JP4979117B2 - Cellulose-containing resin composite - Google Patents

Description

  The present invention relates to a composite comprising a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose.

  In general, glass plates are widely used as display element substrates (particularly active matrix type) for liquid crystal display elements and organic EL display elements, color filter substrates, solar cell substrates, and the like.

However, in recent years, plastic materials have been studied as an alternative to glass plates because they are difficult to reduce in thickness, are easy to break, cannot be bent, have large specific gravity, and are not suitable for weight reduction. For example, Patent Document 1 discloses a transparent resin substrate for a liquid crystal display element comprising a cured product obtained by curing an epoxy resin composition containing an epoxy resin, an acid anhydride curing agent, and a curing catalyst. A transparent resin substrate for a liquid crystal display element having two or more thermoplastic resin films and having an adhesive layer between the thermoplastic resin films is described. Patent Document 3 describes a liquid crystal display element using a transparent substrate obtained by curing and molding a composition containing a specific bis (meth) acrylate with active energy rays or the like.
A glass plate used for the display front plate is also being considered for a plastic plate. For example, Patent Documents 4, 5, and 6 show display front filters using polycarbonate, polyethylene terephthalate, or the like.

  However, these conventional plastic materials for glass replacement have a larger coefficient of linear expansion than glass plates, and particularly when used for active matrix display element substrates, warping, cracking of deposited films, aluminum wiring Problems such as disconnection are likely to occur, and it is difficult to use for these purposes. Accordingly, there is a demand for a plastic material having a low linear expansion coefficient while satisfying transparency, heat resistance, etc. required for a display element substrate, particularly an active matrix display element substrate.

  In order to reduce the coefficient of linear expansion, it is common to combine an inorganic filler such as a glass fiber with a resin. However, when the resin and the inorganic filler are combined, a transparent composite material cannot usually be obtained. This is mainly because the light transmitted through the resin is scattered at the interface because the refractive index of the inorganic filler is different from the refractive index of the resin. In order to solve such a problem, various studies have been made to make the refractive index of the resin and the glass fiber transparent. For example, Patent Document 7 and Patent Document 8 show that a transparent composite material can be obtained by reducing the difference in refractive index between a cyclic olefin resin and glass fiber. Non-Patent Document 1 shows that a transparent composite can be obtained using an epoxy resin and glass fibers having a refractive index close to that. However, since the Abbe numbers of the glass fiber and the resin are different, it is difficult to match the refractive index for light of all wavelengths, and a phenomenon such as scattering of only light of a specific wavelength often occurs.

  On the other hand, as seen in the recent technological focus on global nanotechnology, one direction of material development is the control and focus on smaller structural units. Among these technical trends, the present inventors have developed a microfibrous cellulose (hereinafter referred to as microfiber) obtained from natural cellulose such as pulp having a fiber diameter of 1 μm or less disclosed in Patent Document 9 and Non-Patent Document 2. Fine and highly crystalline cellulose nanofibers (hereinafter referred to as bacterial cellulose, manufactured by acetic acid bacteria disclosed in Patent Document 10 and fibrated cellulose, abbreviated as MFC) and having a thickness in the range of about several nm to 200 nm. (Hereinafter abbreviated as BC). Such a film composed of cellulose nanofibers is known to have a very low linear expansion coefficient as disclosed in Patent Document 11 and Patent Document 12, and further, the gap is filled with a resin to form a hybrid. It is described that the material made to show the low linear expansion coefficient.

  Recently, as disclosed in Non-Patent Document 3, Yano et al. Hybridized an epoxy resin or an acrylic resin to a BC membrane obtained by pressing and drying a BC gel obtained by stationary culture. It has been reported that the hybrid film is effective as an optical film because it has a low linear expansion coefficient and high transparency.

