method, and a polyol component (particularly a diol component) composed of a fluorene compound having a hydroxyl group and the dicarboxylic acid component. Can be produced by a condensation reaction.

(2) Polyurethane resin The polyol component (diol component) constituting the polyurethane resin containing a compound having a fluorene skeleton as a polymerization component (monomer component) is a fluorene compound having a hydroxyl group (9,9-bis ( Monohydroxyphenyl) fluorenes or alkylene oxide adducts thereof) may be used alone or together with the diols exemplified in the section of the polyester resin together with the hydroxyl group-containing fluorene compound. Furthermore, a diol component containing the fluorene compound having a hydroxyl group as a structural unit, for example, a polyester diol produced by a reaction between a diol component composed of 9,9-bis (monohydroxyphenyl) fluorenes and a dicarboxylic acid component, Polyether diols produced by the reaction of diol components composed of 9,9-bis (monohydroxyphenyl) fluorenes and alkylene oxides can also be used as the diol components of polyurethane resins. A diol component can also be used individually or in combination of 2 or more types. If necessary, the diol component may be used in combination with a polyol component such as triol.

  In the polyol component (diol component), the content of the hydroxyl group-containing fluorene compound (9,9-bis (monohydroxyphenyl) fluorene or its alkylene oxide adduct) is, for example, the entire polyol component (diol component). It may be 10 to 100 mol%, preferably 20 to 80 mol%, more preferably about 30 to 70 mol%.

Examples of the diisocyanate compound constituting the polyurethane resin include aromatic diisocyanates [paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis ( Isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane , Polymeric MDI, etc.], alicyclic diisocyanates [cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.], fat Diisocyanate diisocyanate compounds such as [hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.] and the like. These diisocyanate compounds can be used alone or in combination of two or more. If necessary, these diisocyanate compounds may be polyisocyanate compounds (for example, aliphatic triisocyanates such as 1,6,11-undecane triisocyanate methyloctane and 1,3,6-hexamethylene triisocyanate; bicycloheptane triisocyanate). Triisocyanate compounds such as alicyclic triisocyanates, etc.), monoisocyanate compounds (C _1-6 alkyl isocyanates such as methyl isocyanate; C _5-6 cycloalkyl isocyanates such as cycloalkyl isocyanate; C _6- such as phenyl isocyanate) ₁₀ aryl isocyanate and the like). The isocyanate compound includes derivatives such as multimers and modified products of the polyisocyanate compound.

  The polyurethane-based resin is used in a conventional manner, for example, 0.7 to 2.5 mol, preferably 0.8 to 2.2 mol, more preferably 0.9 to 2 mol per mol of the polyol component (diol component). It can be obtained by using it at a ratio of about 2 mol and urethanizing it. In addition, when a diisocyanate component of about 0.7 to 1.1 mol is used with respect to 1 mol of a diol component, a thermoplastic resin can be obtained, and an excess mol (for example, about 1.5 to 2.2 mol) is obtained. When a diisocyanate component is used, a thermosetting resin having a free isocyanate group at the terminal can be obtained.

(3) Polycarbonate-based resin As a polycarbonate-based resin containing a compound having a fluorene skeleton as a polymerization component, according to a conventional method, for example, a fluorene compound having at least the hydroxyl group (particularly 9,9-bis (monohydroxyphenyl)) Reaction of polyol component (particularly diol component) and phosgene (phosgene method) composed of fluorenes or alkylene oxide adducts thereof, or polyol component (diol component) composed of fluorene compound having hydroxyl group And a polycarbonate resin obtained by a reaction (transesterification method) of the ester with carbonate.

  The polyol component (diol component) may be composed of a fluorene compound having a hydroxyl group alone. The fluorene compound having a hydroxyl group and other diols (the diols exemplified in the above-mentioned polyester-based resin, particularly aromatic diols) Or an alicyclic diol). Other diols can be used alone or in combination of two or more. Among other diols, aromatic diols such as bisphenols such as bisphenol A, AD, and F are particularly preferable. The ratio between the fluorene compound having a hydroxyl group and the diol can be selected from the same range as in the case of the polyester resin.

The molecular weight of the polycarbonate resin is not particularly limited. For example, the weight average molecular weight is 1 × 10 ^{3 to} 100 × 10 ⁴ (for example, 1 × 10 ^{4 to} 100 × 10 ⁴ ), preferably 5 × 10 ³ to 50 × 10 ^4. (For example, 1 × 10 ⁴ to 50 × 10 ⁴ ), more preferably about 1 × 10 ^{4 to} 25 × 10 ⁴ (for example, 1 × 10 ⁴ to 10 × 10 ⁴ ).

(4) Acrylic resin A monomer of acrylic resin (a (meth) acrylic monomer having a fluorene skeleton) is obtained by a reaction between the hydroxyl group-containing fluorene compound and a carboxyl group-containing polymerizable monomer. May be obtained. As the polymerizable monomer having a carboxyl group, an unsaturated monocarboxylic acid, particularly (meth) acrylic acid, can be used, and cinnamic acid, crotonic acid, sorbic acid, maleic acid monoalkyl esters (monomethyl malate, etc.) Etc. may be used. Further, reactive derivatives such as acid chloride and C _1-2 alkyl ester may be used in place of the unsaturated carboxylic acid. These monomers may be used alone or in combination of two or more.

