KR101335758B1 - Composite compositions and composites - Google Patents

Abstract

The composite composition of the present invention is a composite composition comprising at least one of a fibrous filler and a resin, a metal oxide, and a flaky inorganic material, wherein the fibrous filler has an average fiber diameter of 4 to 1000 nm. It is preferable that the said fibrous filler is a cellulose fiber. Moreover, it is preferable that a cellulose fiber is a fiber obtained by making a cellulose raw material fine by at least one of a chemical treatment and a mechanical treatment, and it is preferable that some hydroxyl groups in the cellulose molecule contained are oxidized to at least one of an aldehyde group and a carboxyl group. The composite of the present invention is obtained by molding such a composite composition.

Description

COMPOSITE COMPOSITIONS AND COMPOSITES

The present invention relates to a composite composition and composite comprising a fibrous filler and at least one of resin, metal oxide and flaky inorganic material.

In order to reduce the coefficient of thermal expansion of resin, or to raise mechanical strength, such as an elasticity modulus and a bending strength, mix | blending a spherical filler and a fibrous filler is widely performed. In recent years, studies on spherical fine particles such as silica fine particles and metal fine particles and rod-shaped whisker-type nano-sized fillers are in full swing as a substitute for conventional macro fillers. However, few studies have been made on fibrous nanomaterials for these fillers.

Recently, many plastic substitutes using cellulose have been reported. For example, a composite using a microfibril of cellulose as a filler and other microfluidizers obtained by highly miniaturizing a fibrillated substance of cellulose using a device capable of applying an extremely high pressure called a high pressure homogenizer. And composites using microfibrils of cellulose downsized by a grinder method, freeze drying method, steel wire elastic kneading method, and ball mill grinding method as fillers. It is reported that a molded article having a relatively high strength can be obtained by using these fillers (see Patent Document 1, for example).

However, in the conventional microfibrillation method, a large amount of energy is required for downsizing treatment, which is disadvantageous in terms of cost and at the same time, there is a relatively wide distribution in the fiber diameter of the obtained micronized fiber and the degree of miniaturization is also incomplete. In some cases, some of the coarse fibers of 1 µm or more may remain slightly, so that a particularly wide distribution exists in the diameter and density of the microfibril fiber, which may cause a decrease in absolute value or a gap in the strength of the molded article.

Moreover, as described in patent document 2, it is known that the fiber reinforced composite material which is transparent and has a low linear expansion rate is obtained using the bacterial cellulose which a bacterium produces | generates. However, similarly to the case where the cellulose microfibrils are mechanically obtained, the production rate is slow and cannot be said to be advantageous in view of the industrial viewpoint.

Moreover, since cellulose has many hydroxyl groups in a fiber surface, hydrophilicity is high and a dimension and a physical property change large at the time of absorption. For this reason, there exist a problem that the dimension and physical property of a composite material change large at the time of absorption, and the use of a composite material is limited.

Japanese Unexamined Patent Publication No. 2003-201695 Japanese Unexamined Patent Publication No. 2005-60680

An object of the present invention is to provide a composite composition having a low coefficient of thermal expansion, high strength, high transparency, low humidity expansion coefficient (high water resistance), and a composite that is a molded article thereof efficiently.

In order to achieve the above object,

With fibrous fillers,

A composite composition comprising at least one of a resin, a metal oxide, and a flaky inorganic material,

The average fiber diameter of the said fibrous filler is 4-1000 nm, It is a composite composition characterized by the above-mentioned.

Moreover, in the composite composition of this invention, it is preferable that the said fibrous filler is cellulose fiber.

Moreover, in the composite composition of this invention, it is preferable that the said cellulose fiber is a fiber obtained by refine | miniaturizing a cellulose raw material by at least one of a chemical treatment and a mechanical treatment.

Moreover, in the composite composition of this invention, it is preferable that a part of hydroxyl groups in the cellulose molecule which the said cellulose fiber contains is oxidized to at least one of an aldehyde group and a carboxyl group.

Moreover, in the composite composition of this invention, it is preferable that the said cellulose fiber is obtained by using natural cellulose as a raw material, using an N-oxyl compound as an oxidation catalyst, and oxidizing the said raw material by making a raw material react with the said raw material in water.

Moreover, in the composite composition of this invention, it is preferable that the said resin is at least one of a plastic resin and curable resin.

Moreover, in the composite composition of this invention, it is preferable that the said resin contains an epoxy resin.

Moreover, in the composite composition of this invention, it is preferable that the said resin contains a phenol resin.

Moreover, in the composite composition of this invention, it is preferable that the said resin contains at least one of a coupling agent and the hydrolyzate of this coupling agent.

Moreover, in the composite composition of this invention, it is preferable that the said coupling agent is an alkoxysilane or the alkoxy titanium.

Moreover, in the composite composition of this invention, it is preferable that the average particle diameter of the said metal oxide is 1-1000 nm.

In the composite composition of the present invention, the metal oxide is preferably silicon dioxide.

In addition, in the composite composition of the present invention, the flaky inorganic material is mica, vermiculite, montmorillonite, iron montmorillonite, Weidelite, saponite, hectorite, Stevensite, nontronite, margadiite, illite, canneite, It is preferable that it is at least one selected from smectite and layered titanic acid.

Moreover, in the composite composition of this invention, it is preferable that the content rate of the said fibrous filler in the said composite composition is 0.1 to 99.9 weight%.

Moreover, in the composite composition of this invention, it is preferable that the total light transmittance in 30 micrometers in thickness is 80% or more.

Moreover, in the composite composition of this invention, it is preferable that the thermal expansion coefficient in 30 degreeC-180 degreeC is 50 ppm / degrees C or less.

In order to achieve the above object, the present invention is made by molding the composite composition, the composite is characterized in that the thickness is 10 ~ 2000㎛.

Moreover, in the composite of this invention, it is preferable that the coefficient of thermal expansion in 30 degreeC-150 degreeC is 0.4-50 ppm / degreeC.

Moreover, in the composite of this invention, it is preferable that a humidity expansion coefficient is 100 ppm / humidity% or less.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of the composite composition and composite of this invention is described in detail.

The composite composition of the present invention comprises a fibrous filler and at least one of resin, metal oxide and flake inorganic material. And the composite of this invention is manufactured by shape | molding this composite composition to a predetermined shape.

<Composite composition>

(Fibrous filler)

First, a fibrous filler is demonstrated.

The average fiber diameter of the fibrous filler used for this invention is 4-1000 nm, it is preferable that it is 4-300 nm, and it is more preferable that it is 4-200 nm. In addition, when the average fiber diameter exceeds the above upper limit, transparency deteriorates and mechanical strength is not improved. On the other hand, although an average fiber diameter may be less than the said lower limit, it is difficult to obtain such a fibrous filler.

Although it does not specifically limit about the length of the fibrous filler used for this invention, If a mean length of a fibrous filler is 100 nm or more, a reinforcement effect will be easy to be acquired and improvement of intensity | strength will be aimed at.

Here, the measurement of the average fiber diameter of a fibrous filler can be performed as follows.

First, the dispersion of the fibrous filler which is 0.05 to 0.1 weight% by solid content is prepared, This dispersion is cast on the carbon film coating grid, and it is set as the sample for TEM observation. Moreover, when including the fibrous filler of large fiber diameter, you may cast on glass and it may be set as the sample for SEM observation.

At the time of microscopic observation, an electron microscope image is acquired by any magnification of 5000 times, 10000 times, or 50000 times according to the size (fiber diameter) of the fibrous filler to comprise. When the axis | shaft of arbitrary image width | variety is assumed in the image obtained at this time, a sample condition and observation conditions (magnification etc.) are set so that at least 20 fibrous fillers may cross | intersect an axis with respect to an axis | shaft.

Then, with respect to the observed image satisfying this condition, the fiber diameter of the fibrous filler intersecting on each axis is read out visually by pulling two random axes of two vertically and horizontally per image. Further, at least three observation images are acquired while shifting the observation positions so as not to overlap each other on the sample surface, and the fiber diameters are read out as described above for each image. Thereby, the information of a fiber diameter is obtained about at least 20 * 2 * 3 = 120 fibrous fillers. The average fiber diameter is calculated based on the data of the fiber diameter thus obtained.

The fibrous filler used in the present invention may be any fiber, but is preferably composed of cellulose fibers.

Examples of the cellulose fibers include natural cellulose fibers, regenerated cellulose fibers, and the like. On the other hand, as fibers other than cellulose fiber, kitchen fiber, chitosan fiber, etc. are mentioned, for example.

Among these, natural cellulose fibers include purified pulp obtained from conifers and broadleaf trees, cellulose fibers obtained from cotton linter or cotton lint, cellulose fibers obtained from seaweeds such as baronia or shiog, cellulose fibers obtained from Hoya, and bacteria. Cellulose fibers; and the like. On the other hand, as regenerated cellulose fiber, what melt | dissolved the natural cellulose fiber once, and then reproduced in fibrous form with the cellulose composition is mentioned.

Moreover, the cellulose fiber used for this invention is used preferably with high crystallinity. Such cellulose fibers are particularly preferably used as fibrous fillers because of their low coefficient of linear expansion and high mechanical strength. In view of the above, as the cellulose fiber used in the present invention, natural cellulose fiber is more preferable than regenerated cellulose fiber.

Moreover, the cellulose fiber used for this invention may be what was obtained by what kind of well-known method, The manufacturing method is not specifically limited, For example, a cellulose raw material (natural cellulose or regenerated cellulose) is used as a medium stirring mill processing apparatus, and a vibration mill process. Mechanically refined by various micronization apparatuses, such as an apparatus, a high pressure homogenizer processing apparatus, and an ultrahigh pressure homogenizer treatment apparatus, are used. Moreover, the cellulose fiber obtained by the electrospinning method, the steam jet method, APEX (Polymer Group. Inc) method etc. can also be used as another method. However, in consideration of energy efficiency and the like, as the cellulose raw material, the cellulose fiber obtained by the method involving the chemical treatment shown below is most preferable.

