JP2020200486A - Resin composition and composite resin composition including the same, method for producing the same and complex - Google Patents

Abstract

To provide a resin composition that has a cellulose nanofiber dispersed in a polyamide resin, and can give the resin excellent properties (for example, strength, toughness, rigidity, heat resistance or the like).SOLUTION: A composition containing an amide, a polyamide resin, and a solvent containing an amide is mixed. In that way, a resin composition is prepared in which cellulose is made finer (or nano-sized), and the finer cellulose nanofibers are dispersed in the polyamide resin. The resin composition is useful for master batch.SELECTED DRAWING: None

Description

The present invention relates to a resin composition in which cellulose nanofibers are dispersed in a polyamide resin, a composite resin composition and a composite, and a method for producing the same.

Cellulose, which is a plant-derived fiber, has a small environmental load and is a sustainable resource.
It has excellent properties such as high elastic modulus and strength, and low coefficient of linear expansion. In particular, finely divided cellulose nanofibers (cellulose nanofibers) are useful as reinforcing agents for resins, and resin compositions in which cellulose nanofibers are dispersed in a resin are known.

Japanese Unexamined Patent Publication No. 2005-42283 (Patent Document 1) describes a method for producing a composite material having high rigidity and strength by uniformly finely dispersing pulp and / or cellulosic fibers in an aliphatic polyester resin. Has been done. As a method for producing this composite material, pulp (pretreated pulp) in which the outer layers of the primary wall and the secondary wall are damaged and an aliphatic polyester are used as a cellulose amorphous region swelling agent (water, ethylene glycol, ethanol and other defibrating aids). ) Is melt-kneaded in the presence of) to separate the cellulose amorphous region swelling agent (defibration aid). Further, in the examples of this document, the aliphatic polyester is melted at 180 ° C., and the molten aliphatic polyester is kneaded with a mixed solution of pretreated pulp and water (cellulose amorphous region swelling agent).
Water is removed from this kneaded material to produce a composite material, and the aliphatic polyester 1
The ratio of pretreated pulp and water used to 00 parts by weight is 20 to 30 parts by weight and 80 by weight, respectively.
It is stated that it is ~ 100 parts by weight.

However, this method requires a treatment step of damaging the primary wall and the outer layer of the secondary wall of the pulp, and the production efficiency is not sufficient. In addition, when water or alcohols are used as the cellulose amorphous region swelling agent (defibration aid), the aliphatic polyester is hydrolyzed in the kneading process and the molecular weight tends to decrease, so that the mechanical properties (for example, strength) Cannot be improved sufficiently.

Japanese Unexamined Patent Publication No. 2014-227369 (Patent Document 2) describes that fine cellulose fibers having a predetermined fiber width and, if necessary, a resin (first resin) are basic such as amide, urea and derivatives thereof. A fine cellulose fiber-containing material obtained by immersing it in an aqueous solution containing a nitrogen-containing compound (defibration aid), pulling it out of the aqueous solution, and then drying it, and the fine cellulose fiber-containing material and resin (second resin). The composite material obtained by kneading and is described. According to this document, when fine cellulose fibers are treated with a basic nitrogen-containing compound (defibration aid), the binding force between the fine cellulose fibers is weakened, and the treated fine cellulose fibers (fine cellulose-containing material) are described. When the resin (second resin) is kneaded, the resin (second resin) easily enters between the fine cellulose fibers, so that the dispersibility of the fine cellulose with respect to the resin (second resin) can be improved and the machine can be used. It is described that the physical properties can be improved. Further, in the examples of this document, a fine cellulose fiber and a polyethylene emulsion are mixed and extracted as the fine cellulose fiber and the first resin to prepare a fine cellulose composite sheet (sheet), and this sheet is placed in a 50% urea aqueous solution. A cellulose fiber-containing sheet containing 10 parts by weight of urea was produced with respect to 100 parts by weight of the total amount of the sheet, and the fine cellulose fiber-containing sheet and a linear resin as a second resin were produced. It is described that a composite material is produced by melt-kneading low-density polyethylene at 100 to 140 ° C., and that when the appearance of the composite material is observed, yellow to brown coloring is observed. ..

However, this method requires not only the use of fine cellulose fibers that have been finely divided in advance, but also the step of mixing the fine cellulose fibers and the polyethylene emulsion, and the production efficiency is not sufficient. Further, in this method, since the composite material is formed by using the cellulose fiber-containing sheet in which highly hygroscopic urea remains, the molded body of this composite material changes its mechanical properties due to water absorption (for example, decrease in strength, (Rigidity reduction, etc.) is likely to occur, and since a polyethylene-based resin having low compatibility with urea is used as the second resin, there is a possibility that mechanical properties may be lowered due to residual urea. Further, even with this method, it cannot be said that the coloring (yellowing) is sufficiently improved, and further improvement is required.

Japanese Unexamined Patent Publication No. 2013-1805068 (Patent Document 3) describes a resin composition containing modified cellulose nanofibers obtained by cation-modifying cellulose nanofibers and a thermoplastic resin. According to this document, it is possible to suppress the aggregation of cellulose nanofibers due to hydrogen bonds by cation modification, and further, when the modified cellulose nanofibers and the resin are mixed, the modified cellulose nanofibers become uniform in the resin. It is described that it is excellent in mechanical properties, heat resistance, surface smoothness, appearance, etc. because it is dispersed. Further, it is described in this document that it is preferable to use a polyamide resin as the resin because it has a high affinity with a cellulosic material. In the examples of this document, modified cellulose nanofibers and polyamide are used. A resin composition (composite material) is produced by mixing 11 powders to form a slurry, drying and pulverizing the composite powder, and melt-kneading the polyamide 11 pellets at 170 ° C. or higher. Is described.

However, in this document, cellulose (raw cellulose) is finely divided in advance, cellulose nanofibers are cationically modified, a slurry liquid is prepared, dried and pulverized to form a composite powder, and the like. It requires many steps other than kneading, is complicated, and the production efficiency is not sufficient. Further, in this method, since the hydroxyl group on the surface of the cellulose nanofiber is modified, the hydrogen bond point between the hydroxyl group on the surface of the polyamide and the cellulose nanofiber is reduced, and the interfacial strength between the polyamide and the cellulose nanofiber is lowered. There is a risk.

In the comparative example of this document, a resin composition prepared by combining uncationized cellulose nanofibers and polyamide 11 is described, but in this resin composition, untreated cellulose nanofibers are used. Therefore, the dispersibility of the cellulose nanofibers is not sufficient.

JP-A-2005-42283 (Claims, [0012], [0054], Examples) JP-A-2014-227369 (Claims, [0021], [0025], Examples) Japanese Unexamined Patent Publication No. 2013-1805068 (Claims, [0020], Examples)

Therefore, it is an object of the present invention that the cellulose nanofibers are uniformly dispersed in the polyamide resin.
To provide a resin composition, a composite resin composition, a composite, and a method for producing these, which can impart excellent properties (for example, strength, toughness, rigidity, heat resistance, etc.) to a resin (for example, a polyamide resin). It is in.

Another object of the present invention is a resin composition in which cellulose nanofibers are dispersed in a polyamide resin, a composite resin composition, and a composite without subjecting cellulose (raw material cellulose) to a special treatment (pretreatment) in advance. The purpose is to provide the body and methods for producing these.

Still another object of the present invention is to provide a resin composition, a composite resin composition, a composite, and a method for producing the same, in which the physical properties of the resin do not deteriorate due to hydrolysis or the like.

Another object of the present invention is to provide a resin composition, a composite resin composition, and a composite capable of suppressing coloration, and a method for producing these.