The acrylic resin is a homopolymer or copolymer of the (meth) acrylic monomer having the fluorene skeleton, and a copolymer of the (meth) acrylic monomer having the fluorene skeleton and another copolymerizable monomer. It may be a polymer. Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (meth) acrylic acid esters [(meth) such as methyl (meth) acrylate Acrylic acid C _1-6 alkyl ester, etc.]; vinyl cyanides such as (meth) acrylonitrile; aromatic vinyl monomers such as styrene; vinyl carboxylic acid esters such as vinyl acetate; α-olefins such as ethylene and propylene Examples can be given. These copolymerizable monomers can be used alone or in combination of two or more.

  In addition, a monomer having a plurality of (meth) acryloyl groups [for example, (meth) acrylates of the 9,9-bis (hydroxyphenyl) fluorenes exemplified above (di (meth) acrylate, tetra (meth) acrylate, etc.)] Etc.] itself may be used as an acrylic resin (that is, thermosetting acrylic resin, oligomer (resin precursor)).

(5) Polyimide resin (thermoplastic or thermosetting polyimide resin)
The polyamine component (diamine component) constituting the polyimide resin is a fluorene compound having an amino group [9,9-bis (aminophenyl) fluorenes such as 9,9-bis (monoaminophenyl) fluorenes in particular]. May be used alone or in combination with a diamine component (diamine). Examples of diamines include chain C _2-14 aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and dodecanediamine; Cyclic C _6-14 amines such as isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, etc. C _6-20 aromatic diamine; C _{7 - 14} aromatic aliphatic diamines such as m- xylylenediamine, diamino phenyl ether, 2,2-bis (3,4-di Minofeniru) bis (di-aminophenyl) alkanes such as propane can be exemplified. Diamines can be used alone or in combination of two or more.

  The ratio between the fluorene compound having an amino group and the diamine is the former / the latter (molar ratio) = 100/0 to 5/95, preferably 90/10 to 10/90, more preferably 80/20 to 20/80. Degree.

  Examples of the raw material polycarboxylic acids include tetracarboxylic acids or derivatives thereof, such as pyromellitic acid or anhydrides thereof, biphenyltetracarboxylic acid or anhydrides thereof, benzophenone tetracarboxylic acid or anhydrides thereof, and 2,2-bis (3 , 4-Dicarboxyphenyl) propane and other bis (dicarboxyphenyl) alkanes or anhydrides thereof, bis (carboxyphenyl) fluoroalkanes such as 2,2-bis (3,4-carboxyphenyl) hexafluoropropane, bismaleimide Etc. can be exemplified. These polycarboxylic acids can be used alone or in combination of two or more.

[Other compatibilizers]
The compatibilizing agent of the present invention may further contain another compatibilizing agent in addition to the compound having a fluorene skeleton depending on the type of resin to be mixed. Other compatibilizers include (A) ionomer compounds, (B) compounds containing reactive groups or functional groups, and (C) elastomer compounds. These other compatibilizers can be used alone or in combination of two or more. When combined with these other compatibilizing agents, depending on the type of resin, the compatibilizing property and the physical properties of the resulting plastic material are improved.

(A) Ionomer compounds As the ionomer compounds (A), various types are included. For example, (a) a type in which side chain ionic groups partially exist in the main chain of the host polymer (side chain type), (b) a host polymer or oligomer having carboxylic acid groups at both ends, a metal There are types that are polymerized by neutralization of ions (telechelic type), (c) types that have a cation in the main chain, and an anion bound to the cation (ionene).

Examples of counter ions with respect to the ionic group of the host polymer include alkali metal ions such as Li ⁺ and Na ⁺ , alkaline earth metal ions such as Mg ²⁺ and Ca ²⁺ , Zn ²⁺ , Cu ²⁺ and Mn ^2+. These transition metal ions are used. For the cation host polymer, anions such as Cl ⁻ and Br ⁻ are used.

Examples of the ionomer resin include C _2-4 olefin- (meth) acrylic acid copolymer ionomers such as ethylene- (meth) acrylic acid copolymer ionomers, ethylene-vinylsulfonic acid copolymer ionomers, and styrene-methacrylic acid. Copolymer ionomer, sulfonated polystyrene ionomer, fluorinated ionomer, telechelic polybutadiene acrylate ionomer, sulfonated ethylene-propylene-diene copolymer ionomer, (hydrogenated) polypentamer ionomer, poly (vinylpyridium salt) ionomer , Poly (vinyltrimethylammonium salt) ionomer, poly (vinylbenzylphosphonium salt) ionomer, styrene-butadiene acrylic acid copolymer ionomer, polyurethane ionomer, sulfur Examples include fluorinated styrene-2-acrylamido-2-methylpropane sulfate ionomer, acid-amine ionomer, aliphatic or aromatic ionene. These ionomer resins can be used alone or in combination of two or more.