The manufacturing method of the cellulose fiber demonstrated below is a method of manufacturing a cellulose fiber (nanocellulose fiber) by disperse | distributing in a dispersion medium by performing a chemical treatment to a cellulose raw material, and providing it to a mechanical process.

Specifically, [1] an oxidation reaction process in which natural cellulose is used as a raw material, an N-oxyl compound is used as an oxidation catalyst, and a co-oxidant is used to oxidize natural cellulose to obtain reactant fibers, and [2] impurities are removed. And a purification step of obtaining a reactant fiber impregnated with water, and a dispersion step of dispersing the reactant fiber impregnated with water in a dispersion medium. Each process is explained in full detail below.

[1] oxidation reaction processes

First, in the oxidation reaction process, the dispersion liquid which disperse | distributed the cellulose raw material in water is prepared. Here, the thing which performed the process which raises surface areas, such as beating previously, is preferably used for the cellulose raw material used. This is because the reaction efficiency can be increased and the productivity can be increased. Moreover, as a cellulose raw material, it is preferable to use what was preserve | saved by Neva dry after isolation and refine | purification. As a result, the agglomerates of the microfibrils constituting the cellulose raw material tend to swell, so that the reaction efficiency can be increased and the number average fiber diameter after the miniaturization can be reduced.

In addition, when water is used as a dispersion medium of the cellulose raw material in this process, the cellulose concentration in a dispersion liquid (reaction aqueous solution) is arbitrary as long as it is the density | concentration which can fully spread a reagent, but is 5 weight% or less with respect to the weight of a dispersion liquid normally.

Moreover, many N-oxyl compounds which can be used as an oxidation catalyst of cellulose are reported. For example, "Cellulose" Vol. 10, 2003, TEMPO (2,2) described in the article entitled "Catalytical Oxidation of Cellulose Using TEMPO Derivatives: HPSEC and NMR Analysis of Oxidation Products" by I.Shibata and A.Isogai on pages 335-341. Various N-oxyl compound catalysts of 6,6-tetramethyl-1-piperidine-N-oxyl), 4-acetamide-TEMPO, 4-carboxy-TEMPO and 4-phosphonooxy-TEMPO It is preferably used at the reaction rate at room temperature. In addition, the addition of these N-oxyl compounds is enough in a catalytic amount, Preferably it is added to reaction aqueous solution in 0.1-4 mmol / l, More preferably, it is 0.2-2 mmol / l.

As the co-oxidant, for example, hypohalogenic acid or salts thereof, ahalogenic acid or salts thereof, perhalogenic acid or salts thereof, hydrogen peroxide and perorganic acid, etc. may be mentioned. Sodium hypochlorite, sodium hypobromite, or the like is preferably used. When using sodium hypochlorite, it is preferable in the reaction rate to advance the reaction in the presence of an alkali metal bromide, for example sodium bromide. The addition amount of this alkali metal bromide becomes like this. Preferably it is about 1-40 times mole amount with respect to N-oxyl compound, More preferably, it is about 10-20 times mole amount.

Moreover, it is preferable that the pH of reaction aqueous solution is maintained in the range of about 8-11. Although the temperature of aqueous solution is arbitrary in the range of about 4-40 degreeC, reaction can be performed at room temperature and especially temperature control is not needed.

Although the carboxyl group is introduced into the cellulose molecule by the co-oxidant to replace the hydroxyl group, the amount of the carboxyl group required for the fine cellulose fiber used in the present invention varies depending on the type of cellulose raw material. What is necessary is just to set the time to operate a co-oxidant. Specifically, the larger the amount of carboxyl groups, the smaller the maximum fiber diameter and number average fiber diameter of the finally obtained cellulose fiber.

For example, in the case of using wood pulp and surface pulp as the cellulose raw material, the amount of carboxyl groups required is 0.2 to 2.2 mmol / g based on the cellulose raw material, and extracted cellulose from bacterial cellulose (BC) or Hoya is used as the cellulose raw material. In this case, the amount of carboxyl groups required is from 0.1 to 0.8 mmol / g. Thus, the amount of carboxyl groups optimal for each cellulose raw material can be introduce | transduced by controlling the addition amount of reaction agent and reaction time according to the kind of cellulose raw material.

In addition, based on the amount of carboxyl group introduced as described above, the amount of addition of the co-oxidant can be derived. For example, it is preferable to add about 0.5 to 8 mmol of the co-oxidant to 1 g of the cellulose raw material, and the reaction time is about 5 to 120. It is preferable to set it as less than 240 minutes in minutes and long.

Moreover, although a carboxyl group is introduce | transduced into a cellulose molecule by this oxidation reaction process, an aldehyde group may be introduce | transduced depending on the progress of oxidation treatment. Therefore, the hydroxyl group of a cellulose molecule is substituted by at least one of an aldehyde group and a carboxyl group after completion | finish of this oxidation reaction process.

[2] refining processes

In the purification step, it is an object to remove compounds other than reactant fibers and water contained in the reaction slurry, specifically compounds such as unreacted hypochlorous acid and various by-products. Since the reactant fibers are not normally dispersed in nanofiber units at this stage, high purity (more than 99% by weight) can be achieved by repeating the usual purification method, that is, washing and filtration.

The purification method in the purification step may be any device as long as it is an apparatus (for example, a continuous decanter) capable of achieving the above-mentioned object, such as a method using centrifugal dehydration. The reactant fiber thus obtained is in the range of approximately 10 to 50% by weight as a solid content (cellulose) concentration in the squeezed state. In addition, in consideration of dispersion in nanofiber units in a subsequent process, it is not preferable to set the solid content concentration higher than 50% by weight because extremely high energy is required for dispersion.

[3] dispersion processes

In the above-mentioned steps, the reactant fibers impregnated with water are obtained. However, the fine cellulose fibers used in the present invention are obtained in a dispersed state by dispersing them in a solvent and carrying out dispersion treatment.

Here, the solvent as the dispersion medium is usually water, but alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methylcellosolve, ethylcell, etc.) which are soluble in water depending on the purpose other than water are preferred. Sorb, ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone), N, N-dimethylformamide, N, N -Dimethylacetamide, dimethyl sulfoxide, or the like. Moreover, these mixtures can also be used preferably.

Moreover, when diluting and disperse | distributing with the above-mentioned reactant fiber solvent, the dispersion | distribution of the fiber of a nanofiber level can be obtained efficiently by performing the stepwise dispersion which a little solvent is added and disperse | distributes. Moreover, what is necessary is just to select dispersion conditions so that a dispersion may become viscous state or gel form after a dispersion process from an operational problem.

Here, various things can be used as a disperser used in a dispersion process. Specific examples will also depend on the progress of the reaction in the reactant fibers (conversion amount to aldehyde group or carboxyl group), but preferably under conditions under which the reaction proceeds, screw mixers, paddle mixers, disper mixers, turbine mixers, etc. A dispersion of fine cellulose fibers can be obtained sufficiently with a general purpose disperser as an industrial production machine.

In addition, by using a device that has a strong beating ability under high speed rotation such as a homo mixer, a high pressure homogenizer, an ultra high pressure homogenizer, an ultrasonic dispersion treatment, a beater, a disc refiner, a conical refiner, a double disc refiner, a grinder, More efficient and highly downsizing is possible. Furthermore, even when the introduction amount of an aldehyde group or a carboxyl group is relatively small (for example, 0.1-0.5 mmol / g as a total amount of an aldehyde group or a carboxyl group to cellulose), the dispersion of the finely refined fine cellulose fiber is used. Can provide.

Next, a method of recovering fine cellulose fibers from a dispersion in which fine cellulose fibers are dispersed in a dispersion medium will be described.

Specifically, the fine cellulose fibers can be recovered by drying the dispersion of the fine cellulose fibers described above.

Here, for example, a freeze drying method when the dispersion medium is water, a drying by a drum dryer when the dispersion medium is a mixture of water and an organic solvent, and spray drying by a spray dryer may be preferably used.

In the dispersion of the fine cellulose fibers described above, as a binder, a water-soluble polymer (polyethylene oxide, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, starch, natural gum, etc.) And sugars (glucose, fructose, mannose, galactose, trehalose, etc.) may be added. Since these binder components have extremely high boiling points and affinity for cellulose, by addition of these components into the dispersion, agglomeration when dispersed again in the dispersion medium even when dried by a general drying method such as a drum dryer or a spray dryer This prevents and can reliably obtain a dispersion of fine cellulose fibers dispersed as nanofibers. In this case, the k of the binder added in the dispersion is preferably in the range of 10 to 80% by weight based on the reactant fibers.

In addition, the recovered fine cellulose fibers are mixed again in a dispersion medium (water, an organic solvent or a mixture thereof) and applied with a suitable dispersing force (for example, dispersion using various dispersion machines used in the above-described dispersion step) is performed. It can be set as a dispersion of cellulose fibers.

As for the fine cellulose fiber used for this invention, it is preferable that some hydroxyl groups of a cellulose are oxidized by a carboxyl group or an aldehyde group, and it has a cellulose I type crystal structure. In addition, the fine cellulose fiber having a type I crystal structure means that the fiber is obtained by surface oxidation of a cellulose solid raw material derived from nature and refined.

In addition, the fine cellulose fibers having a type I crystal structure show typical peaks at two positions near 2θ = 14 to 17 ° and around 2θ = 22 to 23 ° in the diffraction profile obtained by the wide-angle X-ray diffraction image measurement. It can identify based on having. The introduction of an aldehyde group or a carboxyl group into the cellulose of the fine cellulose fiber can be confirmed by the presence of absorption (near 1608 cm ^-1 ) due to a carbonyl group in the total reflection type infrared spectral spectrum (ATR) for the sample from which water is completely removed. In particular, when acid type carboxyl group (-COOH) is introduce | transduced into cellulose, absorption exists in 1730cm <^-1> in the said measurement.