  However, according to Yano et al.'S report, for example, the BC membrane obtained by static culture is a very dense membrane, so it was impregnated with a resin monomer when preparing a composite containing 65% cellulose fibers. This requires extremely long time and immersion under reduced pressure (after immersion for 12 hours under reduced pressure and then for 4 days at 20 ° C. under normal pressure), which is extremely disadvantageous from the viewpoint of industrial production. In this technique, cellulose, which is the main component of the low linear expansion coefficient, is originally a hygroscopic material, and has a characteristic that physical properties are likely to change with moisture absorption. Accordingly, there has been a demand for reducing the BC or cellulose fraction in the hybrid film as much as possible. Patent Document 12 discloses the fact that the above-mentioned hybrid material can be obtained when bacterial cellulose having a specific shape is used. In order to produce the material industrially, cellulose raw material is disclosed. While the versatility of the conditions required for the membrane is necessary, the structural constraints required for the cellulose membrane to achieve a low linear expansion coefficient need to be clarified.

  Further, it is desirable that the membrane made of BC or fine cellulose that can be a raw material of the hybrid film is supplied by a continuous production process capable of industrial production, not a batch-type stationary culture method. In that case, cellulose can be easily dispersed in a dispersion medium such as water, and then it can be easily formed by a papermaking method or a cast film formation method. However, various devices are required for the dispersion method and the film forming conditions. Only when a hybrid film is formed using a cellulose film having remarkably improved film quality uniformity, it can be applied as a precision material such as an optical film.

That is, in order to be able to provide the technology industrially in providing a transparent film having a low linear expansion coefficient by hybridizing a film made of cellulose nanofibers and a polymer resin, there are some problems described above. There was a need to solve.
JP-A-6-337408 JP-A-7-120740 International Publication Number WO2002 / 074532 JP 2003-295778 A JP 2003-5659 A JP-A-10-90667 JP-A-6-256604 JP-A-6-305077 JP-A 56-1000080 Japanese Examined Patent Publication No. 6-43443 International Publication Number WO2003 / 040189 JP 2004-270064 A Abstracts of Symposium on Composite Materials, 22, 86 (1997) J.Appl.Polym.Sci., Appl.Polym.Symp., 37, 797-813 (1983) Abstracts of 11th Annual Meeting of Cellulose Society, p1-p2

  The objective of this invention is providing the resin material which is excellent in transparency, and has a small linear expansion coefficient, satisfying heat resistance.