  Of these ionomer resins, ethylene- (meth) acrylic acid copolymer ionomers are preferred. These ionomers are particularly effective for improving the compatibility between the aliphatic polymer and the aromatic polymer and the compatibility between the polar polymer and the nonpolar polymer. As the ethylene-methacrylic acid copolymer ionomer, for example, it can be obtained as a high-milan series manufactured by Mitsui DuPont Polychemical Co., Ltd.

(B) Compound containing reactive group or functional group Compound (B) containing reactive group or functional group includes double bond, carboxyl group, epoxy group, oxazoline group, alkoxy group, amino group, mercapto group And a compound or polymer having a reactive group or functional group such as a vinyl group, an acetal group, a maleic acid group, or a carboxyl group. These compounds or polymers can be used alone or in combination of two or more.

  Examples of such a compound include a polymer having a reactive group or a functional group such as a double bond, a carboxyl group, and an epoxy group, and one or both of the polymers to be compatibilized in a molding process. Compatibilizer (B1), oxazoline-based compatibilizer (B2) having a surfactant function based on a graft or block structure by reaction, alkoxy group, amino group, mercapto group, vinyl group, epoxy group, acetal group Examples thereof include a low-viscosity copolymer-based compatibilizer (B3) containing a functional group such as a maleic acid group and a carboxyl group and having a melt flow rate of 1 or more.

  Examples of the compatibilizing agent (B1) include compatibilizing agents described in “Basic and Application of“ Polymer Alloy ”(Edited by Polymer Society, 1993)”, for example, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl. Ethylene-glycidyl (meth) acrylate copolymers such as methacrylate-vinyl alcohol copolymer, ethylene-glycidyl methacrylate-methacrylate copolymer (bond first series manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nippon Polyolefin Co., Ltd.) Such as Lexpearl series), ethylene-maleic anhydride-ethyl acrylate copolymer (bondin made by Sumitomo Chemical Co., Ltd.), ethylene glycidyl methacrylate-acrylonitrile styrene, ethylene glycidyl methacrylate-polystyrene, ethylene glycidyl methacrylate Copolymers of ethylene glycidyl (meth) acrylate such as rate-polymethylmethacrylate and other polymers (Modiper manufactured by NOF Corporation), acid-modified polyethylene wax (high wax manufactured by Mitsui Chemicals, Inc.) , Carboxyl group-containing polyethylene graft polymer, carboxyl group-containing polypropylene graft polymer, and the like. Of these, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-vinyl alcohol copolymers, ethylene-glycidyl (meth) acrylate copolymers such as ethylene-glycidyl methacrylate-methacrylate copolymers are preferred.

  The oxazoline-based compatibilizer (B2) is not particularly limited as long as it is a compound or polymer having an oxazoline group. For example, a bisoxazoline-based compound (for example, a bisoxazoline-styrene-maleic anhydride copolymer), A blend of this bisoxazoline compound and polyolefin (polyethylene, polypropylene, etc.) can be preferably used. These oxazoline compounds can be used alone or in combination of two or more.

  The copolymer-based compatibilizer (B3) includes a functional group such as an alkoxy group, an amino group, a mercapto group, a vinyl group, an epoxy group, an acetal group, a maleic acid group, and a carboxyl group, and has a melt flow rate of 1 or more. Low viscosity copolymers, such as polyethylene-polyamide graft copolymers, polypropylene-polyamide graft copolymers, methyl methacrylate-butadiene-styrene resins, acrylonitrile-butadiene rubbers, ethylene-vinyl alcohol copolymers and polyvinyl chloride Of these, a graft copolymer, vinyl acetate-ethylene copolymer and the like can be preferably used.

(C) Elastomer-based compatibilizer Examples of the elastomer-based compatibilizer (C) include styrene-based elastomers (styrene-butadiene block copolymers, styrene-isoprene block copolymers, or hydrogenated products thereof). It can be preferably used. These elastomer-based compatibilizers (C) can be used alone or in combination of two or more. As the styrene elastomer, for example, Tuftec manufactured by Asahi Kasei Kogyo Co., Ltd. can be obtained.

  The ratio of the compound having a fluorene skeleton and the other compatibilizing agent can be appropriately selected according to the type of resin to be compatibilized. For example, the former / the latter (weight ratio) = 100/0 to 1/99, preferably Is about 99/1 to 10/90, more preferably about 95/5 to 20/80 (especially 90/10 to 30/70).

[Plastic materials]
The compatibilizing agent of the present invention may be applied to a plurality of types of polymers that are compatible with each other, but it is effective to use them to compatibilize a plurality of types of polymers that are incompatible with each other. The compatibilizing agent of the present invention is excellent in the compatibilizing action of the polymer, for example, even if a flame retardant or an inorganic filler is contained, the different polymers are compatibilized without deteriorating the physical properties of the plastic as a polymer alloy. can do. In particular, even if a plastic material is regenerated using a plurality of types of polymers including at least one type of used polymer, practical plastic properties can be secured.

  Examples of the polymer to which the compatibilizing agent of the present invention is applied include, for example, conventional thermoplastic resins, thermoplastic elastomers, rubbers, and thermosetting resins exemplified in the section of the resin having a fluorene skeleton. These resins may be biodegradable plastics such as aliphatic polyester resins, aliphatic polyamide resins, and cellulose derivatives. In addition, it is preferable to use a pulverized material for the thermosetting resin and the crosslinked resin such as crosslinked polyethylene and crosslinked polystyrene.