The finer cellulose fibers can be stably present as finer fiber diameters for the above-mentioned reasons, so that the more the total amount of carboxyl groups and aldehyde groups present in cellulose is, the larger the diameter. For example, in the case of wood pulp or cotton pulp, the sum of the amount of carboxyl groups and aldehyde groups present in the fine cellulose fibers (hereinafter, referred to as "total amount") is 0.2 to 2.2 mmol / g based on the weight of the cellulose fibers, preferably Preferably it is 0.5-2.2 mmol / g, More preferably, it is 0.8-2.2 mmol / g, The cellulose fiber excellent in the stability as a nanofiber is obtained. In the case of cellulose having a relatively large fiber diameter of microfibrils such as BC and Hoya extract cellulose (average fiber diameter of several 10 nm), the total amount is 0.1 to 0.8 mmol / g, preferably 0.2 to 0.8 If it is mmol / g, the cellulose fiber excellent in the stability as a nanofiber will be obtained. In addition, when the total amount is smaller than the lower limit, the difference in physical properties (for example, dispersion stabilization effect in the dispersion) with the micronized cellulose fibers known in the prior art becomes small and difficult to be obtained as a fiber having a small fiber diameter. Because it is not desirable.

In addition, an electrical repulsion force is generated by introducing a carboxyl group to an aldehyde group which is a nonionic substituent. Thereby, since the tendency for microfibrils to disperse without maintaining aggregation increases, stability as a dispersion of nanofibers increases more. For example, in the case of wood pulp or cotton pulp, the amount of carboxyl groups present in the fine cellulose fibers is 0.2 to 2.2 mmol / g, preferably 0.4 to 2.2 mmol / g, more preferably 0.6 to the weight of the cellulose fibers. If it is 2.2 mmol / g, the cellulose fiber which is extremely excellent in stability as a nanofiber is obtained. In the case of cellulose having a relatively large fiber diameter of microfibrils such as BC and Hoya extract cellulose, the amount of carboxyl groups is 0.1 to 0.8 mmol / g, preferably 0.2 to 0.8 mmol / g, which is excellent in stability as nanofibers. Cellulose fibers are obtained.

Here, the quantity (mmol / g) of the aldehyde group and carboxyl group of cellulose with respect to the weight of a cellulose fiber is evaluated by the following method.

60 ml of a slurry having a concentration of 0.5 to 1% by weight was prepared using a cellulose sample obtained by weighing dry weight, and the pH was adjusted to about 2.5 with 0.1 M aqueous hydrochloric acid solution, followed by dropwise addition of 0.05 M sodium hydroxide aqueous solution. Conduct conductivity measurements. This measurement is continued until the pH is about 11. From the amount of sodium hydroxide (V) consumed in the neutralization step of weak acid with a slight change in electrical conductivity, the functional group amount is calculated using the following equation. The functional amount calculated here is called "functional amount 1". This functional group weight 1 shows the quantity of a carboxyl group.

Functional group amount (mmol / g) = V (ml) x 0.05 / weight of cellulose (g)

Next, the cellulose sample is further oxidized at room temperature for 48 hours in a 2% aqueous sodium chlorite solution prepared at pH 4-5 with acetic acid, and the functional group amount is calculated again by the above method. The functional amount calculated here is called "functional amount 2". And the functional group amount (= functional group 2-functional group 1) added by this oxidation is computed. This functional group amount shows the amount of an aldehyde group.

(Suzy)

As resin used by this invention, a well-known thing can be used, Although it does not specifically limit, What contains various curable resin, various plastic resin, various water-soluble resin, etc. are mentioned.

The water-soluble resin is not particularly limited as long as it is dissolved in water. Examples of the water-soluble resin include thermoplastic resins, curable resins, natural polymers, and the like, but preferably polyvinyl alcohol, polyethylene oxide, polyacrylamide, and polyvinylpyrrolidone. Synthetic polymers, starches, polysaccharides such as alginic acids, natural polymers such as hemicellulose, gelatin, nicawa, casein and other proteins such as wood.

Moreover, although it does not specifically limit as a thermoplastic resin, For example, vinyl chloride resin, vinyl acetate resin, polystyrene, ABS resin, acrylic resin, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polypropylene, a fluororesin, a polyamide resin Polyesters such as thermoplastic polyimide resins, polyacetal resins, polycarbonates, polylactic acid, polyglycolic acid, poly-3-hydroxy butyrate, polyhydroxy valerate, polyethylene adipate, polycaprolactone, polypropyllactone, Polyamide, such as polyethyleneglycol, polyglutamic acid, and polyamide, such as polylysine, etc. are mentioned.

On the other hand, as curable resin, a phenol resin, a urea resin, a melamine resin, unsaturated polyester resin, an epoxy resin, an acrylic resin, an oxetane resin, a diallyl phthalate resin, a polyurethane resin, a silicon resin, a maleimide resin, Thermosetting polyimide resin etc. are mentioned.

Among these, as the acrylic resin, in addition to alkyl acrylate or alkyl methacrylate such as acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate, cyclic acrylate or methacrylate, hydroxyethyl acrylate and the like The resin contained above is mentioned.

Moreover, a phenol resin is an organic compound which has one or more phenolic hydroxyl groups in a molecule | numerator. For example, resol resins, such as a novolak, bisphenol, resin which has a naphthol and a naphthol in a molecule | numerator, a para xylylene modified phenol resin, a dimethylene ether type resol, and a methylol type phenol, are mentioned. Further, a compound obtained by further methylolation of these resins, lignin or lignin derivatives containing one or more phenolic hydroxyl groups, lignin decomposed products, modified lignin or lignin derivatives, lignin decomposed products or phenols prepared from petroleum resources The resin containing the thing mixed with resin is mentioned.

Moreover, an epoxy resin is an organic compound which has at least 1 epoxy group. For example, bisphenol-type epoxy resins, such as a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, and a bisphenol S-type epoxy resin, the hydride of these bisphenol-type epoxy resins, and the epoxy which has a dicyclopentadiene skeleton Resin, epoxy resin with triglycidyl isocyanurate skeleton, epoxy resin with cardard skeleton, epoxy resin with polysiloxane structure, alicyclic polyfunctional epoxy resin, alicyclic epoxy resin with hydrogenated biphenyl skeleton, hydrogenated bisphenol Alicyclic epoxy resin etc. which have A frame | skeleton are mentioned.

Moreover, various coupling agents may be sufficient as resin used by this invention.

Although a well-known thing can be used as a coupling agent, A silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. are mentioned, Among these, a silane coupling agent or a titanium coupling agent is preferable. Is used. These are relatively easy to obtain and are highly suitable as coupling agents included in the composite composition because of their high adhesiveness at the interface between the inorganic material and the organic material.

Moreover, it is preferable in a said coupling agent that a silane coupling agent contains at least 1 silicon atom and at least 1 alkoxy group as a functional group. Moreover, an epoxy group or an epoxy cyclohexyl group, an amino group, a hydroxyl group, an acryl group, methacryl group, a vinyl group, a phenyl group, a styryl group, an isocyanate group etc. are mentioned as another functional group. In addition, in this invention, since the effect equivalent to a coupling agent is acquired, the tetraalkoxysilane containing four alkoxy groups is also contained in a silane coupling agent.

Specific examples of the silane coupling agent include tetraalkoxysilane compounds, methyltrialkoxysilanes, alkyl group-containing alkoxysilane compounds such as dimethyl dialkoxysilane, 3-glycidoxypropyl trialkoxysilane, and 3-glycidpropylpropyl dialkoxysilane. , Epoxysilane compounds such as 2- (3,4-epoxycyclohexyl) ethyl trialkoxysilane, aminoalkoxysilane compounds such as 3-aminopropyl trialkoxysilane, N-phenyl-3-aminopropyl trialkoxysilane, 3- (Meth) acrylic alkoxysilane compounds such as acryloxypropyl trialkoxysilane, methacryloxypropyl trialkoxysilane, 3-methacryloxypropylmethyl dialkoxysilane, and 3-methacryloxypropyl trialkoxysilane, and vinyl trialkoxysilane Phenyl group-containing trialkoxy such as vinylalkoxysilane compound, phenyltrialkoxysilane, diphenyldialkoxysilane, 4-hydroxyphenyl trialkoxysilane Styryl-group containing alkoxysilane compounds, such as a cysilane compound and 3-isocyanate propyl trialkoxysilane, etc. are illustrated. Among these, the tetraalkoxysilane compound, the alkyl group containing alkoxysilane compound, and the phenyl group containing alkoxysilane compound have a high effect of improving water resistance, and are preferable.

In addition, the alkoxy titanium compound which has a substituent similar to an alkoxysilane compound is mentioned as a specific example of a titanium type coupling agent. For example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctylphosphite) titanate , Tetraoctyl bis (ditridecylphosphite) titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostaroyl diacryl titanate, isopropyl tri (di Octylphosphate) titanate, isopropyl trixylphenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate, bis (dioctyl) Pyrophosphate) Ethylene Titanate, Bis (Dioctyl Pyrophosphate) Oxyacetate Titanate And tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate.

Moreover, you may use the hydrolyzate of a coupling agent as mentioned above instead of a coupling agent. What is necessary is just to select a coupling agent or its hydrolyzate suitably in consideration of compatibility with a dispersion medium, stability of a hydrolyzate, etc. In addition, the hydrolyzate of a coupling agent can be easily created by stirring-mixing acidic aqueous solutions, such as an acetic acid aqueous solution, with a coupling agent. The hydrolyzate of the coupling agent may be produced by any method as long as the molecular structure is the same as the hydrolyzate of the coupling agent, even if the hydrolyzable group (alkoxide group) is not hydrolyzed.