That is, the present invention
[1] It comprises a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose, wherein (a) component is 5% by weight to 60% by weight and (b) component is 40% by weight to 95% by weight. %, And the non-woven fabric (a) containing cellulose has a porosity of 50% or more and 95% or less, and is scanned vertically with 850 nm light with respect to the non-woven fabric in a state of being immersed in toluene. And cellulose having an average transmittance T _{r, av} defined by the following formula (1) of 0.70 or more and a film quality uniformity parameter H defined by the following formula (2) is 0.018. The composite_body | complex characterized by using the nonwoven fabric containing the cellulose which is the following.
However,
_{Tr, av} is filled with toluene in a state where the nonwoven fabric is adhered to the inner surface of the test tube, irradiated with light of 850 nm from the direction perpendicular to the nonwoven fabric, and linearly along the surface of the nonwoven fabric. Obtained by carrying out the same measurement in the state where only toluene was injected except for the average value T _{r, 1 of the} transmittance obtained when scanning for a total length of 30000 μm (data points: 750) every 40 μm. The ratio of the average transmittance T _{r, 2} is defined by the following equation.
T _{r, av} = T _{r, 1} / T _{r, 2} (1)
H is filled with toluene with the nonwoven fabric attached to the inner surface of the test tube, irradiated with light of 850 nm to the test tube from a direction perpendicular to the nonwoven fabric, and linearly along the surface of the nonwoven fabric every 40 μm. The transmittance obtained by performing the same measurement in the state in which only toluene was injected except for the standard deviation _{Tr, sd1 of the} transmittance and the nonwoven fabric obtained when scanning was performed for a total length of 30000 μm (data score: 750). It is defined by the following equation using T _{r, av} obtained by equation (1) in the same measurement as T _{r, sd} defined by the difference between standard deviations T _{r, sd2} .
H = T _{r, sd} / T _{r, av} (2)
Here, _{Tr, sd} = _{Tr, sd1} - _{Tr, sd2} .
[2] The composite according to [1], wherein the pores of the nonwoven fabric (a) containing cellulose are filled with a resin (b) other than cellulose.
[3] The composite as described in [1] or [2], wherein a non-woven fabric containing cellulose having a porosity of 70% to 95% is used as the non-woven fabric (a) containing cellulose.
[4] Nonwoven fabric comprising cellulose fibers entangled with cellulose fibers having a maximum fiber thickness of 1500 nm or less obtained by forming a film from a dispersion containing cellulose fibers by a papermaking method or a coating method as a nonwoven fabric (a) containing cellulose. The complex according to any one of [1] to [3], wherein:
[5] A nonwoven fabric obtained by a papermaking method as a nonwoven fabric (a) containing cellulose, and as a dispersion for papermaking, the dispersion average diameter of cellulose fibers is 1 μm to 300 μm, and the cellulose fiber concentration is 0.01 A dispersion having a weight percentage of not less than 1.0% and not more than 1.0% is used, and as a filter cloth, the cellulose fiber in the dispersion for papermaking has the ability to filter 95% or more by filtration at 25 ° C under atmospheric pressure, Using a filter cloth having a water permeation amount of 0.005 cc / cm ² · s or more at 25 ° C. under atmospheric pressure, installing the filter cloth on the wire of the paper making apparatus and filtering the papermaking dispersion liquid on the filter cloth. The cellulose fiber is deposited on the filter cloth to produce a wet nonwoven fabric with a solid content of 4% by weight or more of the fine cellulose fiber, and the nonwoven fabric is peeled off from the filter cloth before or after the drying process. Cellulose fibers maximum fiber thickness is 1500nm or less, characterized by using a nonwoven fabric comprising entangled that [1] to composite according to any one of [4].
[6] As the nonwoven fabric (a) containing cellulose, the maximum fiber thickness produced by the production method including a step of replacing the dispersion medium in the papermaking dispersion with an organic solvent before the drying step is 1500 nm or less. The composite as described in [5], wherein a nonwoven fabric in which cellulose fibers are entangled is used.
[7] The composite according to any one of [1] to [6], wherein the linear expansion coefficient is 0.5 ppm / ° C. or more and 60 ppm / ° C. or less.
[8] The composite according to any one of claims 1 to 7, which has a linear expansion coefficient of 1 ppm / ° C to 50 ppm / ° C.
[9] The relationship of the storage elastic modulus in the dynamic viscoelasticity measurement satisfies the following formula, and the storage elastic modulus E ′ ₁₅₀ at 150 ° C. of the composite in the dynamic viscoelasticity measurement is 100 MPa or more [1] to [8 ] The composite_body | complex of any one of these.
_{E '30 / E' 150 ≦} 1000
E ′ ₃₀ : Storage elastic modulus of the composite at 30 ° C. E ′ ₁₅₀ : Storage elastic modulus of the composite at 150 ° C. [10] The relationship of the storage elastic modulus in the dynamic viscoelasticity measurement satisfies the following formula, The composite according to any one of [1] to [9], wherein the storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the composite in elasticity measurement is 100 MPa or more.
_{E '30 / E' 250 ≦} 1000
E ′ ₃₀ : Storage elastic modulus of the composite at 30 ° C. E ′ ₂₅₀ : Storage elastic modulus of the composite at 250 ° C. [11] Total light transmittance is 60% or more [1] to [10 ] The composite_body | complex of any one of these.
[12] For the nonwoven fabric (a) containing cellulose,
(1) A method in which a monomer is impregnated and polymerized.
(2) A method in which a thermosetting resin precursor or a photocurable resin precursor is impregnated and cured.
(3) A method of drying after impregnating a solution of a resin other than cellulose.
(4) A method of impregnating a thermoplastic resin melt and cooling after defoaming.
The method for producing a composite according to any one of [1] to [11], wherein the resin (b) other than cellulose is filled and composited by any one of the methods.
[13] A plastic substrate for display comprising the composite according to any one of [1] to [11].
[14] A plastic substrate for a display front plate, comprising the composite according to any one of [1] to [11] and having a thickness of 500 μm or less.
[15] A display using the plastic substrate according to any one of [13] to [14].
[16] The display according to [15], wherein the display is a liquid crystal display.
[17] The display according to [15], wherein the display is an organic electroluminescence (organic EL) display.
[18] The display according to [15], wherein the display is a plasma display.
[19] The display according to [15], wherein the display is a field emission display.
[20] The display according to [15], wherein the display is a surface electric field display.
It is.