Further, these resins may be polymers recovered after use (used polymers), that is, polymers to be recycled (recycled), for example, recycled polyolefin resins (recycled C and the like such as recycled polyethylene and polypropylene). _2-4 polyolefin), recycled polystyrene resin (recycled polystyrene, recycled ABS resin, etc.), recycled polyester resin (recycled poly C _2-4 alkylene terephthalate resin such as recycled polyethylene terephthalate), recycled polyamide resin (recycled) Polyamide 6, Recycled polyamide 66, Recycled polyamide 46, Recycled polyamide 6T, Recycled polyamide MXD, etc.), Recycled polycarbonate resin (Recycled bisphenol A type polycarbonate, etc.) may be used. Conventionally, in recycled plastics, other types of incompatible polymers are mixed in waste plastics, and thus molded articles and materials from recycled plastics having practically sufficiently high physical properties have not been obtained. When the compatibilizing agent of the present invention is used, it is possible to achieve the compatibilization of the waste plastic containing a plurality of incompatible polymers, and a recycled plastic material can be obtained without causing deterioration of physical properties.

  Among these resins, combinations of incompatible polymers include, for example, a combination of an aliphatic polymer and an aromatic polymer, a combination of a polar polymer and a nonpolar polymer, a combination of a polyolefin resin and an engineering plastic, etc. Can be mentioned. These resins may be a combination of three or more polymers. Further, it may be a combination of an unused polymer (virgin polymer) and a recycled resin.

  Among these, it is practically effective particularly for a combination of polyolefin resin and engineering plastic. Polyolefin resins include polypropylene (PP), polyethylene (PE) (for example, very low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, etc.), polymethylpentene, amorphous Polyolefins and mixtures thereof are included.

  Engineering plastics include polyester resins (polyethylene terephthalate (PET), polybutylene terephthalate, polyarylate, liquid crystal polyester, etc.), styrene resins (acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), etc.) , Polyamide resins (polyamide 6T, polyamide MXD, etc.), polyimide resins (polyether imide, polyamide imide, polyamino bismaleimide, bismaleimide triazine resin, etc.), polycarbonate resins (bisphenol A type polycarbonate (PC), etc.), polyphenylene Ether resins (modified polyphenylene oxide, etc.), polysulfone resins (polysulfone, polyethersulfone, etc.), polyphenylene sulfi System resin (polyphenylene sulfide, etc.), polyacetal resin (polyacetal), polyether ketone-based resin (polyether ketone, polyether ether ketone, etc.), and mixtures thereof.

  More specifically, as a combination of polyolefin resin and engineering plastic, for example, PE and PET, PP and PET, PS and PE, PS and PP, PE and ABS resin, PP and ABS resin, PC and PE, PC And a combination of PP and the like. Examples of other combinations include PS and ABS resin, PC and ABS resin, PET and ABS resin, PS and PET, PC and PET, polyamide and PET, and the like.

  The ratio of the plurality of types of polymers may be selected according to the physical properties required for the obtained alloy plastic material, and is not particularly limited. For example, when two kinds of polymers are combined, the first polymer / second polymer = 99/1 to 1/99, preferably 95/5 to 5/95, more preferably about 90/10 to 10/90. is there.

  The ratio of the compatibilizer to the polymer to be compatibilized depends on the type of polymer and the type and amount of other components mixed in, and also considers the productivity and the quality and performance of the target product for each application. Can be selected as appropriate. In general, the proportion of the compatibilizing agent may be small if the plurality of types of polymers are the same type of polymer (that is, a relatively compatible polymer), and may be large if the polymers are incompatible. Become.

  The proportion of the compatibilizer is, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, more preferably 100 parts by weight with respect to the total of 100 parts by weight of the plural types of polymers to be compatibilized. It is about 0.5-30 weight part (especially 1-15 weight part). If the proportion of the compatibilizer is too small, it is difficult to obtain a compatibilizing effect. On the other hand, if the amount is too large, the compatibilizing effect is saturated, which is economically disadvantageous. In addition, the compatibilizing agent of this invention has the effect | action which improves a flame retardance and a mechanical characteristic, and if it exists in the said range, the said characteristic of a plastic material can be provided effectively.

  As described above, the plastic material of the present invention is a plastic material obtained by compatibilizing a plurality of types of polymers with the above-mentioned ratio of compatibilizing agent, and is composed of the compatibilizing agent and a plurality of types of the polymers. ing. The alloy structure of the plastic material of the present invention has various structures depending on the kind and ratio of the polymer to be mixed. Generally, when a highly compatible polymer is mixed, a homogeneous composition is easily obtained and the compatibility is low. When a polymer is mixed, it is likely to have a phase separation structure, for example, a sea-island structure composed of a matrix phase and a dispersed phase. Since the plastic material of the present invention often uses a plurality of incompatible polymers, it usually has a phase separation structure. In the case of a sea-island structure, the average diameter of the dispersed phase is, for example, about 0.01 to 100 μm, preferably 0.01 to 50 μm, and more preferably about 0.01 to 30 μm, from the viewpoint of the physical properties of the plastic material.