As a result of diligent studies to achieve the above problems, the present inventors have made amides (amide-based solvents).
When a composition containing a solvent containing, a polyamide resin, and cellulose (raw material cellulose or cellulose fiber) is kneaded, amides (amide-based solvent) act as a defibrating agent for cellulose, so that cellulose is microfibrillated. The cellulose nanofibers can be used to form a resin composition in which the cellulose nanofibers are uniformly dispersed in a polyamide resin, and the characteristics of a composite resin composition and a composite using this resin composition (for example, strength, rigidity, heat resistance). Since the amides (amide-based solvent) also act as a plasticizer for the polyamide resin, the preparation temperature (or kneading temperature) of the composite resin composition can be lowered, which accompanies the thermal history. The present invention has been completed by finding that coloring can be suppressed.

That is, the resin composition of the present invention contains a polyamide resin, cellulose nanofibers, and a solvent, and the solvent contains amides (amide-based solvent). The ratio of amides may be 30 to 350 parts by weight with respect to 100 parts by weight of the total amount of the polyamide resin and the cellulose nanofibers. The ratio of polyamide resin to cellulose nanofibers is the former / latter (weight ratio) = 10 /
It may be 90 to 90/10.

The cellulose nanofibers may be unmodified cellulose nanofibers. The resin composition of the present invention may further contain a compound having a 9,9-bis (aryl) fluorene skeleton.
The compound having a 9,9-bis (aryl) fluorene skeleton may be a compound represented by the following formula (1).

(In the formula, ring Z is an arene ring, X is a group represented by the following formula (2-1), (2-2), or (2-3) (for example, (2-2)), and n Indicates an integer of 1 to 3, R ³ and R ⁴ indicate a substituent, p indicates an integer of 0 or 1 or more, and k indicates an integer of 0 to 4.)

(In the formula, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkylene group, and m1 and m2 are integers of 0 or 1 or more, respectively).

The proportion of the compound having a 9,9-bis (aryl) fluorene skeleton is the polyamide resin 1
It may be 0.1 to 30 parts by weight with respect to 00 parts by weight, or 0.1 to 50 parts by weight with respect to 100 parts by weight of cellulose nanofibers.

The present invention includes a method for producing a resin composition by kneading a composition containing a solvent containing amides (amide-based solvent), a polyamide resin, and cellulose. The production method of the present invention is described in 9 above.
, The composition may be kneaded in the presence of a compound having a 9-bis (aryl) fluorene skeleton.

The present invention includes a composite resin composition containing a polyamide resin and unmodified cellulose nanofibers dispersed in the polyamide resin. The average fiber diameter of the unmodified cellulose nanofibers may be 1 to 750 nm, and the maximum fiber diameter may be 2000 nm or less. The composite resin composition of the present invention may further contain a compound having a 9,9-bis (aryl) fluorene skeleton.

The average fiber diameter of the unmodified cellulose nanofibers may be 1 to 750 nm, and the maximum fiber diameter may be 2000 nm or less. The composite resin composition of the present invention may further contain a compound having a 9,9-bis (aryl) fluorene skeleton.

The present invention includes a method for producing a composite resin composition by removing a solvent containing amides from the resin composition.

The present invention includes a composite containing the composite resin composition and a resin.

In addition, in this specification, a resin composition containing a solvent is simply referred to as a "resin composition", and the resin composition in which a solvent is removed from the resin composition is referred to as a "composite resin composition".

In the resin composition of the present invention, since amides act as a defibrating agent for cellulose, cellulose (raw cellulose) can be easily microfibrillated without special treatment (pretreatment) on cellulose (raw cellulose). It is converted into cellulose nanofibers, and these cellulose nanofibers can be uniformly dispersed in a polyamide resin. Further, when this resin composition is used, the mechanical properties (for example, strength, toughness, rigidity, etc.) and heat resistance of the composite resin composition and the composite can be greatly improved. In addition, since amides are used as defibration aids, they may be hydrolyzed.
The physical properties of the polyamide resin are not impaired. Further, since the amides also act as a plasticizer for the polyamide resin, it is not necessary to excessively raise the preparation temperature (kneading temperature) for forming the composite resin composition, and the coloring due to the heat history can be suppressed.

FIG. 1 is a scanning electron micrograph of cellulose nanofibers in the resin composition obtained in Example 1. FIG. 2 is a scanning electron micrograph of cellulose nanofibers in the resin composition obtained in Example 2. FIG. 3 is a scanning electron micrograph of cellulose nanofibers in the resin composition obtained in Example 3. FIG. 4 is a photograph showing the appearance of injection-molded articles of the composites (pellets) of Examples 2 to 3 and Comparative Example 1.

The resin composition (masterbatch or resin reinforcing agent) of the present invention is a composition containing a polyamide resin, cellulose nanofibers, and a solvent containing amides, in which the cellulose nanofibers are dispersed in the polyamide resin.

[Polyamide resin]
Polyamide resins are advantageous from the viewpoint of having excellent mechanical properties (for example, tensile strength (strength) and impact strength (rigidity)) and having high affinity with cellulose nanofibers.

Examples of the polyamide resin (PA) include homopolyamide and copolyamide in which a homopolyamide component is copolymerized. Examples of the homopolyamide include an aliphatic polyamide resin (for example, polyamide 46, polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 612, etc.) and an alicyclic polyamide resin (for example, diaminomethylcyclohexane and adipine). Semi-aromatic polyamide resin or aromatic polyamide resin (eg, polymer of trimethylhexamethylenediamine and terephthalic acid, polyamide MXD (eg, polymer of xylylene diamine and adipic acid)) Examples of the copolyamide include aliphatic polyamide resins such as copolyamide 6/66, copolyamide 6/11, copolyamide 6/12, and copolyamide 66/12. These polyamide resins can be exemplified. , Can be used alone or in combination of two or more.

Among these polyamide resins, aliphatic polyamide resins (homopolyamide, copolyamide) are usually used. Among these aliphatic polyamide resins, an aliphatic polyamide resin having a C _6-16 alkylene group in the main chain of the polymer (particularly, a polyamide resin having a C _10-14 alkylene group in the main chain (for example) from the viewpoint of low melting point. Polyamide 11,
Polyamide 12, polyamide 6/11, polyamide 66/12, etc.)) are preferable.

The polyamide resin may be crystalline or amorphous, or may be a transparent polyamide resin (amorphous transparent polyamide resin). As the polyamide resin, a crystalline resin is usually used from the viewpoint of the mechanical properties of the composite (composite material or compound) and its molded product.

The weight average molecular weight of the polyamide resin is determined by gel permeation chromatography (GP).
In C), it can be selected from the range of 5000 to 1,000,000 in terms of polystyrene, for example, 1000 to 800000 (for example, 1500 to 10000), preferably 20.
000 to 600,000 (eg, 23,000 to 70000), more preferably 2500
It may be about 0 to 500,000 (for example, 30,000 to 50,000).

The melting point of the polyamide resin is, for example, 250 ° C. or lower (for example, 100 to 250 ° C.), preferably 220 ° C. or lower (for example, 120 to 220 ° C.), and more preferably 200 ° C. or lower (for example, about 150 to 190 ° C.). There may be.

[Cellulose nanofibers]
Cellulose nanofibers (or cellulose nanofibers) are cellulose fibers in which the average fiber diameter of cellulose (raw cellulose or cellulose fibers having a fiber diameter of micrometer size or more, for example, pulp) is miniaturized (or microfibrillated) to the nano order. is there. The cellulose nanofibers referred to here may be unmodified cellulose nanofibers or modified cellulose nanofibers. In the case of modified cellulose, it is preferable that the modified amount is low from the viewpoint of not impairing the hydrogen bonding property with the polyamide.