In addition, the water-soluble resin, thermoplastic resin, curable resin, and coupling agent mentioned above may be used individually, or may be used in combination of 2 or more.

(Metal oxide)

The metal oxide used in the present invention is not particularly limited in kind, but includes oxides of single metals such as SiO ₂ (silica), Al ₂ O ₃ (alumina), TiO ₂ (titania), ZrO ₂ (zirconia), and the like. And composite oxides such as SiO ₂ -Al ₂ O ₃ (such as mullite), SiO ₂ -TiO ₂ , SiO ₂ -ZrO ₂ , and spinel, titania-containing silica, zirconia-containing silica, and the like.

Such a metal oxide may be formed in any form, but preferably becomes a particulate. In this case, not only the particle | grains of a metal oxide may be comprised by 1 type of oxide fine particles, but may be comprised by the mixture which mixed 2 or more types of oxide fine particles. Such oxide fine particles can be obtained by a method such as a sol-gel method, a wet method, a gas phase method, or a dry method.

Among the metal oxides, especially SiO _2, Al ₂ O _3, or it is preferred to use a composite oxide thereof. These are relatively inexpensive and can improve the mechanical strength, heat resistance and wear resistance of the composite.

In particular, in order to improve the wear resistance of the composite, it is preferable to use fine particles of Al ₂ O ₃ as the metal oxide. These microparticles are the least expensive, and they are also resistant to corrosion by acids and alkalis, thereby enhancing the chemical stability of the composite.

Further, when the composite is provided in the applications such as electronic components, it is preferable to use the fine particles (silica fine particles) of SiO ₂ as the metal oxide. Since the fine particles have a low dielectric constant, the dielectric constant of the composite can be lowered to suppress transmission delay in electronic components and the like.

Examples of the silica fine particles include dry powdery silica fine particles and colloidal silica (silica sol) dispersed in a solvent. From the point of dispersibility, it is preferable to use colloidal silica (silica sol) dispersed in water or an organic solvent or these mixed solvents. Examples of the solvent include alcohols such as water, methanol, ethanol, isopropyl alcohol, butyl alcohol and n-propyl alcohol, ketones, esters, and glycol ethers, but are suitable for ease of dispersion of the fibrous filler. The solvent can be selected.

As for the average particle diameter of such a metal oxide, 1-1000 nm is preferable, More preferably, it is 1-50 nm, More preferably, it is 5-50 nm, Most preferably 5-40 nm from the point of balance of transparency and workability. Becomes Moreover, if it is less than the said lower limit, there exists a possibility that the viscosity of the produced composite composition may increase extremely. On the other hand, if the upper limit is exceeded, the transparency of the composite may be significantly deteriorated, which is not preferable.

Moreover, when using a silica fine particle as a metal oxide, in order not to reduce the light transmittance of wavelength 400-500 nm, it is preferable to use the silica fine particle which suppressed the ratio of the silica fine particle whose primary particle diameter is 200 nm or more to 5% or less, It is more preferable to make the ratio 0%. In order to raise the filling amount of a silica particle, you may mix and use the silica particle from which an average particle diameter differs. As the silica fine particles, a porous silica sol as shown in JP-A-7-48117 or a composite metal oxide of aluminum, magnesium, zinc, or silicon may be used.

(Inorganic Materials for Flakes)

Examples of the flaky inorganic material used in the present invention include clay minerals composed of natural or synthetic materials. Specifically, it is selected from the group consisting of mica, vermiculite, montmorillonite, iron montmorillonite, Weidelite, saponite, hectorite, stevensite, nontronite, margadiite, illite, carnemite, layered titanic acid, smectite, and the like. At least 1 type is mentioned.

The flaky inorganic material is in the form of scales, and typically, the thickness of one particle is about 1 to 10 nm and the aspect ratio is preferably 20 to several thousand, more preferably 20 to several hundreds of scales. By stacking such scale-shaped clay particles in any layer in the composite, the path through which gas passes is long, and consequently, the gas barrier property of the composite is improved.

Moreover, you may make it contain the cationic substance which has hydrophobicity between layers of the flaky inorganic material in a composite composition as needed. Clay minerals generally contain hydrophilic exchange cations between layers. In the present invention, the hydrophilic exchange cation present between the layers of the flaky inorganic material, which is a clay mineral, can be organically exchanged with a hydrophobic cation. As the hydrophobic cationic material, for example, a quaternary ammonium salt such as dimethyl distearyl ammonium salt or trimethyl stearyl ammonium salt, or an ammonium salt having a benzyl group or a polyoxyethylene group is used, or a phosphonium salt, a pyridinium salt or an imidazolium salt It can also be organicized using the ion exchangeability of clay.

In addition, the composite composition of this invention may contain either of the above-mentioned resin, a metal oxide, and flaky inorganic material, and may contain 2 or more. For example, the composite composition of this invention may contain a fibrous filler, resin, a metal oxide, and a flaky inorganic material.

In the composite composition of the present invention, the content of the fibrous filler is preferably 0.1 to 99.9 wt%, more preferably 0.1 to 75 wt%. In addition, the content rate of a fibrous filler is not specifically limited, It adjusts suitably according to the characteristic required at the time of shape | molding a composite composition. In the composite composition, the content of the fibrous filler may be increased in order to more reflect the properties of the fibrous filler, and the content of the resin may be increased in order to more reflect the properties of the resin.

Moreover, when manufacturing the composite used for optical use using the composite composition of this invention, it is preferable that the average thermal expansion coefficient (average linear expansion coefficient) of 30-180 degreeC of a composite composition is 50 ppm / degrees C or less, More preferably, It is 30 ppm / degrees C or less, More preferably, it is 20 ppm / degrees C or less.

Moreover, it is preferable that the total light transmittance in 30 micrometers of thickness is 80% or more, and, as for the composite composition of this invention, it is more preferable that it is 90% or more. This finally obtains a composite having high transparency and suitable for optical applications.

<Complex>

The composite of the present invention is obtained by molding the composite composition of the present invention into a predetermined shape.

The composite of the present invention is used, for example, as a substrate for solar cells, a substrate for organic EL, a substrate for electronic paper, or a plastic substrate for liquid crystal display elements, but in this case, the total light transmittance is preferably 70% or more, more preferably. Is 80% or more, more preferably 88% or more.

In addition, the composite of the present invention may be, for example, used in optical applications, that is, a transparent substrate, an optical lens, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a solar cell substrate, a touch panel, and an optical element. When using as an optical waveguide, an LED sealing material, etc., it is preferable that the average thermal expansion coefficient (average linear expansion coefficient) of 30-150 degreeC is 50 ppm / degrees C or less, More preferably, it is 30 ppm / degrees C or less. In particular, when used for a sheet-like active matrix display element substrate, it is preferable that the said average thermal expansion coefficient is 30 ppm / degrees C or less, More preferably, it is 20 ppm / degrees C or less. It is because there exists a possibility that problems, such as a curvature and a disconnection of wiring, may arise in a manufacturing process when it exceeds the said upper limit. In addition, although a lower limit is not specifically set, it is 0.4 ppm / degreeC as an example.

Moreover, when using the composite of this invention as a plastic substrate for liquid crystal display elements, a substrate for color filters, a plastic substrate for organic electroluminescent display elements, a solar cell board | substrate, a touch panel, etc., a humidity expansion coefficient becomes like this. It is 100 ppm / humidity% or less, More preferably, it is 50 ppm / humidity% or less, More preferably, it is 30 ppm / humidity% or less. Further, the swelling ratio (swelling magnification) at the time of absorption of the composite of the present invention is preferably 50 times or less, more preferably 30 times or less, still more preferably 10 times or less.

Moreover, when shape | molding the composite of this invention in plate shape, it is preferable that the thickness is 10-2000 micrometers, It is more preferable that it is 10-500 micrometers, It is more preferable that it is 20-200 micrometers. When the thickness of the substrate is within this range, the composite of the present invention is required as a transparent substrate and combines sufficient mechanical strength and light transmittance. Moreover, by carrying out thickness of a board | substrate in the said range, it is excellent in flatness and can reduce weight of a board | substrate compared with a glass substrate.

When using the composite composition of this invention as an optical sheet, you may provide the coating layer of resin on both surfaces for smoothness improvement. As resin to coat, what has the outstanding transparency, heat resistance, and chemical resistance is preferable, Specifically, polyfunctional acrylate, an epoxy resin, etc. are mentioned. It is preferable that it is 0.1-50 micrometers, and, as for the average thickness of a coating layer, it is more preferable that it is 0.5-30 micrometers.

Moreover, when using the optical sheet obtained from the composite composition of this invention especially as a plastic substrate for display elements, you may provide the gas barrier layer and transparent electrode layer with respect to water vapor and oxygen as needed.

When the composite composition of the present invention contains a curable resin, the curing method of the curable resin is not particularly limited, but a curing accelerator such as a crosslinking agent such as an acid anhydride or an aliphatic amine or a cationic curing catalyst or an anionic curing catalyst may be used. Can be.

Among them, as a cationic curing catalyst, for example, releasing a substance which initiates a cationic polymerization by heating (for example, an onium salt-based cation curing catalyst or an aluminum chelate-based cation curing catalyst) or cationic polymerization by an active energy ray Releasing a substance which initiates the reaction (for example, an onium salt-based cationic curing catalyst). Specifically, examples of the aromatic sulfonium salts include hexafluoroantimonate salts such as SI-60L, SI-80L, SI-100L, and Asahi Kogyo Co., Ltd. SP-66 and SP-77. Examples of the aluminum chelate include ethyl acetate acetate aluminum diisopropylate, aluminum tris (ethylacetate acetate), and the like, as the boron trifluoride complex, a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, And boron trifluoride piperidine complex.