  The plastic material may contain a flame retardant and / or an inorganic filler. The compatibilizing agent of the present invention has a strong effect of compatibilizing a plurality of incompatible polymers, and even if it contains a flame retardant or an inorganic filler, the deterioration of plastic properties is suppressed.

Flame retardants include various types of flame retardants, such as inorganic flame retardants (boric acid flame retardants, phosphorus flame retardants, other inorganic flame retardants), organic flame retardants (nitrogen flame retardants, halogen-based flame retardants). And various flame retardants such as colloidal flame retardant materials (Sb ₂ O ₃ etc.). These flame retardants can be used alone or in combination of two or more.

  In the inorganic flame retardant, examples of the boric acid flame retardant include zinc borate and barium metaborate. Examples of phosphorus flame retardants include ammonium phosphate, melamine phosphate, red phosphorus, phosphate ester [tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate. 2,3-dibromopropyl-2,3-dichloropropyl phosphate and the like]. Examples of other inorganic flame retardants include inorganic substances such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, tin oxide hydrate, and borax. Examples thereof include metal hydrates, zinc carbonate, magnesium carbonate-calcium, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, and expanded graphite.

  In the organic flame retardant, examples of the nitrogen flame retardant include phosphonitrile, guanidine phosphate, guanidine sulfamate, guanyl urea phosphate, and guanidine carbonate. Examples of the halogen-based flame retardant include tetrabromobisphenol A derivative (TBA), tetrabromobisphenol S derivative, hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), butanetetrabromobutane (TBB), hexabromocyclo Brominated flame retardants such as decane (HBCD), and chlorinated flame retardants such as chlorinated paraffin, chlorinated polyphenyl, chlorinated diphenyl, perchloropentacyclodecane, and chlorinated naphthalene. These halogen flame retardants exhibit even higher flame retardancy when used in combination with antimony trioxide and the like.

  The proportion of the flame retardant can be appropriately selected according to the required flame retardant physical properties, but is, for example, 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, further based on 100 parts by weight of the polymer component. Preferably it is about 3-70 weight part (especially 5-50 weight part).

  The inorganic filler is not particularly limited, and a conventional inorganic filler can be used. For example, non-fibrous filler (mineral, oxide, hydroxide, carbonate, sulfate, silicate, nitride, carbons, Metal powder, ceramic powder, etc.), fibrous filler (glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, etc.).

  In the non-fibrous filler, examples of the mineral include zeolite, talc, kaolin, bentonite, and clay. Examples of the oxide include metal oxides such as alumina, silica, zinc oxide, titanium dioxide, iron oxide, magnesium oxide, and zirconium oxide. Examples of the hydroxide include metal hydroxides such as aluminum hydroxide, calcium hydroxide, and magnesium hydroxide. Examples of the carbonate include metal carbonates such as magnesium carbonate, heavy calcium carbonate, and light calcium carbonate. Examples of the sulfate include metal sulfates such as calcium sulfate and barium sulfate. Examples of the silicate include metal silicates such as calcium silicate, aluminum silicate, magnesium silicate, and magnesium aluminosilicate. Examples of the nitride include metal nitrides such as aluminum nitride, silicon nitride, and titanium nitride. Examples of carbons include carbon black.

  These inorganic fillers can be used alone or in combination of two or more. When an inorganic filler is contained in the plastic material, mechanical properties such as strength and various resistances (heat resistance, water resistance, warm water resistance, moisture resistance, etc.) can be improved.

  The proportion of the inorganic filler can also be appropriately selected according to the required flame retardant physical properties, but is, for example, 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the polymer component, Preferably it is about 3-70 weight part (especially 5-50 weight part).

  From the viewpoint of dispersibility in the plastic material, the total ratio of the flame retardant and the inorganic filler is preferably 200 parts by weight or less (0.1 to 200 parts by weight) with respect to 100 parts by weight of the total polymer component. The amount is preferably about 100 parts by weight or less (1 to 100 parts by weight).

  The plastic material of the present invention further includes other additives such as stabilizers (anti-aging agents, antioxidants, ozone degradation inhibitors, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), tackifiers, Plasticizers, softeners, lubricants, mold release agents, antistatic agents, modifiers, colorants, coupling agents, preservatives, antifungal agents and the like may be included as appropriate.

  The method for producing the plastic material is not particularly limited, and examples thereof include a usual melt kneading method. In the melt kneading, for example, a kneader such as a roll kneader, a Banbury mixer, an intermix, a single screw extruder, a twin screw extruder, or the like can be used. These kneaders may be used in combination of two or more. In addition, as a method of mixing a plurality of types of polymers, for example, a method of using a master chip mixed in advance as it is or diluted, or a method of mixing a plurality of types in an extruder or a molding machine for producing a target molded body. And a method in which a polymer and a compatibilizing agent are added and mixed.