As the cellulose, pulp having a low content of non-cellulose components such as lignin and hemicellulose, for example, plant-derived raw material cellulose {for example, wood [for example, coniferous tree (for example, coniferous tree)
Pine, fir, touhi, tsuga, sugi, etc.), broadleaf trees (beech, hippo, poplar, maple, etc.)], herbaceous plants [hemp (hemp, flax, Manila hemp, ramie, etc.), straw, bagasse, honey, etc.], Manufactured from seed hair fiber (cotton linter, Bombax cotton, kapok, etc.), bamboo, sugar cane, etc.}, animal-derived cellulose raw material (shoe cellulose, etc.), bacterial-derived cellulose raw material (cellulose contained in Natade Coco, etc.) Pulp and the like can be exemplified. These celluloses can be used alone or in combination of two or more. Among these celluloses, a plant-derived cellulose raw material is preferable, and wood pulp (for example, coniferous tree pulp, hardwood pulp, etc.), seed hair fiber-derived pulp (for example, cotton linter pulp) -derived cellulose, and the like. Is even more preferable. The pulp may be mechanical pulp obtained by mechanically treating the pulp material, but chemical pulp obtained by chemically treating the pulp material is preferable because the content of the non-cellulose component is small.

The cellulose (raw material cellulose) preferably has high crystallinity, and the crystallinity of the cellulose nanofibers is, for example, 40 to 100% (for example, 50 to 100%), preferably 6.
It may be about 0 to 95%, more preferably 70 to 90% (particularly 75 to 90%).
Usually, the crystallinity may be 60% or more. Further, as the crystal structure of cellulose, for example, type I, type II, type III, type IV and the like can be exemplified, and a type I crystal structure having an excellent elastic modulus and the like is preferable.

The cellulose nanofibers are preferably microfibrillated, and the Canadian freedom value (Canadian standard drainage degree) of the cellulose nanofibers is 0 to 200 ml when measured using a slurry liquid having a concentration of 0.1% by mass. It may be preferably 0 to 100 ml, more preferably about 0 to 50 ml. The smaller the Canadian freeness value, the greater the degree of fibrillation. That is, the Canadian freeness value is also an index of filtration performance in relation to the entanglement of fibers due to fiber branching. The Canadian freedom value is a value measured in accordance with JIS P8121 "Pulp drainage test method; Canadian standard type".

The average fiber diameter of cellulose nanofibers (for example, unmodified cellulose nanofibers) is 1 to 10.
It can be selected from a wide range of 00 nm, for example, 1 to 750 nm (for example, 2 to 750 nm).
, Preferably 5 to 500 nm, more preferably 10 to 300 nm (eg, 15 to 25).
It may be about 0 nm), particularly about 50 to 200 nm (for example, 55 to 150 nm), for example, 200 to 900 nm, preferably 300 to 800 nm, and more preferably about 350 to 700 nm. Good. If the average fiber diameter is too large, properties such as strength of the resin composition may deteriorate. The maximum fiber diameter of cellulose nanofibers is
For example, 2000 nm or less (for example, the minimum fiber diameter is 10 nm and the maximum fiber diameter is 200.
0 nm), preferably 1500 nm or less (minimum fiber diameter is 15 nm, maximum fiber diameter is 1)
500 nm), more preferably 1000 nm or less (eg, minimum fiber diameter is 20 nm, maximum fiber diameter is 1000 nm), especially 750 nm or less (eg, minimum fiber diameter is 25 nm).
The maximum fiber diameter is 750 nm), usually 500 nm or less (for example, the minimum fiber diameter is 50).
It may be nm and the maximum fiber diameter may be 500 nm). In addition, cellulose nanofibers
In many cases, the fiber diameter does not substantially contain micrometer-sized cellulose fibers.

Further, in the present invention, cellulose (raw cellulose or cellulose fiber) is kneaded in a state of being impregnated or impregnated with a resin solution containing amides, and a shearing force acts directly on cellulose (raw cellulose or cellulose fiber). It is possible to suppress the cutting of cellulose (raw material cellulose or cellulose fiber) in the longitudinal direction, and it is possible to obtain a fiber having a relatively long fiber length. That is, the average fiber length of the cellulose nanofibers can be selected from the range of about 0.01 to 500 μm, and is, for example, 1 μm or more (for example, 5 to 300 μm), preferably 1.
0 μm or more (for example, 20 to 200 μm), more preferably 30 μm or more (particularly 50 to 50 to 200 μm)
It may be 150 μm).

The ratio (aspect ratio) of the average fiber length to the average fiber diameter of the cellulose nanofibers is, for example, 5 or more (for example, about 5 to 10000), preferably 10 or more (for example, 10 to 500).
It may be about 0), more preferably 100 or more (for example, about 100 to 1000). If the aspect ratio is too small, the reinforcing property of the resin may decrease.

The ratio of cellulose nanofibers to polyamide resin is the former / latter (weight ratio) = 1/99 ~
You can choose from a wide range of 99/1 (eg 5/95 to 90/10), eg 10/9
0 to 90/10 (eg, 15/85 to 80/20), preferably 20/80 to 80/2
It may be 0 (for example, 25/75 to 75/25), more preferably 30/70 to 70/30 (for example, 40/60 to 60/40), and particularly about 30/70 to 50/50. For example, it may be about 10/90 to 80/20, preferably 20/80 to 70/30, and more preferably about 25/75 to 60/40. The proportion (content) of the cellulose nanofibers can be selected from a wide range of 5 to 1000 parts by weight (for example, 50 to 1000 parts by weight) with respect to 100 parts by weight of the polyamide resin, for example, 10 to 900 parts by weight (for example). 20 to 800 parts by weight), preferably 30 to 700 parts by weight (for example, 50 to 600 parts by weight), more preferably 60 to 500 parts by weight (for example, 65 to 400 parts by weight), particularly 70 to 350 parts by weight (for example, 70 to 350 parts by weight). For example, it may be about 80 to 300 parts by weight, usually about 90 to 250 parts by weight, and may be, for example, about 50 to 200 parts by weight, preferably about 75 to 125 parts by weight.

If the proportion (content) of the cellulose nanofibers is too small, the nanonization of the cellulose fibers in the kneading process may not proceed sufficiently and the average fiber diameter may increase. On the contrary, if it is too large, the solvent is removed. Cellulose nanofibers are likely to strongly agglomerate through hydrogen bonds, and when they are subjected to kneading again, the agglomerates are less likely to loosen, and dispersibility is reduced.

(Modified cellulose nanofibers or modified cellulose nanofibers)
Cellulose nanofibers are at least some functional or reactive groups (eg, hydroxyl groups).
May be modified cellulose nanofibers (or modified cellulose nanofibers) that have been modified (for example, cationized treatment, anionized treatment, etc.), but even without these modification treatments, cellulose nanofibers may be added to the polyamide resin. Since the fibers can be uniformly dispersed, the cellulose nanofibers are preferably unmodified cellulose nanofibers that have not been subjected to these modification treatments.

As the cationizing agent (or anionizing agent) for cationizing or anionizing treatment, for example, a cationic polymer having a functional group (for example, an epoxy group) capable of binding (reacting) with a hydroxyl group of cellulose nanofibers (for example, an epoxy group). Alternatively, it may be an anionic polymer). The proportion of cationic polymer (or anionic polymer) is, for example, cellulose nanofibers 10.
It may be 1 part by weight or less (for example, 0.9 parts by weight or less), preferably 0.5 parts by weight or less, and more preferably 0.1 part by weight or less with respect to 0 parts by weight.

(Modifier or additive)
The present invention may further include a modifier. Examples of the modifier include a fluorene compound (a compound having a 9,9-bis (aryl) fluorene skeleton) and the like.

Such a fluorene compound (a compound having a 9,9-bis (aryl) fluorene skeleton) has a 9,9-bisarylfluorene skeleton and is selected from a carboxyl group or a reactive derivative thereof, an epoxy group and a hydroxyl group. It also has at least one reactive group. Examples of the reactive derivative of the carboxyl group include an alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group and ethoxycarbonyl group).
Examples thereof include acid halide groups (haloformyl groups such as acid chloride groups and acid bromide groups). The epoxy group may be a glycidyl group as long as it contains an oxylan ring.