On the other hand, examples of the anionic curing accelerator include tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7 and triethylenediamine, and 2-ethyl-4-methylimide. Imidazoles such as sol and 1-benzyl-2-phenylimidazole, phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium tetraphenylborate, quaternary ammonium salts, organometallic salts and derivatives thereof; Among these, imidazoles, such as a phosphorus compound and 1-benzyl-2- phenylimidazole, are preferable because it is excellent in transparency. These hardening accelerators may be used independently or may use 2 or more types together.

In the composite composition of this invention, a thermoplastic or thermosetting oligomer or a polymer can be used together as needed. Moreover, the composite composition of this invention may contain a small amount of fillers, such as antioxidant, a ultraviolet absorber, a dye pigment, another inorganic filler, etc. in the range which does not impair a characteristic as needed.

The composite composition of the present invention is prepared by mixing the respective components by any method. For example, the method of mixing a fibrous filler and resin, a metal oxide, and at least 1 of flaky inorganic material as it is is mentioned. Moreover, you may make it mix, heating as needed.

In addition, if a uniform dispersion of the fibrous filler is prepared using a solvent (dispersion medium) and then desolvented, a uniform composite composition having excellent dispersibility of the fibrous filler and dispersibility of the metal oxide or flaky inorganic material can be obtained. Can be obtained.

As a solvent to be used, the solvent which can maintain the dispersibility of a fibrous filler, for example, and can melt | dissolve or disperse resin, a metal oxide, and flaky inorganic material is preferable. As such a solvent, for example, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dioxane, acetone, methyl ethyl ketone, methyl cellosolve, tetrahydrofuran, penta Erythritol, dimethyl sulfoxide, dimethylformamide, N-methyl- 2-pyrrolidone, etc. are mentioned, These can also be used individually or in mixture of 2 or more types. In addition, it is also possible to gradually change the polarization ratio of the original dispersion medium to the polarity of the desired dispersion medium to disperse the fibrous filler in the dispersion medium having different polarities.

Furthermore, the method of obtaining the sheet which has predetermined thickness, such as a solar cell board | substrate, an organic EL board | substrate, an electronic paper board | substrate, and a plastic substrate for liquid crystal display elements using the composite composition of this invention, should just be a general sheet formation method, and it limits especially It doesn't work. For example, a method of sheet-forming a composite composition comprising a fibrous filler and a resin, a metal oxide and a flaky inorganic material, or casting a dispersion medium of the fibrous filler and removing the solvent to obtain a sheet of the fibrous filler, Later, a method of impregnating the resin or a solution containing a fibrous filler, a resin, a metal oxide, a flaky inorganic material, and a solvent, followed by removal of the solvent, to obtain a sheet, and the like.

One of the preferred embodiments in such a process is to disperse at least one of a fibrous filler and a resin, a metal oxide and a flaky inorganic material in advance in a solvent to prepare a dispersion, and then the resulting dispersion is flexible to a filter paper, a membrane filter or a supernet. And other components such as solvent and the like are filtered and / or dried to obtain a sheet made of the composite composition. In addition, in the said filtration drying process, you may carry out under reduced pressure and pressurization, in order to improve work efficiency. Moreover, when forming continuously, the method of forming a thin layer sheet continuously using the paper machine used in the paper industry is also included.

In the case of being flexible and producing a sheet, it is preferable that the sheet formed after filtration and / or drying is produced on a substrate which can be easily peeled off. As such a base material, what is made of metal or resin is mentioned. Examples of the metal substrate include stainless steel substrates, brass substrates, zinc substrates, copper substrates, iron substrates, and the like. The resin substrates are acrylic substrates, fluorine substrates, polyethylene terephthalate substrates, and vinyl chloride substrates. , A polystyrene base material, a base made of polyvinylidene chloride, and the like.

Example

Next, a specific embodiment of the present invention will be described.

[Production A of Fine Cellulose Fibers]

( Production Example  A)

Firstly, it consists mainly of cellulose fibers of fiber diameters of more than 1000 nm, with a dry weight of 2 g of undried pulp and 0.025 g of TEMPO (2,2,6,6-tetramethyl-1-piperidine-N -Oxyl) and 0.25 g of sodium bromide were dispersed in 150 ml of water to prepare a dispersion.

Next, an aqueous 13 wt% sodium hypochlorite aqueous solution was added to this dispersion so that the amount of sodium hypochlorite was 2.5 mmol relative to 1 g of pulp to initiate the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution was added dropwise into the dispersion to maintain the pH at 10.5. Thereafter, at the time when no change was observed in pH, the reaction was regarded as being finished, and the reaction product was filtered through a glass filter, and the filtrate was washed with a sufficient amount of water, and filtration was repeated five times. This obtained the reactant fiber containing water of 25 weight% of solid content concentration.

Next, water was added to the obtained reactant fibers to prepare a 2% by weight slurry. The slurry was then treated with a rotary blade mixer for about 5 minutes. Since the viscosity of the slurry increased remarkably with the treatment, water was added little by little, and dispersion processing by the mixer was continued until the solid content concentration became 0.2% by weight. This obtained the cellulose nanofiber dispersion liquid.

This cellulose nanofiber dispersion liquid was cast on the carbon film coating grid which completed the hydrophilic treatment, and then negatively dyed with 2% uranyl acetate. And the cast cellulose nanofiber dispersion liquid was observed by TEM, but the maximum fiber diameter was 10 nm, and the number average fiber diameter was 6 nm.

Moreover, although the cast cellulose nanofiber dispersion liquid was dried, the transparent membrane cellulose was obtained. A wide-angle X-ray diffraction image was obtained for this film cellulose, and it became clear that the film cellulose consisted of cellulose nanofibers having a cellulose I-type crystal structure.

Moreover, the total reflection type infrared spectroscopy was performed about the same membrane cellulose and the ATR spectrum was obtained. In the pattern of the ATR spectrum, the presence of the carbonyl group was confirmed, and the amount of the aldehyde group and the amount of the carboxyl group in the cellulose evaluated by the method described above were 0.31 mmol / g and 0.97 mmol / g, respectively.

[Production A of Composite]

( Example  1A)

The cellulose nanofiber dispersion liquid (solid content 10 weight part) of 0.2 weight% of solid content concentration obtained by manufacture example A was filtered under reduced pressure, water was removed, and it substituted 5 times with methanol. Next, the cellulose nanofiber methanol dispersion liquid was filtered under reduced pressure, methanol was removed, and the operation of substituting 90 weight part of alicyclic epoxy monomers containing 1 weight part of thermal cationic catalysts (SI-100L) was repeated 5 times. And the obtained cellulose nano fiber dispersion | distribution epoxy resin (10 weight% of cellulose solids) was cast, it heated at 100 degreeC for 2 hours, and then it heated at 150 degreeC for 2 hours and hardened | cured. This obtained the composite of thickness 1mm. The obtained composite was cut | disconnected to width 10mm, and the test piece for bending strength measurement was produced. It was 48 N when the bending strength was measured about this test piece.

( Example  2A)

The cellulose nanofibers were obtained by filtering under reduced pressure the cellulose nanofiber dispersion liquid (15 weight part of solid content) of 0.2 weight% of solid content concentration obtained by manufacture example A, and removing water, and further freeze-drying. Next, the mixture obtained by adding 15 weight part of cellulose nanofibers to 85 weight part of phenol novolak resins, and 15 weight part of hexamethylenetetramine was mixed for 3 minutes with the mixer. In addition, the mixture was kneaded with two heating rolls at 100 ° C to obtain a thermosetting resin molding material. The obtained molding material was heated at 125 ° C. for 2 hours by compression molding, and then further heated at 150 ° C. for 2 hours to cure. This obtained the composite of thickness 1mm. The obtained composite was cut | disconnected to width 10mm, and the test piece for bending strength measurement was produced. It was 60 N when the bending strength was measured about this test piece.

( Example  3A)

Tetraethoxysilane was added to the cellulose nanofiber dispersion liquid (100 weight part of solid content) of 0.2 weight% of solid content concentration obtained by manufacture example A, and the weight same as the weight of cellulose nanofiber solid content was stirred for 30 minutes at room temperature. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a mold release treatment, and further dried in a vacuum oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. The total light transmittance, thermal expansion coefficient, and humidity expansion coefficient of the film were measured. The total light transmittance was 90%, the thermal expansion coefficient was 11 ppm / 占 폚, and the humidity expansion coefficient was 26 ppm / humidity%.

( Example  4A)

Phenyltriethoxysilane was added to the cellulose nanofiber dispersion liquid (100 weight part of solid content) of 0.2 weight% of solid content concentration obtained by manufacture example A, and the weight of cellulose nano fiber solid content was added, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a mold release treatment, and further dried in a vacuum oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. About this film, the total light transmittance, the coefficient of thermal expansion, and the coefficient of humidity were measured. The total ray transmittance was 89%, the coefficient of thermal expansion was 10 ppm / 占 폚, and the humidity expansion coefficient was 23 ppm / humidity%.

( Example  5A)

3-glycidoxypropyl triethoxysilane was added to the cellulose nanofiber dispersion liquid (100 weight part of solid content) of 0.2 weight% of solid content concentration obtained by the production example A, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a mold release treatment, and further dried in a vacuum oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. About this film, the total light transmittance, the coefficient of thermal expansion, and the coefficient of humidity were measured. The total ray transmittance was 88%, the coefficient of thermal expansion was 11 ppm / 占 폚, and the humidity expansion coefficient was 25 ppm / humidity%.