  In order to sufficiently compatibilize a plurality of types of polymers, it is preferable to sufficiently mix them at a temperature equal to or higher than the melting point of the polymers to be mixed. Although mixing temperature can be suitably selected according to the kind of resin to be used, it is 180-450 degreeC, for example, Preferably it is 100-400 degreeC, More preferably, it is about 150-350 degreeC. Furthermore, when mixing with an extruder, the rotational speed of the screw is 10 rpm or more (for example, 10 to 1000 rpm), preferably 20 rpm or more (for example, 20 to 500 rpm), and more preferably about 30 to 300 rpm. Good.

[Molded body, coating agent, adhesive]
Such plastic materials can be used as various molded articles, coating or coating agents, adhesives, and the like. In addition, according to each application, it is necessary to appropriately select the type and amount of the compatibilizer depending on the type and amount of the polymer to be used, depending on the device characteristics, productivity, required quality, and physical properties. is there.

  The molded body of the present invention is obtained by using the plastic material and using a conventional method such as an extrusion molding method, an injection molding method, a thermoforming method (blow molding method, vacuum molding method, pressure forming method, vacuum / pressure forming method, press). For example, a molding method, a calendering method, a foam molding method, and a compression molding method. Of these molding methods, an extrusion molding method, a thermoforming method, an injection molding method, and the like are widely used.

  In the extrusion molding method, molded bodies having various shapes can be obtained. For example, hollow or solid molded bodies, sheets or film-shaped molded bodies, fibrous molded bodies having various cross-sectional shapes can be obtained. Examples of the shape of the hollow or solid molded body include a cylindrical shape and a rectangular shape. Moreover, a sheet | seat or a film-form molded object can be obtained by the method of extruding from a T die, and the method of extruding using inflation, for example. Furthermore, the fibrous shaped product can be obtained by an extruder melt spinning method. Examples of the fibrous molded body include multifilaments, monofilaments, flat yarns, staple fibers, and nonwoven fabrics (spunbond nonwoven fabrics, flash spun nonwoven fabrics, etc.).

  In addition, when obtaining a fibrous molded object by an extrusion method, a fibrous molded object is comprised with a very thin fiber, and the linear velocity in manufacture is very large. Therefore, a plastic material in which a plurality of types of polymers are mixed needs to have a small proportion of a minor component (or a dispersed phase) in the phase separation structure and high fluidity.

  Therefore, in the fibrous molded body, the melt flow rate (MFR) of the plastic material is usually 0.1 to 10 g / 10 min at the molding temperature in order to obtain high productivity and excellent quality and physical properties, preferably It is about 0.3 to 8 g / 10 minutes, more preferably about 0.5 to 7 g / 10 minutes. Further, when two types of polymers are used, for example, the melt flow rate (MFR1) of the minor component polymer is preferably larger than the melt flow rate (MFR2) of the major component polymer. For example, the ratio of MFR2 to MFR1 (MFR2 / MFR1) is usually 0.9 or less (for example, 0.1 to 0.9), preferably 0.8 or less (for example, 0.1 to 0.8). More preferably, it is about 0.7 or less (for example, 0.1 to 0.7). When MFR2 is larger than MFR1, the extruded form becomes non-uniform, and when it is subsequently stretched, the stretch becomes non-uniform and leads to a decrease in quality in node formation. It is necessary to select an optimum value for the MFR value according to the production method, production brand, and the like. The structure of the two-component polymer may be a sea-island structure, and usually a small amount of components forms the island component.

  In addition, the phase separation structure of the plastic material has a domain cross-sectional area (S1) composed of a small amount of components (for example, island components or dispersed layers) and a fiber cross-sectional area so as not to deteriorate productivity, quality, and physical properties. The ratio (S1 / S) to (S) is usually 0.3 or less (for example, 0.01 to 0.3), preferably 0.2 or less (for example, 0.01 to 0.2), Preferably it is about 0.15 or less (for example, 0.01 to 0.15). When this ratio is too large, the productivity is lowered due to yarn breakage, and the quality and physical properties are lowered due to yarn unevenness.

  In order to form such a phase-separated structure, for example, when two kinds of polymers are used, the ratio of the minor component is usually 30% by weight or less (based on the total amount of the polymer) ( For example, 0.1 to 30% by weight), preferably 20% by weight or less (for example, 0.1 to 20% by weight), more preferably about 15% by weight or less (for example, 0.1 to 15% by weight). . When there are too many small components, the fiber is likely to be cut or partially deformed, and the productivity, quality, and physical properties are lowered.

  Since the plastic material of the present invention combines a plurality of types of polymers, it is also possible to form a structure having hard fiber portions and flexible fiber portions in a streak shape, and the bending rigidity and knot strength of the fibers are increased. Therefore, the plastic material of the present invention is suitable for fibrous shaped bodies, particularly fibrous shaped bodies such as monofilaments and spunbond fibers.

  For other molded bodies, for example, in the case of a sheet or film-shaped molded body, the fluidity of the plastic material can be appropriately selected depending on the production method. For example, in the extrusion method using a T die, the fluidity of the polymer may be relatively low. For example, the MFR is usually 15 g / 10 min or less (for example, 1 to 15 g / 10 min), preferably 10 g / It is 10 minutes or less (for example, 1-10 g / 10min), More preferably, it is about 1-8 g / 10min. Further, in the extrusion molding method using inflation, the fluidity of the polymer may be relatively high, and the MFR is usually 30 g / 10 min or less (for example, 5 to 30 g / 10 min), preferably 25 g / 10 min. The following (for example, 5 to 25 g / 10 minutes), more preferably about 5 to 20 g / 10 minutes.