  The composite of the present invention is industrially useful because it is excellent in transparency and has a low coefficient of linear expansion while satisfying heat resistance. In particular, these characteristics are useful for various displays.

  Next, the present invention will be described in more detail.

  In the present invention, the cellulose-containing non-woven fabric (a) is a resin impregnated property obtained by using a fixed length drying with a drum dryer or organic solvent substitution / drying method with a gel-like film obtained by a stationary culture method using bacteria. Prepare a non-woven fabric (paper) or a dispersion containing cellulose in which fine cellulose fibers such as BC and MFC are highly dispersed, and form this by either the papermaking method or the coating method. It is produced by mixing non-cellulose fibers such as thermoplastic fibers, glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, and silica with cellulose together in the dispersion. Including non-woven fabrics.

  The thickness of the nonwoven fabric is not particularly limited, but is preferably 5 μm or more and 500 μm or less, more preferably 10 μm or more and 300 μm or less, and particularly preferably 20 μm or more and 200 μm or less. From the viewpoint of the strength of the nonwoven fabric, the thickness is preferably 5 μm or more, and a nonwoven fabric having a thickness of 500 μm or less does not require much time to impregnate the resin, and is therefore suitable for the industrial production process of compounding. It is preferable. In particular, from the viewpoint of industrial production, a method of forming a film from a dispersion of cellulose fibers is more preferable than forming a film by stationary culture because of its large area and excellent quality stability. In the case of the stationary culture method using bacteria, it is particularly preferable to use a high-porosity nonwoven fabric by appropriately selecting the drying method described later in order to enhance the resin impregnation property.

  Moreover, it is preferable that the fiber diameter of a cellulose fiber is comprised from the thin thing. More specifically, it is preferable not to contain fibers having a fiber diameter of a certain value or more, that is, the maximum fiber diameter of the fibers constituting the nonwoven fabric is preferably 1500 nm or less, more preferably 1000 nm or less, and particularly preferably 500 nm or less. When it is, the composite_body | complex of this invention can be produced suitably. In particular, when the maximum fiber diameter is 1500 nm or less, the composite of the present invention has extremely high transparency, and thus can be suitably used as a film or sheet-like molded body that can be developed for optical applications. Moreover, it is preferable because the mechanical strength is high and the coefficient of linear expansion is low.

  It is confirmed by SEM images as follows that the maximum fiber thickness of the fine cellulose fibers and other fibers used as the material for producing the composite of the present invention is 1500 nm or less. That is, the surface of the nonwoven fabric containing cellulose that is a material for producing the composite of the present invention is randomly observed at three locations with a scanning electron microscope (SEM) at a magnification equivalent to 10,000 times. When no single fiber having a fiber thickness exceeding 1500 nm can be confirmed in all the obtained SEM images, it is defined that the maximum fiber thickness is 1500 nm or less. However, in the image, when it is possible to clearly confirm that several fine fibers are bundled and have a fiber thickness of 1500 nm or more, the fibers are not regarded as fibers having a fiber thickness of 1500 nm or more.