A typical fluorene compound is represented by the following formula (1).

[In the formula, ring Z represents an arene ring, X represents a group represented by the following formulas (2-1), (2-2), or (2-3), n is an integer of 1-3, R ³ And R ⁴ indicate a substituent, p indicates an integer of 0 or 1 or more, and k indicates an integer of 0 to 4].

(In the formula, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkylene group, and m1 and m2 are integers of 0 or 1 or more, respectively).

In the above formula (1), examples of the arene ring represented by the ring Z include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like, and the polycyclic arene ring is a fused polycyclic arene. A ring (condensed polycyclic hydrocarbon ring), a ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring), and the like are included.

Examples of the fused polycyclic arene ring include a condensed bicyclic arene (for example, a fused bicyclic C _10-16 arene such as naphthalene) ring and a condensed tricyclic arene (for example, anthracene, phenanthrene, etc.) ring. Examples thereof include fused bicyclic and tetracyclic arene rings. Examples of preferable fused polycyclic arene rings include naphthalene rings and anthracene rings, and naphthalene rings are particularly preferable. The two rings Z may be the same or different rings.

The ring-assembled arene ring includes a bi-C _6-12 arene ring such as a beerene ring, for example, a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.), a tellarene ring, for example. Tel C ₆ such as terphenylene ring
_{A -12} arene ring can be exemplified. A preferred ring of sets arene ring is B C _6-10.
Examples include an arene ring, particularly a biphenyl ring.

In the above formula (1), the alkyl group represented by R ¹ is a linear or branched C _1-6 such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group.
Alkyl groups can be exemplified. Preferred alkyl groups are C _1-4 alkyl groups, especially C _1-2 alkyl groups. m1 may be an integer of 0 or 1 or more (for example, 1 to 6, preferably 1 to 4, more preferably about 1 to 2). m1 may usually be 0 or 1-2.

The alkylene group R ² includes a linear or branched alkylene group, and the linear alkylene group includes, for example, a C _2-6 alkylene group such as an ethylene group, a trimethylene group, or a tetramethylene group (preferably). Linear C _2-4 alkylene group, more preferably linear C _2-3
An alkylene group (particularly an ethylene group) can be exemplified, and examples of the branched chain alkylene group include, for example.
Branched chain C _3- such as propylene group, 1,2-butanjiyl group, 1,3-butanjiyl group
Examples thereof include a _6- alkylene group (preferably a branched chain C _3-4 alkylene group, particularly a propylene group).

The number m2 of the oxyalkylene group (OR ² ) can be selected from the range of 0 or an integer of 1 or more (for example, 0 to 15, preferably 0 to 10), and is, for example, 0 to 8 (for example, 1 to 8), preferably 0 to 8. It may be 0 to 5 (for example, 1 to 5), more preferably 0 to 4 (for example, 1 to 4), particularly 0 to 3 (for example, 1 to 3), and usually 0 to 2 (for example, 0 or 1). It may be. In the case m2 is 2 or more, kinds of the alkylene group R ² may be the same or different.
The type of the substituents R ^2, in the same or different ring Z, may be the same or different.

In the above formula (1), the number of substitutions n of the group X is the same or different depending on the type of ring Z.
Any of the above integers may be used, for example, 1 to 4, preferably 1 to 3, and more preferably 1 or 2.
In particular, it may be 1. The number of substitutions n may be the same or different in each ring Z.

The group X can be substituted at an appropriate position of the ring Z. For example, when the ring Z is a benzene ring, the 2-, 3-, 4-position (particularly, 3-position and / or) of the phenyl group can be substituted. In many cases, it is substituted at the 4-position), and when the ring Z is a naphthalene ring, it is often at the 5-8-position of the naphthyl group. For example, the naphthalene ring is relative to the 9-position of fluorene. 1-position or 2-position is replaced (
(Replaced in relation to 1-naphthyl or 2-naphthyl), with respect to this substitution position, at the 1,5-position,
In many cases, the group X is replaced by a relationship such as the 2,6-position (especially when n is 1, the relationship between the 2,6-position). When n is 2 or more, the replacement position is not particularly limited. Further, in the ring-aggregated arene ring Z, the substitution position of the group X is not particularly limited, and for example, even if it is substituted with an arene ring bonded to the 9-position of fluorene and / or an arene ring adjacent to this arene ring. Good. For example, the 3- or 4-position of the biphenyl ring Z may be bonded to the 9-position of fluorene, and when the 4-position of the biphenyl ring Z is bonded to the 9-position of fluorene, the group X
The substitution position of may be any of 2-, 3-, 2'-, 3'-, and 4'-positions, and usually,
It may be replaced with the 2-, 3'-, 4'-position, preferably the 2-, 4'-position (particularly the 2-position).

In the formula (1), examples of the substituent R ^3, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Linear or branched C _1-1 such as s-butyl group and t-butyl group
₀ Alkyl groups, preferably linear or branched C _1-6 alkyl groups, more preferably linear or branched C _1-4 alkyl groups, cycloalkyl groups (cyclopentyl groups, cyclohexyl groups, etc.) C _5-10 cycloalkyl group such as), aryl group [phenyl group, alkylphenyl group (methylphenyl (trill) group, dimethylphenyl (xysilyl) group, etc.), biphenyl group, naphthyl group, etc. C _6-12 aryl Groups], aralkyl groups (C _6-10 aryl-C _1-4 alkyl groups such as benzyl group and phenethyl group), alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, etc.
Linear or branched C _1-10 alkoxy groups such as t-butoxy groups), cycloalkoxy groups (eg C _5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups (eg) , C _6-10 aryloxy groups such as phenoxy groups)
, C _6-10 aryl-C _1-4 such as aralkyloxy group (eg, benzyloxy group)
Alkyloxy group, etc.), alkylthio group (eg, C _1-10 alkylthio group such as methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc.), cycloalkylthio group (eg, cyclohexylthio group) C _5-10 cycloalkylthio groups such as C _5-10 cycloalkylthio groups, arylthio groups (eg C _6-10 arylthio groups such as thiophenoxy groups), aralkylthio groups (eg C _6-10 aryl-C _1- such as benzylthio groups) ₄ Alkylthio groups, etc.), acyl groups (eg, C _1-6 acyl groups such as acetyl groups), nitro groups, cyano groups, dialkylamino groups (eg, diC _1-4 alkylamino groups such as dimethylamino groups, etc.) ), Dialkylcarbonylamino group (for example, diC _1-4 alkyl-carbonylamino group such as diacetylamino group) and the like can be exemplified.

Among these substituents R ^3, typically, a halogen atom, a hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group), an alkoxy group, an acyl group, a nitro group, a cyano group, a substituted amino group Etc. can be exemplified. Preferred examples of the substituent R ^3, an alkyl group (methyl group, e.g., a straight chain or branched chain C _1-4 alkyl group such as ethyl group), an alkoxy group (
Linear or branched C _1-4 alkoxy groups such as methoxy groups), especially alkyl groups (
In particular, a linear or branched C _1-3 alkyl group such as a methyl group) is preferable. When the substituent R ³ is an aryl group, the substituent R ³ may form the ring-aggregated arene ring together with the ring Z. Type of the substituent R ³ is the same or different ring Z, it may be the same or different.

The coefficient p of the substituent R ³ can be appropriately selected depending on the type of ring Z and the like. For example, it may be an integer of about 0 to 8, an integer of 0 to 4, preferably 0 to 3 (for example, 0). It may be an integer of ~ 2), especially 0 or 1. In particular, when p is 1, ring Z is a benzene ring, a naphthalene ring or a biphenyl ring, the substituent R ³ may be a methyl group.