  In the case of using two types of polymers in the sheet or film-shaped molded body as well as the fibrous molded body, for example, the melt flow rate (MFR1) of the minor component polymer is the melt flow rate of the major component polymer. It is preferably larger than (MFR2), and the same applies to the ratio of MFR2 to MFR1.

  About the phase-separation structure in a sheet | seat or a film-like molded object, the magnitude | size (D1) of the domain comprised by the small amount component (for example, an island component or a dispersion layer) in a film, and the thickness (D) of a sheet | seat or a film The ratio (D1 / D) is usually 0.5 or less (for example, 0.01 to 0.5), preferably 0.3 or less (for example, 0.01 to 0.3), more preferably 0.2. It is about the following (for example, 0.01 to 0.2). When the size of the minor component in the sheet or film is too large, the physical properties are deteriorated, and when stretched, the sheet or film becomes non-uniform, resulting in tearing and uneven thickness.

  In the sheet or film-shaped molded body, in the phase separation structure, it is generally not necessary to reduce the ratio of a small amount of component unlike the fibrous molded body. The ratio of the minor component is usually 40% by weight or less (for example, 1 to 40% by weight), preferably 30% by weight or less (for example, 1 to 30% by weight), more preferably 20%, based on the total amount of the polymer. It is about wt% or less (for example, 1 to 20 wt%). When there are too many small components, tearing at the time of molding tends to occur, the productivity is lowered, and uneven thickness of the film or the like becomes remarkable.

  In the thermoforming method, for example, various containers (bottles), for example, beverage containers, food containers, chemicals, etc. are obtained by performing secondary processing using the film or sheet-like molded body obtained by the extrusion molding method. A container or the like may be manufactured.

  In thermoforming, it is necessary to adjust the fluidity of the plastic material (sheet or film-like molded product) to be low. For example, MFR is usually 10 g / 10 min or less (for example, 0.5 to 10 g / 10 min), Preferably it is 7 g / 10 minutes or less (for example, 0.5-7 g / 10 minutes), More preferably, it is about 0.5-5 g / 10 minutes.

  Also in the container, generally, in the phase-separated structure, it is not necessary to reduce the ratio of a small amount of components as in the fibrous molded body, and it is the same as the sheet-shaped or film-shaped molded body. If the proportion of the minor component is too large, tearing is likely to occur during molding, the productivity is lowered, and the thickness unevenness of the film or sheet and the compatibility non-uniformity become remarkable.

  In injection molding as well, various shapes of molded products, such as components and equipment that make up transportation vehicles such as automobiles, office automation (OA) equipment such as personal computers, displays, copiers, and printers, televisions, refrigerators, etc. Household appliances, building materials such as wall materials and floor materials, various appliances (housing, casing, parts, etc.), containers and the like can be obtained. In injection molding, relatively high fluidity is required. For example, MFR is usually 50 g / 10 min or less (for example, 0.1 to 50 g / 10 min), preferably 30 g / 10 min or less (for example, 1 ˜30 g / 10 min), more preferably 20 g / 10 min or less (for example, 5-20 g / 10 min).

  In injection molding, the phase separation structure is not particularly limited, but if the proportion of a small amount of components (for example, island components or dispersed layers) is too large, productivity, operability, quality, physical properties, and the like deteriorate. In the phase separation structure, the ratio of the minor component is usually 45% by weight or less (for example, 1 to 45% by weight), preferably from 45% by weight to the total amount of the polymer in terms of productivity, quality, physical properties, etc. It is about 40% by weight or less (for example, 1 to 40% by weight), more preferably about 30% by weight or less (for example, 1 to 30% by weight).

  For other molded products, the phase separation structure and the mixing ratio of the polymers are the same as those of the injection molding. In the molded article of the present invention, when fusion is required, a polymer having a low softening point as a large component (for example, polyethylene) is preferable, and when high flexibility, surface hardness and heat resistance are required, A polymer having a high softening point (for example, polyethylene terephthalate) is preferred as a large component.

  The coating or coating agent of the present invention may be used by mixing the plastic material with various solvents or additives. Such coatings or coating agents include, for example, coating agents for organic or inorganic linear materials, twisted string materials, etc., coating agents or laminating agents for metal plates, plastic films and sheets, fiber or pulp nonwoven fabrics, powders, etc. It can be used as a paint such as a body paint, a water dispersion paint or an organic paint.

  In addition to the plastic material, the adhesive of the present invention may contain various solvents and additives as necessary. As such an adhesive, for example, it can be used as an adhesive for adhering metals, ceramics, organic structures and the like.

  The compatibilizing agent of the present invention can ensure a practical plastic physical property even when a plastic material is regenerated using a plurality of types of polymers including at least one type of used polymer due to its excellent compatibilizing action. It can be effectively used as a compatibilizing agent for regenerating. Furthermore, since the plastic material containing the compatibilizing agent of the present invention can compatibilize a plurality of types of polymers without deteriorating the physical properties of the plastic even when a flame retardant or an inorganic filler is contained, it can be used in a wide range of fields and applications. It can be used, for example, for various molded products [containers (containers for beverages, food containers, chemical containers, etc.), various equipment, instruments (housing, casing, parts, etc.)], coating agents, adhesives, etc. Useful as a plastic material.