( Example  6A)

Titanium alkoxide was added to the cellulose nanofiber dispersion liquid (100 weight part of solid content) of 0.2 weight% of solid content concentration obtained by manufacture example A, and the weight same as the weight of cellulose nanofiber solid content was stirred for 30 minutes at room temperature. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a mold release treatment, and further dried in a vacuum oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. About this film, the total light transmittance, the coefficient of thermal expansion, and the coefficient of humidity expansion were measured. The total ray transmittance was 88%, the coefficient of thermal expansion was 12 ppm / 占 폚, and the humidity expansion coefficient was 27 ppm / humidity%.

( Example  7A)

The cellulose nanofiber dispersion liquid (solid content 100 weight part) of the solid content concentration 0.2 weight% obtained by the preparation example A, 80 weight part of epoxy resins (Denacol EX-214L, Nagase ChemteX Corp.), and 5 weight part of tetramethylethylenediamine were mixed, Stirred for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of 50 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 80%, the thermal expansion coefficient was 15 ppm / 占 폚, the humidity expansion coefficient was 110 ppm / humidity%, and the swelling ratio was 16 times.

( Example  8A)

The cellulose nanofiber dispersion liquid (solid content 100 weight part) and 110 weight part of epoxy resins (Denacol EX-1410L, Nagase Chemtex make) obtained by the preparation content A of 0.2 weight% were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of 50 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 80%, the thermal expansion coefficient was 14 ppm / 占 폚, the humidity expansion coefficient was 61 ppm / humidity%, and the swelling ratio was 1.8 times.

( Example  9A)

100 weight part of cellulose nanofiber dispersion liquid (solid content 100 weight part) of the solid content concentration obtained by the manufacture example A, 110 weight part of epoxy resins (Denacol EX-1410L, Nagase ChemteX Corp.), and 5 weight part of tetramethylethylenediamine were mixed, Stirred for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of 50 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 80%, the thermal expansion coefficient was 12 ppm / 占 폚, the humidity expansion coefficient was 90 ppm / humidity%, and the swelling ratio was 3.1 times.

( Example  10A)

100 weight part of cellulose nanofiber dispersion liquid (100 weight part solids) of the solid content concentration obtained by the manufacture example A, 110 weight part of epoxy resins (Denacol EX-1610L, Nagase ChemteX Corp.), and 5 weight part of tetramethylethylenediamine were mixed, Stirred for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of 50 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 80%, the thermal expansion coefficient was 13 ppm / 占 폚, the humidity expansion coefficient was 76 ppm / humidity%, and the swelling ratio was 2.4 times.

( Example  11A)

100 weight part of cellulose nanofiber dispersion liquid (100 weight part of solid content) and resol type phenol resin (PR-967, Sumitomo Bakelite product) of 0.2 weight% of solid content concentration obtained by manufacture example A were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of 25 micrometers in thickness. The total light transmittance, the humidity expansion coefficient, and the swelling ratio were measured for this film. The total light transmittance was 50%, the humidity expansion coefficient was 50 ppm / humidity%, and the swelling ratio was 1.2 times. Moreover, since this sample asked, the sample for thermal expansion coefficient measurement was not obtained.

( Example  12A)

The cellulose nanofiber dispersion liquid (solid content 100 weight part) and the resol type phenol resin (PR-967, Sumitomo Bakelite make) of 0.2 weight% of solid content concentration obtained by manufacture example A were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of 58 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 40%, the thermal expansion coefficient was 20 ppm / 占 폚, the humidity expansion coefficient was 45 ppm / humidity%, and the swelling ratio was 1.2 times.

( Comparative Example  1A)

The sulfurous acid bleached conifer pulp was swelled in water, and then finely dispersed in a mixer. The obtained short fiber pulp dispersion liquid was filtered under reduced pressure, water was removed, and substituted with methanol five times. Subsequently, the short fiber pulp methanol dispersion liquid was filtered under reduced pressure, methanol was removed, and the operation | work which replaced with 90 weight part of alicyclic epoxy monomers containing 1 weight part of thermal cationic catalysts (SI-100L) was repeated 5 times. And the obtained short fiber pulp disperse epoxy resin (10 weight% of cellulose solids) was cast, and it heated at 100 degreeC for 2 hours, and then it heated at 150 degreeC for 2 hours and hardened. This obtained the composite of thickness 1mm. The obtained composite was cut | disconnected to width 10mm, and the test piece for bending strength measurement was produced. It was 28 N when the bending strength was measured about this test piece.

Moreover, the short fiber pulp methanol dispersion liquid was observed by SEM, The maximum fiber diameter was 70 micrometers, and the number average fiber diameter was 40 micrometers.

( Comparative Example  2A)

The sulfurous acid bleached conifer pulp was swelled in water, and then finely dispersed in a mixer. The obtained short fiber pulp dispersion liquid was filtered under reduced pressure, water was removed, and further freeze-dried to obtain fine cellulose fibers. Next, the mixture obtained by adding 15 weight part of fine cellulose fibers to 85 weight part of phenol novolak and 15 weight part of hexamethylenetetramine was mixed for 3 minutes with the mixer. In addition, the mixture was kneaded with two heating rolls at 100 ° C to obtain a thermosetting resin molding material. The obtained molding material was heated at 125 ° C. for 2 hours by compression molding, and then further heated at 150 ° C. for 2 hours to cure. This obtained the composite of thickness 1mm. The obtained composite was cut | disconnected to width 10mm, and the test piece for bending strength measurement was produced. It was 40 N when the bending strength was measured about this test piece.

Moreover, the short fiber pulp methanol dispersion liquid was observed by SEM, The maximum fiber diameter was 70 micrometers, and the number average fiber diameter was 40 micrometers.

( Comparative Example  3A)

The cellulose nanofiber dispersion liquid (solid content 0.15 weight%) obtained by the production example A was evaporated in the oven of 50 degreeC according to the mold release process, and further dried in the vacuum oven of 120 degreeC. This obtained the transparent film of thickness 30micrometer. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the film were measured. The total light transmittance was 91%, the thermal expansion coefficient was 10 ppm / 占 폚, the humidity expansion coefficient was 125 ppm / humidity%, and the swelling ratio was 140 times.

[Production B of Fine Cellulose Fibers]

( Production Example  B)

Firstly, it consists mainly of cellulose fibers of fiber diameters of more than 1000 nm, with a dry weight of 2 g of undried pulp and 0.025 g of TEMPO (2,2,6,6-tetramethyl-1-piperidine-N -Oxyl) and 0.25 g of sodium bromide were dispersed in 150 ml of water to prepare a dispersion.

Next, an aqueous 13 wt% sodium hypochlorite aqueous solution was added to this dispersion so that the amount of sodium hypochlorite was 2.5 mmol per 1 g of pulp to initiate the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution was added dropwise using an automatic titrator to maintain the pH at 10.5. Thereafter, the reaction was terminated when no change was observed in pH, and neutralized to pH 7 with 0.5M aqueous hydrochloric acid solution. The reaction was filtered and the filtrate was washed with a sufficient amount of water and filtration was repeated six times. This obtained the reactant fiber containing water of 2 weight% of solid content concentration.

Next, water was added to the obtained reactant fibers to prepare a 0.2 wt% reactant fiber dispersion.

This reactant fiber dispersion was treated 20 times at a pressure of 200 bar (20 MPa) using a high pressure homogenizer (manufactured by APV GAULIN LABORATORY, type 15MR-8TA). This obtained the transparent cellulose nanofiber dispersion liquid.

This cellulose nanofiber dispersion was cast onto a carbon film-coated grid on which a hydrophilic treatment was completed, and then negatively dyed with 2% uranyl acetate. And the cast cellulose nanofiber dispersion liquid was observed by TEM, The maximum fiber diameter was 10 nm and the number average fiber diameter was 8 nm.

Moreover, although the cast cellulose nanofiber dispersion liquid was dried, the transparent membrane cellulose was obtained. A wide-angle X-ray diffraction image was obtained for the film cellulose, and it became clear that the film cellulose was made of cellulose nanofibers having a cellulose I-type crystal structure.

Moreover, the total reflection type infrared spectroscopy was performed about the same membrane cellulose and the ATR spectrum was obtained. From the pattern of the ATR spectrum, the presence of the carbonyl group was confirmed, and the amount of aldehyde group and carboxyl group in cellulose evaluated by the above-described method were 0.31 mmol / g and 1.7 mmol / g, respectively.

[Production B of Composite]

( Example  1B)

100 weight part (solid content 0.2g) of cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by Production Example B, and colloidal silica (Snowtex 20, particle diameter 10-20nm, content 20-21wt% of silicic acid anhydride, Nissan Chemical Industrial Co., Ltd.) 1 weight part (solid content is 0.2 g) were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the obtained films were measured. The total light transmittance was 87%, the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 9 ppm / ° C., and the humidity expansion coefficient was 70 ppm /. Humidity% and swelling rate were 2 times.

( Example  2B)

100 weight part (solid content 0.2g) of cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by manufacture example B, and colloidal silica (Snowtex N, particle diameter 10-20nm, content 20-21wt% of silicic acid anhydride, Nissan Chemical Industrial Co., Ltd.) 1 weight part (solid content is 0.2 g) were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. About the obtained film, the coefficient of thermal expansion, the coefficient of humidity expansion, and the coefficient of swelling were measured, but the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 10 ppm / ° C., the humidity expansion coefficient was 61 ppm / humidity%, and the swelling rate was 1.6 times.

( Example  3B)

100 weight part (solid content 0.2g) of cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by Production Example B, and colloidal silica (Snowtex O, particle diameter 10-20nm, content 20-21wt% silicic acid anhydride, Nissan Chemical Industrial Co., Ltd.) 1 weight part (solid content is 0.2 g) were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. The total light transmittance, the coefficient of thermal expansion, the coefficient of humidity expansion, and the swelling coefficient were measured for the obtained film. The total ray transmittance was 90%, the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 11 ppm / ° C., and the humidity expansion coefficient was 65 ppm /. Humidity% and swelling ratio were 1.7 times.