As a substituent R ^4, a cyano group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom)
, Carboxyl group, alkoxycarbonyl group (eg C ₁ such as methoxycarbonyl group)
_-4 Alkoxy-carbonyl group, etc.), alkyl group (methyl group, ethyl group, propyl group, etc.)
Examples thereof include C _1-6 alkyl groups such as isopropyl group, butyl group and t-butyl group) and aryl groups (C _6-10 aryl groups such as phenyl group).

Among these substituents ^{R 4,} linear or branched _{C 1-4} alkyl group (particularly, _{C 1-3} alkyl group such as methyl group), a carboxyl group or a _{C 1-2} alkoxy - carbonyl group,
A cyano group and a halogen atom are preferable. The substitution number k is an integer of 0 to 4 (for example, 0 to 3), preferably an integer of 0 to 2 (for example, 0 or 1), particularly 0. Incidentally, the substitution number k may be the same or different from each other, when k is 2 or more, the type of the substituent R ⁴ may be the same or different from each other, be replaced with two benzene rings of the fluorene ring the kind of the substituent R ⁴ may be the same or different. The substitution position of the substituent R ⁴ is not particularly limited, for example,
It may be in the 2-position to the 7-position (2-position, 3-position and / or 7-position, etc.) of the fluorene ring.

Specific fluorene compounds having a group X represented by the formula (2-1) include n = 1, p.
9,9-bis (carboxyaryl) fluorene with = k = 0, m1 = 0, eg 9
, 9-bis (3-carboxyphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (5-carboxy-1-naphthyl) fluorene, 9,9
-Bis (6-carboxy-2-naphthyl) Fluorene and other 9,9-bis (carboxy C)
_6-10 aryl) fluorene; 9,9-bis (carboxyalkyl-aryl) fluorene compounds having n = 1, p = k = 0, m1 = 1-3, such as 9,9-bis (4- (carboxy) Methyl) phenyl) fluorene, 9,9-bis (4- (2-carboxyethyl)
Phenyl) fluorene, 9,9-bis (3- (carboxymethyl) phenyl) fluorene, 9,9-bis (5- (carboxymethyl) -1-naphthyl) fluorene, 9,9-bis (6- (carboxymethyl) ) 9,9-Bis (carboxy C _1-6 alkyl C _6-10 aryl) fluorene such as -1-naphthyl) fluorene can be exemplified. These fluorene compounds can be used alone or in combination of two or more.

Specific fluorene compounds having an epoxy group-containing group X represented by the formula (2-2) include 9,9-bis (glycidyloxyaryl) having n = 1, p = k = 0, and m2 = 0. Fluorene, eg, 9,9-bis (3-glycidyloxyphenyl) fluorene, 9,9
9,9-Bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, etc. Bis (glycidyloxy C _6-10 aryl) fluorene;
9,9-bis (glycidyloxy (poly) alkoxyaryl) fluorene with n = 1, p = k = 0, m2 = 1-5, for example 9,9-bis (4- (2-glycidyloxyethoxy)). Phenyl) fluorene, 9,9-bis (4- (2-glycidyloxypropoxy)
9 such as phenyl) fluorene, 9,9-bis (5- (2-glycidyloxyethoxy) -1-naphthyl) fluorene, 9,9-bis (6- (2-glycidyloxyethoxy) -2-naphthyl) fluorene, etc. , 9-Bis (Glysidyloxy (Poly) C _2-4 Alkoxy C
_6-10 aryl) Fluorene; 9,9-bis (alkyl-glycidyloxyaryl) fluorene with n = 1, p = 1, k = 0, m2 = 0, eg, 9,9-bis (3-methyl-) 9,9-bis (C _1-4 alkyl-glycidyloxy C _6-10 aryl) fluorene such as 4-glycidyloxyphenyl) fluorene; n = 1, p = 1, k = 0, m2 =
1,9-bis (alkyl-glycidyloxy (poly) alkoxyaryl) 1 to 5
Fluorene, for example 9,9-bis (C _1-4 alkyl-glycidylxi (poly) C _2-4 alkoxy, such as 9,9-bis (3-methyl-4- (2-glycidyloxyethoxy) phenyl) fluorene. C _6-10 aryl) fluorene; n = 1, p = 1, k = 0, m2
9,9-bis (aryl-glycidyloxyaryl) fluorene with = 0, eg
9,9-Bis (3-phenyl-4-glycidyloxyphenyl) fluorene, etc. 9,9
-Bis (C _6-10 aryl-glycidyloxy C _6-10 aryl) fluorene; n =
9,9-bis (aryl-glycidyloxy (aryl-glycidyloxy), 1, p = 1, k = 0, m2 = 1-5
Poly) Alkoxyaryl) Fluorene, eg, 9,9-bis (3-phenyl-4- (3-phenyl-4-)
2,9-bis (C _6-10 ) such as 2-glycidyloxyethoxy) phenyl) fluorene
Aryl-glycidyloxy (poly) C _2-4 alkoxy C _6-10 aryl) Fluorene; 9,9-bis (di (glycidyloxy) aryl) with n = 2, p = 0, k = 0, m2 = 0 Fluorene, for example 9,9-bis (di (glycidyloxy) C _6-10 aryl) fluorene such as 9,9-bis (3,4-di (glycidyloxy) phenyl) fluorene; n = 2, p = 0 , K = 0, m2 = 1-5, 9,9-bis (di (glycidyloxy (poly) alkoxy) aryl) fluorene, eg, 9,9-bis (3,4-di (2)
Examples thereof include 9,9-bis (di (glycidyloxy (poly) C _2-4 alkoxy) C _6-10 aryl) fluorene such as _{−glycidyloxyethoxy} ) phenyl) fluorene. These fluorene compounds can be used alone or in combination of two or more.

The fluorene compound having an epoxy-containing group X represented by the above formula (2-2) may be a monomer or a multimer (for example, a dimer, a trimer, etc.). Good, but yellowing (
It is preferable not to contain a multimer from the viewpoint of sufficiently suppressing (coloring). The fluorene compound having a glycidyl group usually contains at least a monomer, and may be, for example, a mixture of a monomer, a dimer and a trimer.

Further, as a specific fluorene compound having a hydroxyl-containing group X represented by the formula (2-3), a compound (glycidyloxy) corresponding to the fluorene compound having a group X represented by the formula (2-3). A compound in which a group is replaced with a hydroxyl group) can be exemplified.

Among these fluorene compounds, preferred fluorene compounds include, for example, 9,
9-bis (glycidyloxy C _6-10 aryl) fluorene, 9,9-bis (glycidyloxy (poly) C _2-4 alkoxy C _6-10 aryl) fluorene, 9,9-bis (
C _1-4 alkyl-glycidyloxy C _6-10 aryl) fluorene, 9,9-bis (
C _1-4 alkyl-glycidyloxy (poly) C _2-4 alkoxy C _6-10 aryl)
Fluorene, 9,9-bis (C _6-10 aryl-glycidyloxy C _6-10 aryl) Fluorene, 9,9-bis (C _6-10 aryl-glycidyloxy (poly) C _2-4 )
Alkoxy C _6-10 aryl) fluorene, 9,9-bis (di (glycidyloxy) C
_6-10 aryl) fluorene, 9,9-bis (di (glycidyloxy (poly) C _2-4 )
Monomers of fluorene compounds having a group X represented by the above formula (2-2) such as alkoxy) C _6-10 aryl) fluorene, and multimers (dimers, trimers, etc.); 9,9 -Bis (
Hydroxy C _6-10 aryl) Fluorene, 9,9-bis (Hydroxy (poly) C _2-
4 Alkoxy C _6-10 aryl) Fluorene, 9,9-bis (C _1-4 alkyl-hydroxy C _6-10 aryl) fluorene, 9,9-bis (C _1-4 alkyl-hydroxy (poly) C _{2- 4-} alkoxy C _6-10 aryl) fluorene, 9,9-bis (C _6-1)
0 Aryl-Hydroxy C _6-10 Aryl) Fluorene, 9,9-Bis (C _6-10 Aryl-Hydroxy (Poly) C _2-4 Alkoxy C _6-10 Aryl) Fluorene, 9,
The above formula (2-3) such as 9-bis (dihydroxy C _6-10 aryl) fluorene and 9,9-bis (dihydroxy (poly) C _2-4 alkoxy) C _6-10 aryl) fluorene.
Examples thereof include a fluorene compound having a group X represented by. In addition, "(poly) C _2-4
"Alkoxy" means that the number of repetitions m2 of the C _2-4 alkoxy group is an integer of 1 or more.