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

Example 1
Waste PET flakes (manufactured by Yono PET Bottle Co., Ltd.) 80 parts by weight, PE gas pipe waste material pellets (manufactured by Osaka Resin Kogyo Co., Ltd.) 20 parts by weight, and as a compatibilizer, fluorene polyester (OKP4, Osaka Gas) 2 parts by weight of Chemical Co., Ltd.) was melt kneaded under the following extrusion conditions using a twin screw extruder (BT-30-L, manufactured by Plastic Engineering Laboratory Co., Ltd., L / D ratio = 30). And extruded into strands to obtain chips.

<Extrusion conditions>
Temperature setting: Feed 260 ° C, Kneading part 300 ° C, Head 260 ° C
Rotation speed: 60rpm
The obtained chip was molded under the following molding conditions using an injection molding machine (N100BII, manufactured by Nippon Steel Works, Ltd., L / D ratio = 22), and a test piece (width) according to JIS K-6760 1/2 inch × length 8.5 inch × thickness 1/8 inch).

<Injection molding conditions>
Temperature setting: Feed 260 ° C, Nozzle 280 ° C, Mold 60 ° C
Injection pressure: 35-40 kg / cm ²
The test piece was subjected to a mechanical strength test in accordance with JIS K-6760. As a result, the tensile yield point strength was 32 MPa.

Example 2
Except for using 1 part by weight of fluorene-based polyester (OKP4, manufactured by Osaka Gas Chemical Co., Ltd.) and 1 part by weight of an ethylene-glycidyl methacrylate copolymer (Bond First E, manufactured by Sumitomo Chemical Co., Ltd.) as a compatibilizing agent. A test piece was prepared in the same manner as in Example 1. The tensile yield point strength was 36 MPa.

Example 3
Except for using 1 part by weight of fluorene-based polyester (OKP4, manufactured by Osaka Gas Chemical Co., Ltd.) and 1 part by weight of a bisoxazoline-styrene-maleic anhydride copolymer (manufactured by Mikuni Pharmaceutical Co., Ltd.) as a compatibilizer. A test piece was prepared in the same manner as in Example 1. The tensile yield point strength was 34 MPa.

Example 4
As compatibilizers, 1 part by weight of fluorene-based polyester (OKP4, manufactured by Osaka Gas Chemical Co., Ltd.) and ethylene- (meth) acrylic acid copolymer ionomer (Himiran 1707Na, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 1 weight A test piece was prepared in the same manner as in Example 1 except that the part was used. The tensile yield point strength was 34 MPa.

Comparative Example 1
A test piece was prepared in the same manner as in Example 1 except that no compatibilizer was used. The tensile yield point strength was 22 MPa.

  As is clear from the above results, the molded bodies obtained in Examples 1 to 4 have a higher tensile yield point strength than the molded body obtained in Comparative Example 1 in which no compatibilizer was used. It had sufficient strength for practical use.

Claims (6)

A compatibilizing agent composed of a polyester resin obtained by polymerizing a compound represented by the following formula (1) as a monomer component .

[Wherein R ^{1 to} R ⁴ are the same or different and represent a non-reactive group or a reactive group,
The non-reactive group is an alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, acyl group, alkoxycarbonyl group, N, N-disubstituted amino group, halogen atom, nitro group or cyano group. And
The reactive group is a hydroxyl group, a mercapto group, an amino group, an N-monosubstituted amino group, a carboxyl group or a group — [X— (R ⁵ O) _k —Y] (wherein R ⁵ is an alkylene group) The group X is an oxygen atom (ether group) or an imino group, the group Y is a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and k is 0 or an integer of 1 or more, provided that k is When 0, Y is not a hydrogen atom)
n1 and n2 are the same or different and represent an integer of 0 or 1 to 5, and m1 and m2 are the same or different and represent an integer of 0 or 1 to 4] In the formula (1), the non-reactive group is an alkyl group, an aryl group, or an aralkyl group, and the reactive group is a hydroxyl group, an amino group, or a group — [X— (R ⁵ O) _k —Y] ( In the formula, R ⁵ is an alkylene group, the group X is an oxygen atom (ether group) or an imino group, the group Y is a hydrogen atom, a glycidyl group or a (meth) acryloyl group, and k is 0 or 1 The compatibilizer according to claim 1, wherein the integer is represented by the above integer, provided that when k is 0, Y is not a hydrogen atom. The compatibilizer according to claim 1, further comprising at least one compatibilizer selected from the group consisting of an ionomer compound, an ethylene-glycidyl (meth) acrylate copolymer , and an oxazoline compatibilizer .   A recycled plastic material comprising a polyolefin-based resin, a polyester-based resin, and the compatibilizing agent according to claim 1.   The recycled plastic material according to claim 4, further comprising at least one selected from a flame retardant and an inorganic filler.   A molded body formed of the recycled plastic material according to claim 4.