( Example  4B)

100 weight part (solid content 0.2g) of cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by manufacture example B, and colloidal silica (Snowtex XS, particle diameter 4-6 nm, content of silicic acid anhydride 20-21 wt%, Nissan Chemical Industrial Co., Ltd.) 1 weight part (solid content is 0.2 g) were mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. The total light transmittance, the coefficient of thermal expansion, the coefficient of swelling and the coefficient of swelling were measured for the obtained film. The total ray transmittance was 89%, the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 10 ppm / ° C., and the humidity expansion coefficient was 68 ppm /. Humidity% and swelling rate were 1.9 times.

( Example  5B)

100 weight part (solid content 0.2g) of cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained in Production Example B, and colloidal silica (Snowtex CM, particle diameter 20-30nm, content 30-31wt% silicic acid anhydride, Nissan Chemical) 0.7 parts by weight (solid content: 0.2 g) was mixed and stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the transparent film of thickness 30micrometer. The total light transmittance, the coefficient of thermal expansion, the coefficient of swelling and the coefficient of swelling of the obtained film were measured. The total ray transmittance was 88%, the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 11 ppm / ° C., and the humidity expansion coefficient was 70 ppm /. Humidity% and swelling rate were 1.9 times.

( Comparative Example  1B)

The cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by the production example B was evaporated in the oven of temperature 50 degreeC according to the mold release process, and further dried in the vacuum oven of 120 degreeC. This obtained the transparent film of thickness 30micrometer. The total light transmittance, the coefficient of thermal expansion, the coefficient of swelling and the coefficient of swelling of the obtained film were measured. The total ray transmittance was 91%, the coefficient of thermal expansion in the range of 30 ° C. to 180 ° C. was 10 ppm / ° C., and the humidity expansion coefficient was 115 ppm /. Humidity% and swelling ratio were 100 times.

[Production C of Fine Cellulose Fibers]

( Production Example  C)

First, it consists mainly of fibers with a fiber diameter of more than 1000 nm, with a dry weight of 2 g of undried pulp and 0.025 g of TEMPO (2,2,6,6-tetramethyl-1-piperidine-N- Oxyl) and 0.25 g of sodium bromide were dispersed in 150 ml of water to prepare a dispersion.

Next, an aqueous 13 wt% sodium hypochlorite aqueous solution was added to this dispersion so that the amount of sodium hypochlorite was 2.5 mmol per 1 g of pulp to initiate the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution was added dropwise using an automatic titrator to maintain the pH at 10.5. Thereafter, the reaction was terminated when no change was observed in pH, and neutralized to pH 7 with 0.5M aqueous hydrochloric acid solution. And the reaction was filtered and the filtrate was wash | cleaned with sufficient quantity of water, and filtration was repeated 6 times. This obtained the reactant fiber containing 2 weight% of solid content water.

Next, water was added to the obtained reactant fibers to prepare a 0.2 wt% reactant fiber dispersion.

This reactant fiber dispersion was treated 10 times at a pressure of 20 MPa using a high pressure homogenizer (manufactured by APV GAULIN LABORATORY, type 15MR-8TA). This obtained the transparent cellulose nanofiber dispersion liquid.

This cellulose nanofiber dispersion was cast onto a carbon film-coated grid on which a hydrophilic treatment was completed, and then negatively dyed with 2% uranyl acetate. And the cast cellulose nanofiber dispersion liquid was observed by TEM, The maximum fiber diameter was 10 nm and the number average fiber diameter was 6 nm.

Moreover, although the cast cellulose nanofiber dispersion liquid was dried, the transparent membrane cellulose was obtained. A wide-angle X-ray diffraction image was obtained for the film cellulose, and it became clear that the film cellulose was made of cellulose nanofibers having a cellulose I-type crystal structure.

Moreover, the total reflection type infrared spectroscopy was performed about the same membrane cellulose and the ATR spectrum was obtained. From the pattern of the ATR spectrum, the presence of the carbonyl group was confirmed, and the amount of the aldehyde group and the amount of the carboxyl group in the cellulose evaluated by the method described above were 0.31 mmol / g and 1.7 mmol / g, respectively.

[Production of Composite C]

( Example  1C)

The cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by manufacture example C, and synthetic smectite (lucentite SWF) were mixed so that the weight ratio of cellulose nanofiber and synthetic smectite might be 25 to 75, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. in accordance with a mold release treated to obtain a transparent film having a thickness of 50 μm. The total light transmittance, the coefficient of thermal expansion, and the swelling ratio of the obtained film were evaluated. The total light transmittance was 91%, the linear expansion coefficient in the range of 30 ° C to 180 ° C was 4 ppm / ° C, and the swelling rate was 15 times.

( Example  2C)

The cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by manufacture example C, and synthetic smectite (lucentite SWF) were mixed so that the weight ratio of cellulose nanofiber and synthetic smectite might be 55 to 45, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. in accordance with a mold release treatment to obtain a transparent film having a thickness of 20 μm. The total light transmittance, the coefficient of thermal expansion, and the swelling ratio of the obtained film were evaluated. The total light transmittance was 91%, the linear expansion coefficient in the range of 30 ° C to 180 ° C was 5 ppm / ° C, and the swelling ratio was 48 times.

( Example  3C)

The cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by manufacture example C, and synthetic saponite (Smectone SA) were mixed so that the weight ratio of cellulose nanofiber and synthetic saponite might be 25 to 75, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. in accordance with a mold release treatment to obtain a transparent film having a thickness of 47 μm. The total light transmittance, the coefficient of thermal expansion, and the swelling ratio of the obtained film were evaluated. The total light transmittance was 90%, the linear expansion coefficient in the range of 30 ° C to 180 ° C was 3.2 ppm / ° C, and the swelling ratio was 12 times.

( Example  4C)

The cellulose nanofiber dispersion and the synthetic saponite (Smectone SA) of 0.2 weight% of solid content concentration obtained by the production example C were mixed so that the weight ratio of cellulose nanofiber and synthetic saponite might be 50-50, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated with moisture in an oven at a temperature of 50 ° C. in accordance with a mold release treatment to obtain a transparent film having a thickness of 41 μm. The total light transmittance, the coefficient of thermal expansion, and the swelling ratio of the obtained film were evaluated. The total light transmittance was 90%, the linear expansion coefficient in the range of 30 ° C to 180 ° C was 5.8 ppm / ° C, and the swelling ratio was 32 times.

( Example  5C)

100 weight part of cellulose nanofiber dispersion liquid (solid content 100 weight part) of the solid content concentration obtained by manufacture example C, flaky inorganic material (Lucent SWF, Corp. make), and epoxy resin (Denacol EX-214L, Nagase Chemtex) Company) 600 weight part was mixed, and it stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of thickness 24micrometer. About the obtained film, the total light transmittance, the coefficient of thermal expansion, the coefficient of swelling and the swelling were measured. The total light transmittance was 91%, the coefficient of thermal expansion was 14 ppm / 占 폚, the humidity expansion coefficient was 60 ppm / humidity%, and the swelling ratio was 2.1 times.

( Example  6C)

100 weight part of cellulose nanofiber dispersion liquid (solid content 100 weight part) of the solid content concentration obtained by manufacture example C, flaky inorganic material (Lucent SWF, Corp. make), and epoxy resin (Denacol EX-214L, Nagase Chemtex) Manufactured) 200 parts by weight were mixed and stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of 50 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the obtained film were measured. The total light transmittance was 92%, the thermal expansion coefficient was 13 ppm / 占 폚, the humidity expansion coefficient was 57 ppm / humidity%, and the swelling ratio was 1.7 times.

( Example  7C)

100 weight part of cellulose nanofiber dispersion liquid (solid content 100 weight part) of flakes concentration 0.2weight% obtained by manufacture example C, flaky inorganic material (Smecton SA, the product made by Kunimine industry), and epoxy resin (Denacol EX-214L, Nagase) 600 parts by weight of Chemtex Co., Ltd. was mixed and stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of 30 micrometers in thickness. The total light transmittance, the coefficient of thermal expansion, the coefficient of humidity expansion, and the swelling ratio were measured with respect to the obtained film.

( Example  8C)

100 weight part of cellulose nanofiber dispersion liquid (solid content 100 weight part) of flakes concentration 0.2weight% obtained by manufacture example C, flaky inorganic material (Smecton SA, the product made by Kunimine industry), and epoxy resin (Denacol EX-214L, Nagase) 200 parts by weight of Chemtex Co., Ltd. was mixed and stirred at room temperature for 30 minutes. The obtained mixed solution was evaporated in an oven at a temperature of 50 ° C. according to a mold treated with a release treatment, and further dried in an oven at 120 ° C. This obtained the film of 58 micrometers in thickness. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the obtained film were measured. The total light transmittance was 91%, the thermal expansion coefficient was 13 ppm / 占 폚, the humidity expansion coefficient was 71 ppm / humidity%, and the swelling ratio was 2.4 times.

( Comparative Example  1C)

The cellulose nanofiber dispersion liquid of 0.2 weight% of solid content concentration obtained by the manufacture example C was stirred for 30 minutes at room temperature, and moisture was evaporated in oven with the temperature of 50 degreeC according to the mold release process, and the transparent film with a thickness of 18 micrometers was obtained. The total light transmittance, thermal expansion coefficient, humidity expansion coefficient, and swelling ratio of the obtained film were evaluated. The total light transmittance was 90%, the thermal expansion coefficient in the range of 30 ° C to 180 ° C was 12 ppm / ° C, the humidity expansion coefficient was 200 ppm / humidity%, and the swelling rate was 185 times.