In the present invention, by including the fluorene compound as a modifier or an additive in the resin composition, more excellent dispersibility (or affinity) can be exhibited, and properties such as mechanical strength can be improved. In particular, a fluorene compound having an epoxy-containing group X represented by the formula (2-2) is advantageous because its toughness can be sufficiently improved. On the other hand, a fluorene compound having a group X represented by the formula (2-1) or (2-3) can improve the characteristics of mechanical strength, and even if these compounds are added, the viscosity increases. Since it can be suppressed, it is advantageous because coloring can be suppressed to the same extent as that of cellulose nanofibers.

In order to enhance the dispersibility, the fluorene compound may be contained, and the cellulose nanofibers are not necessarily in the form of modifying the fluorene compound, but may be in the form of being modified or bound with the fluorene compound. ..

Furthermore, the average fiber diameter of the cellulose nanofibers can be reduced, probably because the hydrogen bonds acting between the fibers can be relaxed in the process of microfibrillation of cellulose. Further, the cellulose nanofibers can effectively exhibit the dispersibility (or affinity) improving effect and the fiber diameter reducing effect even if the binding ratio of the fluorene compound is small.

The proportion of the compound having a 9,9-bis (aryl) fluorene skeleton is the polyamide resin 1
For example, 0.1 to 30 parts by weight (for example, 0.5 to 25 parts by weight), preferably 1 to 25 parts by weight, and more preferably 5 to 20 parts by weight (for example, 10 to 20 parts by weight) with respect to 00 parts by weight. It may be about 0.1 to 50 parts by weight with respect to 100 parts by weight of the cellulose nanofibers.
It may be preferably about 1 to 40 parts by weight (for example, 3 to 30 parts by weight), more preferably about 5 to 25 parts by weight (for example, 10 to 20 parts by weight). If the proportion of the fluorene compound is too large, the mechanical properties of the composite resin composition and the composite may be deteriorated, and if it is too small, the effect of the fluorene compound on improving the dispersibility of the cellulose nanofibers may be reduced. There is.

[solvent]
The resin composition of the present invention contains amides (amide-based solvent) as a solvent capable of swelling the amorphous region (amorphous portion) of cellulose. What is a solvent that can swell the amorphous region (amorphous part) of cellulose?
It is a low molecular weight compound capable of hydrogen bonding with a hydroxyl group on the surface of cellulose (or cellulose fiber). Usually, when forming (preparing) a composite (composite material or compound) of cellulose nanofibers and a resin, water and alcohols (particularly water) are often used as the low molecular weight compound. However, when these low molecular weight compounds (water, alcohols) are used to form (prepare) a composite (composite material or compound) of cellulose nanofibers and polyamide resin, the polyamide resin is hydrolyzed (alcolysis) during the kneading process. ) Decomposition and a decrease in molecular weight may result in a decrease in mechanical properties. On the other hand, in the present invention, the amorphous region of cellulose (
Since the amides (amide-based solvent) are contained as a solvent capable of swelling the amorphous portion) and the decomposition reaction of the polyamide resin does not occur, the physical properties of the polyamide resin can be maintained. Further, since amides (amide-based solvent) act as a defibrating agent for cellulose, cellulose nanofibers can be uniformly dispersed in a polyamide resin even if a cellulose raw material having a large fiber diameter such as pulp is used, and the polyamide resin. Since it also acts as a plasticizer, the composite resin composition (master batch or resin reinforcing agent) formed (prepared) of the resin composition, the composite of this resin composition, or the coloring (yellowing) of the molded product thereof. It also has the advantage of being able to be suppressed.

Amides include, for example, aliphatic amides, aromatic or heterocyclic amides (eg 2-
Examples thereof include pyrrolidones such as pyrrolidone and N-methyl-2-pyrrolidone, and caprolactams such as N-methylcaprolactam). These amides can be used alone or in combination of two or more. Among these amides, aliphatic amides are usually used.

Examples of aliphatic amides include N-mono or di-substituted monoacylamines (eg, N-mono or di-substituted C _1-8 acylamines (eg, formamides (eg, formamide)). , N-mono or diC _1-4 alkylformamides (eg, N-methylformamide, N, N-dimethylformamide, etc.), acetamides (eg, N-methylacetamide, N, N-dimethylacetamide, etc.) Or the C
N-mono such as _1-4 acetamide) or C _1-4 acylamines which may be di-substituted) and the like can be exemplified. These aliphatic amides can be used alone or in combination of two or more.

Among these aliphatic amides, C _1-4 which may be preferably N-mono or di-substituted from the viewpoint of excellent solubility of the polyamide resin and efficient action as a defibration aid and a plasticizer.
Acylamines, more preferably N-mono or di-substituted formamides or acetamides, especially N, N-diC _1-4 alkyl C _1-3 acylamines (eg, N, N-dimethylformamide or N, N-dimethyl). It may be (acetamide, etc.).

The solvent may be an amide alone or a combination of the amide and another solvent (solvent excluding the amide). Examples of other solvents include sulfoxides (for example, dimethyl sulfoxide), which are solvents capable of swelling an amorphous region (amorphous portion) of cellulose and dissolving a polyamide resin. These solvents can be used alone or in combination of two or more.

The ratio of the amides to the other solvent can be selected from a wide range of the former / latter (weight ratio) = 100/0 to 50/50, for example, 100/0 to 70/30, preferably 100/0 to 90. /
10 (eg 99.9 / 0.1-90 / 10), more preferably 100 / 0-95 /
It may be about 5 (for example, 99/1 to 95/5).

The ratio of the solvent (particularly the amides alone) can be selected from a wide range of 1 to 800 parts by weight (for example, 10 to 750 parts by weight) with respect to 100 parts by weight of each component of the polyamide resin and the cellulose nanofibers. It may be about 50 to 700 parts by weight, preferably 100 to 600 parts by weight, and more preferably about 150 to 500 parts by weight (for example, 200 to 400 parts by weight).
The ratio of the solvent (particularly amides alone) can be selected from a wide range of 1 to 400 parts by weight (for example, 10 to 380 parts by weight) with respect to 100 parts by weight of the total amount of the polyamide resin and the cellulose nanofibers. For example, it may be about 30 to 350 parts by weight, preferably 50 to 300 parts by weight, more preferably 70 to 250 parts by weight (for example, 150 to 200 parts by weight), and for example, 80 to 250 parts by weight, preferably 80 to 250 parts by weight. It may be about 100 to 200 parts by weight.

If the proportion of the solvent (particularly amides alone) is too high, the viscosity of the system will increase as the nano-ization of the cellulose raw material progresses, so that the resulting cellulose nanofibers will become fragmented.
In addition to the aspect ratio becoming smaller, there are some captives who do not have sufficient defibration (or nano-ization) of cellulose. Also, if the proportion of solvent (especially amides alone) is too low, cellulose defibration (especially amides alone)
Or nano) may not be sufficient.

[Method for producing resin composition (or kneading composition)]
The resin composition of the present invention includes a solvent containing amides, a polyamide resin, and cellulose (raw cellulose or cellulose fibers having a fiber diameter of micrometer size or more, for example, pulp).
It can be produced by kneading a composition containing and. In this method, since amides act as a cellulose defibrating agent, large shearing acts with kneading, and while efficiently defibrating cellulose fibers, microfibrillation can be performed to the nano-order level, and cellulose nanofibers can be produced. Can be uniformly dispersed in resin. Therefore, the cellulose nanofibers can be dispersed in the polyamide resin without subjecting the cellulose to a refinement treatment or the hydroxyl group on the surface of the cellulose to be modified in advance. Further, there is no need to prepare a dispersion liquid (slurry liquid) of cellulose nanofibers, preparation of an emulsion of cellulose nanofibers and a resin, and the like, and the resin composition can be prepared by a one-step operation of kneading.

As the cellulose, the cellulose (raw material cellulose or cellulose fiber) exemplified in the section of cellulose nanofibers can be used. The average fiber diameter of this cellulose (raw material cellulose) can be selected according to the type, for example, 1 μm to 1 mm, preferably 5 to 500 μm (for example, 10 to 10).
It may be about 300 μm), more preferably about 20 to 100 μm (particularly, 30 to 50 μm). The average fiber length of cellulose is, for example, 0.1 to 100 mm, preferably 0.5 to 50 mm (for example, 0.5 to 30 mm), and more preferably 1 to 10 mm (particularly, 1 to 5 mm). You may.

The ratio of the polyamide resin to the solvent (particularly amides alone) may be any of the ratios exemplified in the section of the resin composition, and the ratio of cellulose (raw cellulose or cellulose fiber) to the solvent (particularly amides alone) is also , The proportion of cellulose nanofibers exemplified in the section of resin composition may be used.

The kneading is not particularly limited as long as a solvent containing a polyamide resin and amides and cellulose (raw material cellulose or cellulose fiber) can be kneaded, but usually, a resin solution of a polyamide resin and a solvent containing amides and cellulose are mixed. Often kneaded. Kneading can be performed by a conventional method, for example, a mixing roller, a kneader, a Banbury mixer, an extruder (such as a single-screw or twin-screw extruder), and a kneader or a twin-screw extruder that can act on a high shearing force. It may be preferably used.

The kneading step may be performed in an open system in the air or in an atmosphere of an inert gas (such as a rare gas such as nitrogen or argon), and is usually performed in a closed kneading system.

In a preferred embodiment, under heating, for example, in order to suppress vaporization (or evaporation) of the amides, a temperature lower than the boiling point of the amides (for example, 40 to 150 ° C., preferably 60 to 130).
A method of kneading at ° C., more preferably about 70 to 120 ° C.) for a certain period of time can be mentioned.
In this method, cellulose nanofibers having a small fiber diameter can be uniformly dispersed in the resin in a short time. The kneading time is not particularly limited, but in the method of the present invention, the resin composition is often obtained in a short time, so that the kneading time is, for example, 1 minute to 5 hours, preferably 3 minutes to 3 hours, more preferably. May be about 5 minutes to 1 hour (particularly 8 to 30 minutes).

In the resin composition of the present invention, since the amides act as a plasticizer, it is not necessary to raise the preparation temperature (kneading temperature) for preparing the composite resin composition, and coloring due to heat history can be suppressed.

In the kneading step, each component may be added to the kneading system in a plurality of times. For example, a composition containing at least a resin solution and a cellulose raw material may be kneaded, and a polyamide resin and / or a modifier may be added.

After kneading, the resin composition may be obtained by a conventional drying method (for example, hot air drying, vacuum drying, etc.).

[Composite resin composition and method for producing the same]
The composite resin composition of the present invention contains a polyamide resin and cellulose nanofibers. The composite resin composition of the present invention is obtained by removing a solvent having amides from the resin composition (solvent removing step), and maintains the morphology of the cellulose nanofibers (for example, dimensional size, fibril structure, etc.). You may. In the present invention, the composite resin composition may also be a masterbatch or a resin reinforcing agent. The solvent containing amides can be removed, for example, by venting under reduced pressure from the vent portion during the kneading process.

Further, in order to prepare a composite resin composition containing cellulose nanofibers having a predetermined concentration, the resin composition may be diluted with a polyamide resin to adjust the concentration before and after the solvent removal step. For example
If the solvent is removed from the resin composition, kneading may not be possible. In such a case, a polyamide resin may be added to adjust the concentration of the cellulose nanofibers so that kneading is possible. Also,
The solvent may be removed while kneading by adding a polyamide resin. On the other hand, when kneading is possible even if the solvent is removed from the resin composition, the solvent may be removed by reducing the pressure in the kneading process of the resin composition, and if necessary, a polyamide resin is added and kneaded while the solvent is kneaded. May be removed by reducing the pressure. As described above, the composite resin composition of the present invention may usually be kneaded in a system from which the solvent has been removed. The kneading may be the method exemplified in the kneading step in the method for producing the precursor composition, and the kneading apparatus, kneading temperature, kneading time and the like are also the kneading temperature exemplified in the kneading step in the method for producing the precursor composition. , May be kneading time.

The proportion (content) of the cellulose nanofibers in the composite resin composition diluted with the polyamide resin and adjusted in concentration is, for example, 1 to 9 with respect to the total amount of the polyamide resin and the cellulose nanofibers.
It may be 0% by weight, preferably 5 to 70% by weight, more preferably about 10 to 50% by weight, for example, 25 to 70% by weight (for example, 25 to 65% by weight), preferably 30 to 6% by weight.
It may be 0% by weight (for example, 30 to 55% by weight), more preferably about 40 to 50% by weight.

[Composite and its manufacturing method]
The composite (composite material) of the present invention comprises the composite resin composition (masterbatch) and a resin (second).
(Resin) and can be obtained by kneading (or mixing). The composite may be prepared, for example, by kneading (or mixing) the composite resin composition and the second resin. Also,
In the composite, the resin composition and the second resin may be kneaded (or mixed) to remove the solvent.

The resin (second resin) is preferably a polyamide resin from the viewpoint of affinity. This polyamide resin may be a polyamide resin different from the polyamide resin constituting the resin composition, but the same polyamide resin is preferable from the viewpoint of affinity.

In the composite, the proportion (content) of the cellulose nanofibers is, for example, 1 to 30% by weight with respect to the total amount of the polyamide resin constituting the resin reinforcing agent (master batch), the second resin, and the cellulose nanofibers. It may be preferably about 2 to 25% by weight, more preferably about 5 to 20% by weight.

The kneading temperature may be, for example, a temperature equal to or higher than the melting point (or softening point) of the resin (polyamide resin and the second resin) (or a temperature equal to or higher than the melting point and lower than the decomposition temperature of cellulose), and is, for example, 150 to 300 ° C. , Preferably 170-250 ° C, more preferably 180-230 ° C.
It may be about. The kneading time is, for example, 30 seconds to 1 hour, preferably 1 minute to 30 minutes.
More preferably, it may be about 2 to 10 minutes.

The composite may be molded by, for example, 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, a casting molding method or the like. The molded product of the composite is not limited to a two-dimensional structure (film, sheet, plate, etc.), but may have a three-dimensional structure (for example, a tube, a rod, a tube, a hollow product, etc.). Further, the molded product may be a housing, a casing or the like.

The resin composition, composite resin composition, and composite of the present invention may be prepared with various additives, if necessary.
For example, stabilizers (antioxidants, UV absorbers, light-resistant stabilizers, heat stabilizers, etc.), antistatic agents, flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), difficult Flame retardants, impact resistance improvers, fluidity improvers, reinforcing materials (fillers, etc.), colorants, lubricants, mold release agents, hue improvers,
It may contain a dispersant, an antibacterial agent, a preservative and the like. These additives may be used alone or in combination of two or more.