[Evaluation of Composites]

The characteristic evaluation method is as follows.

(a) flexural strength

The bending strength of the test piece for bending strength measurement is based on JIS K 7171, and the bending strength measuring device is operated under a 36 mm extension distance, a crosshead speed of 1 mm / min, 23 ° C, and a relative humidity of 60%. It was measured using Orient Tech Co., Ltd. product, UCT-30T type tensilron).

(b) coefficient of thermal expansion

Using a thermal stress distortion measuring device (manufactured by Seiko Electronics Co., Ltd., TMA / SS120C type), the temperature was raised from 30 ° C to 150 ° C at a rate of 5 ° C for 1 minute under a nitrogen atmosphere, and then cooled to 0 ° C once. Then, the temperature was further increased at a rate of 5 ° C. for 1 minute, and the value at 30 ° C. to 150 ° C. was measured and determined. The load was 5 g, and the measurement was performed in the tensile mode.

In addition, about Example 1B-5B and Comparative Example 1B, after raising a temperature from 30 degreeC to 200 degreeC at the ratio of 5 degreeC for 1 minute, it cooled to 0 degreeC once, and raised temperature at the rate of 5 degreeC for 1 minute again. The value at the time of 30 degreeC-180 degreeC was measured and calculated | required.

In addition, about Example 1C-8C and Comparative Example 1C, after raising a temperature from 30 degreeC to 200 degreeC at the ratio of 5 degreeC for 1 minute, it cooled to -50 degreeC once, and temperature was further adjusted at the rate of 5 degreeC for 1 minute. It raised and measured and calculated | required the value at 30 degreeC-180 degreeC.

(c) total light transmittance

Total light transmittance was measured with the spectrophotometer (The Shimadzu Corporation make, U3200).

In addition, about Example 1C-8C and Comparative Example 1C, the total light transmittance was measured with the haze meter (the NDH-2000 made from Nippon Color Corporation).

(d) humidity expansion coefficient

Two points which become a reference | standard of a dimensional measurement were drawn on the obtained film, it was left to stand for 24 hours in the atmosphere of 23 degreeC of room temperature, and 60% of humidity, and it put into a 100 degreeC dryer for 3 hours, and dried.

The distance between two points previously drawn immediately after drying was measured with a three-dimensional measuring instrument, and this distance was used as a reference for the distance between two points. Then, after leaving the film after drying for 24 hours in the atmosphere of room temperature 23 degreeC and 60% of humidity again, the distance between two points previously drawn was measured with the three-dimensional measuring instrument, and the dimensional change rate from a reference distance was computed. In addition, the humidity of the external appearance after drying was 0%, and the humidity expansion coefficient per 1% humidity in the range of 0% to 60% humidity was calculated.

(e) swelling rate

The obtained film was immersed in 23 degreeC pure water for 1 hour, and the film thickness change rate before and behind impregnation was measured. And the swelling ratio was computed as the magnification with respect to the film thickness before impregnation of the film thickness after impregnation.

The measurement results are shown in Tables 1-3.

As can be seen from Table 1, the test pieces (composites obtained using the composite composition of the present invention) obtained in Examples 1A and 2A are all mechanical strengths compared with the test pieces containing the conventional fibrous fillers obtained in Comparative Example 1A. And it was confirmed that dimensional stability is high and excellent in various characteristics.

In addition, the films obtained in Examples 3A to 12A (composites obtained using the composite composition of the present invention) are films formed from a composite composition containing a fibrous filler and a resin or a coupling agent (or a hydrolyzate of the coupling agent), but these are humidity It was confirmed that the expansion coefficient (absorption dimensional change rate) and the coefficient of thermal expansion were relatively small and were excellent in transparency.

As can be seen from Table 2, it was confirmed that the films (composites obtained using the composite composition of the present invention) obtained in Examples 1B to 5B were all smaller than the films obtained in Comparative Example 1B and had excellent water resistance. .

As can be seen from Table 3, it was confirmed that the films (composites obtained using the composite composition of the present invention) obtained in Examples 1C to 8C were all smaller in swelling ratio and superior in water resistance as compared with the films obtained in Comparative Example 1C. . Moreover, it was confirmed that the film obtained in Examples 1C-8C is excellent in dimensional stability by heat, and also high transparency from a comparatively small coefficient of thermal expansion.

In addition, the main raw material used by each Example and each comparative example is as follows.

Epoxy resin

: Ceroxide 2021 Daicel Chemical

: Dena Call EX-214L manufactured by Nagase Chemtex

: Denacol EX-1410L Nagase Chemtex

: Dena Call EX-1610L manufactured by Nagase Chemtex

Phenolic resin

: Resol type phenol resin PR-967 Sumitomo bakelite agent

Thermocationic catalyst

: SI-100L Samshin Chemical

Phenolic Novolak Resin

: PR-HF-6 Sumitomo Bakelite

Coupling agent

: Tetraethoxysilane Wako Pure Chemicals

: Phenyltriethoxysilane amax

: 3-glycidoxypropyl triethoxysilane Shin-Etsu Chemical Co., Ltd.

: Titanium alkoxides KR-ET Ajinomoto Fine Technose

Crosslinking material (hexamethylenetetramine)

: Orotropin Sumitomo Chemical Co., Ltd.

Metal oxide

: Colloidal Silica Snowtex 20 made by Nissan Chemical Co., Ltd.

: Colloidal Silica Snowtex N manufactured by Nissan Chemical Co., Ltd.

: Colloidal Silica Snowtex O made by Nissan Chemical Co., Ltd.

: Colloidal Silica Snowtex XS manufactured by Nissan Chemical Co., Ltd.

: Colloidal Silica Snowtex CM manufactured by Nissan Chemical Industries, Ltd.

Flaky inorganic material

: Smekton SA Kunimine Industry

: Lucentite SWF Corp Chemical

Industrial availability

The composite composition of the present invention contains at least one of a fibrous filler and a resin, a metal oxide, and a flaky inorganic material, and the average fiber diameter of the fibrous filler is 4 to 1000 nm. For this reason, at least one of a fibrous filler, resin, metal oxide, and flaky inorganic material brings about mechanical and chemical action to the composite formed by molding the composite composition. As a result, a composite having a low thermal expansion coefficient, high strength, high transparency, and low humidity expansion coefficient (high water resistance and high dimension stability) is obtained. Therefore, the composite of the present invention is used in automobile parts such as automobile exteriors and dashboards, components of transport equipment such as railroads, aircrafts, ships, building materials such as chassis, wall plates and top plates in houses and offices, columns, or reinforced concrete. Structural members such as reinforcing bars, electronic circuits such as electronic circuits and substrates of displays, office equipment such as home appliances such as PCs and mobile phones, office equipment such as stationery, household goods such as furniture, disposable containers, sports Small items used in homes such as supplies and toys, outdoor installations such as signs and signs, shock absorbers such as bulletproof shields and bulletproof vests, body armor such as helmets, artificial bones, medical supplies, abrasives, soundproof walls, firewalls, vibration It can be used for absorbing members, tools, mechanical parts such as leaf springs, musical instruments, packing materials and the like. Thus, the composite compositions and composites of the present invention have industrial applicability.

Claims (19)

Cellulose fibers having an average fiber diameter of 4 to 1000 nm,
A composite composition comprising at least one of a resin, a metal oxide, and a flaky inorganic material, mixed with the cellulose fiber,
The cellulose fiber is a composite composition, characterized in that the cellulose fibers are refined by acting a co-oxidant on the cellulose raw material, and a portion of the hydroxyl group in the cellulose molecule is oxidized to at least one of the aldehyde group and the carboxyl group. The method according to claim 1,
The total amount of the aldehyde group and the carboxyl group amount is 0.2 to 2.2 mmol / g based on the weight of the cellulose fiber. The method according to claim 1,
Said cellulose fiber is further refined by mechanical treatment of a cellulose raw material. The method according to claim 1,
The cellulose fiber is a composite composition obtained by oxidizing the natural cellulose by preparing natural cellulose as the cellulose raw material, using an N-oxyl compound as an oxidation catalyst, and acting the co-oxidant on the natural cellulose in water. . The method according to claim 1,
The cellulose fiber is a composite composition having a type I crystal structure. The method according to claim 1,
The resin composition is at least one of a plastic resin and a curable resin. The method according to claim 1,
The resin composition is a composite comprising an epoxy resin. The method according to claim 1,
The resin composition is a composite comprising a phenol resin. The method according to claim 1,
And the resin comprises at least one of a coupling agent and a hydrolyzate of the coupling agent. The method of claim 9,
And said coupling agent is an alkoxysilane or alkoxy titanium. The method according to claim 1,
Composite composition of the average particle diameter of the said metal oxide is 1-1000 nm. The method according to claim 1,
The metal oxide is silicon dioxide composite composition. The method according to claim 1,
The flaky inorganic material is 1 selected from mica, vermiculite, montmorillonite, iron montmorillonite, Weidelite, saponite, hectorite, stevensite, nontronite, margadiite, illite, cannemite, smectite and layered titanic acid. Composite composition of at least a species. The method according to claim 1,
The composite composition of the cellulose fiber content in the composite composition is 0.1 to 99.9% by weight. The method according to claim 1,
A composite composition having a total light transmittance of 80% or more at a thickness of 30 μm. The method according to claim 1,
The composite composition whose thermal expansion coefficient in 30 degreeC thru | or 180 degreeC is 50 ppm / degrees C or less. The composite is formed by molding the composite composition according to any one of claims 1 to 16, and has a thickness of 10 to 2000 µm. 18. The method of claim 17,
A composite having a thermal expansion coefficient of 0.4 to 50 ppm / ° C at 30 ° C to 150 ° C. 18. The method of claim 17,
Composites with a coefficient of humidity expansion of 100 ppm /% humidity.