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

(measuring equipment)
Scanning electron microscope (FE-SEM): "JIM-6700F" manufactured by JEOL Ltd.

(Example 1)
GP Cellulose fluff pulp (G) cut into chips of about 3 mm square
100 parts by weight of polyamide 12 (Diamide L1940 manufactured by Daicel Evonik, hereinafter referred to as PA), 200 parts by weight of N, N-dimethylformamide (hereinafter, DMF) solution, 9,9-bis (hereinafter referred to as PA) with respect to 100 parts by weight of ladder4800). 4-Glysidyloxyphenyl) fluorene (hereinafter, BPFG) 15 parts by weight is kneaded with a kneader (“KRC kneader S1”, manufactured by Kurimoto, Ltd.), kneading temperature 130 ° C., discharge rate 30 g / min, residence time 4 Minutes, rotation speed 300 rp
The resin composition 1 was prepared by kneading under the condition of m.

Further, this resin composition 1 is subjected to a cylinder temperature of 100 by a twin-screw extruder (manufactured by Technobel Co., Ltd.).
By kneading under the conditions of ~ 130 ° C. and rotation speed 600 rpm, PA / CNF (polyamide / polyamide /) containing 32% by weight of DMF and 31.6% by weight of pulp fraction (content of cellulose nanofibers)
Cellulose nanofibers) Masterbatch 1 (pellets) was obtained.

The scanning electron microscope (SEM) observation results of the fibers of CNF in the obtained masterbatch 1 are shown in FIG. As is clear from the results of FIG. 1, the cellulose nanofibers in the resin composition 1 are
The nano-sized fibers were dispersed substantially uniformly, and the average fiber diameter was 367 nm. The average fiber diameter is an arithmetically averaged value obtained by randomly selecting fibers from the SEM image. The same applies to the following Examples 2 to 3 and Comparative Example 1.

Using the obtained PA / CNF masterbatch 1 and PA, the solvent is removed by vacuum venting while kneading with a twin-screw extruder (manufactured by Technobel) under the conditions of a cylinder temperature of 140 to 180 ° C. and a rotation speed of 180 rpm. By doing so, a composite having a pulp content (content of cellulose nanofibers) of 10% by weight was prepared.

(Example 2)
Resin composition 2 in the same manner as in Example 1 except that 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (hereinafter referred to as BPEF) is added instead of BPFG in the kneading process with the kneader. Was prepared.

DMF was set to 3 in the same manner as in Example 1 except that the resin composition 2 was used instead of the resin composition 1.
PA / containing 4.0% by weight and pulp fraction (content of cellulose nanofibers) 30.7% by weight
CNF (polyamide / cellulose nanofiber) masterbatch 2 (pellets) was obtained.

The scanning electron microscope observation results of the CNF fibers in the obtained masterbatch 2 are shown in FIG. As is clear from the results of FIG. 2, the cellulose nanofibers in the resin composition 2 had nano-sized fibers dispersed substantially uniformly, and the average fiber diameter was 566 nm.

A composite having a pulp fraction (content of cellulose nanofibers) of 10% by weight was prepared in the same manner as in Example 1 except that PA / CNF masterbatch 2 was used instead of PA / CNF masterbatch 1. did.

(Example 3)
In the same manner as in Example 1 except that BPFG is not added in the kneading process with the kneader.
The resin composition 3 was prepared.

DMF was set to 3 in the same manner as in Example 1 except that the resin composition 3 was used instead of the resin composition 1.
PA / containing 6.3% by weight and pulp fraction (content of cellulose nanofibers) 31.9% by weight
CNF masterbatch 3 (pellets) was obtained.

The results of scanning electron microscope observation of the fibers of CNF in the obtained master batch 3 are shown in FIG. As is clear from the results of FIG. 3, the cellulose nanofibers in the resin composition 3 had nano-sized fibers dispersed substantially uniformly, and the average fiber diameter was 664 nm.

A composite having a pulp fraction (content of cellulose nanofibers) of 10% by weight was prepared in the same manner as in Example 1 except that PA / CNF masterbatch 3 was used instead of PA / CNF masterbatch 1. did.

(Comparative Example 1)
PA, 233 with respect to 100 parts by weight of the fluff pulp (Grade4800) of Example 1.
The weight part is a twin-screw extruder (manufactured by Technobel), cylinder temperature 170-190 ° C, rotation speed 1
It was melt-kneaded under the condition of 80 rpm to obtain PA / CF (polyamide / cellulose fiber) master batch 4 (pellets) having a pulp fraction of 30% by weight. Using the obtained PA / CF masterbatch 4 and PA, a cylinder temperature of 170-18 was used in a twin-screw extruder (manufactured by Technobel).
By kneading under the conditions of 0 ° C. and a rotation speed of 180 rpm, a composite having a pulp fraction (content of cellulose fibers) of 10% by weight was prepared.

A multipurpose test piece (JISK7139, type A1) was molded from each of the composites obtained in Examples 1, 2, 3 and Comparative Example 1 by a hybrid injection molding machine (manufactured by Nissei Resin Industry Co., Ltd.). The appearance of Examples 2, 3 and Comparative Example 1 was evaluated according to the following criteria.

◯: Milky white to pale yellow ×: Yellow to brown.

FIG. 4 shows photographs of the appearance of each injection molded product, and Table 1 shows the evaluation results.

Also, from the multipurpose test piece, a test piece for measuring deflection temperature under load (HDT) (80 mm x 10 m)
m × 4 mm) was prepared. Then, the tensile test characteristics (maximum point strength, elongation, elastic modulus) of the tensile test piece are determined according to JIS K 7161, and the bending characteristics (bending strength, flexural modulus) of the bending test piece are determined according to JIS K 7191. , HDT measurement was performed. The results are shown in Table 1.

The resin composition, composite resin composition (master batch or resin reinforcing agent) and composite of the present invention can be used in a wide range of applications, as reinforcing materials for resins (polyamide resins), additives, materials for films and sheets, and the like. Further, since the composite (composite material) has excellently balanced properties such as toughness, strength, and elastic modulus, for example, various resin molded products [for example, packaging materials for electrical and electronic parts, building materials (wall materials). , Civil engineering materials, agricultural materials, packaging materials (containers, cushioning materials, etc.), daily necessities (daily supplies, etc.)], various materials such as liquid crystal display substrates and solar cell substrates; optical sheets, etc.; high strength Because it has automobile parts (body, hood, door, drive shaft, etc.), sporting goods (golf shaft, tennis racket frame, etc.),
It can also be used for leisure goods (fishing rods, etc.). In addition, molding members in various fields (for example,
It can be used for molded bodies such as casings and housings.

Claims (6)

A method for producing a resin composition containing a polyamide resin, cellulose nanofibers, and a solvent containing amides, wherein a mixing roller, a kneader, a Banbury mixer, or an extruder is used to use a solvent containing amides and a polyamide resin. A method for producing a resin composition by kneading a composition containing a raw material cellulose having an average fiber diameter of 1 μm to 1 mm at a temperature of 40 to 150 ° C. and lower than the boiling point of amides. The method according to claim 1, wherein the ratio of amides is 30 to 350 parts by weight with respect to 100 parts by weight of the total amount of the polyamide resin and the raw material cellulose. The method according to claim 1 or 2, wherein the ratio of the polyamide resin to the raw material cellulose is the former / the latter (weight ratio) = 10/90 to 90/10. The method according to any one of claims 1 to 3, wherein the cellulose nanofibers are unmodified cellulose nanofibers. The method according to any one of claims 1 to 4, wherein the amides are aliphatic amides. The method according to any one of claims 1 to 5, which is kneaded using a kneader or a twin-screw extruder.