  An example of such a measurement is shown in FIGS. FIG. 1 shows CJF002 bacteria similar to the Enterobacter family (Ministry of International Trade and Industry, Institute of Biotechnology, Biotechnology Research Institute, Patent Microorganism Depositary Center, Microbial indication “Enterobactersp. CJF-002”, accession number “FERM P-17799”, below , Simply a non-woven fabric obtained by a papermaking method using bacterial cellulose (hereinafter also referred to as BC) produced by Enterobacter genus CJF002 or CJF002. FIG. 2 shows an ultra-high pressure homogenizer using purified cotton linter. It is a part of the image regarding the nonwoven fabric similarly obtained by the papermaking method created with the refined linter fiber obtained by processing (operating pressure; 100 MPa, the number of times of passage to the homovalve; 20 passes). Both of them are obviously non-woven fabrics that can be used in the present invention because there are no fibers having a fiber thickness exceeding 1500 nm.

Furthermore, the cellulose which is the raw material of the nonwoven fabric (a) of the present invention is purified pulp obtained from wood (coniferous and hardwood), cellulose obtained from cotton such as cotton linter and cotton lint, and cellulose obtained from seaweed such as valonia and falcon. Natural cellulose such as cellulose obtained from sea squirt, cellulose produced by bacteria, or a fiber obtained by refining it and a fiber obtained by refining regenerated cellulose fiber can be used. In particular, from the viewpoint of a low linear expansion coefficient and mechanical strength, those having higher crystallinity are preferable, and in this respect, it is preferable to use fibers obtained from natural cellulose rather than regenerated cellulose. Among them, so-called bacterial cellulose (BC) produced by microorganisms such as acetic acid bacteria belonging to the Acetobacter family and CJF002 bacteria belonging to the Enterobacter family is a never-dry aqueous dispersion composed of fine fibers having a fiber diameter of 100 nm or less (in some cases Can be prepared as a gel), it is possible to prepare a dispersion for use in papermaking or coating under relatively mild dispersion conditions, which is technically advantageous. In contrast, general-purpose cellulose raw materials such as wood pulp and cotton linter are originally composed of fine fibers called microfibrils of 100 nm or less, but are naturally present in a dry state. Bundling proceeds and exists as thicker fibers (the same applies to regenerated cellulose fibers). In order to use such a general-purpose cellulose raw material in the present invention, it is repeatedly refined by using a miniaturization apparatus having a capability of separating multiple bundled fibers such as a high-pressure homogenizer and an ultra-high pressure homogenizer such as MFC. It is necessary to create a state where many fibers having a diameter of 100 nm or less are contained and no fiber having a fiber diameter of 1500 nm or more is present at all. Among them, fibers obtained by refining cellulose obtained from cotton particularly have a high crystallinity, and thus have an effect on physical properties. Even if the fibers are used, a highly transparent resin composite can be obtained. . The use of cellulose obtained from cotton as a starting material is particularly preferable because it is economically superior to the case of using BC.
Furthermore, in this invention, you may use the nonwoven fabric manufactured using the cellulose by which the surface was chemically modified as a nonwoven fabric (a). Chemical modification of the surface includes oxidation of the hydroxyl group (aldehyde or carboxylation at the C6 position), esterification of the hydroxyl group (acetate esterification, nitrate esterification, sulfate esterification, fatty acid esterification, etc.), cross-linking reaction between the surface OH (Cross-linking with formaldehyde, cross-linking with various cross-linking agents such as bifunctional urethane, etc.), oxidation reaction with cleavage between glucopyranoses, and the like are meant, but not limited thereto. However, destruction of the cellulose structure inside the fiber by these reactions must be avoided. The destruction of the cellulose structure is a state in which any one of the peak patterns (Non-patent Document 4) attributed to the C1-C6 position attributed to cellulose in the solid-state NMR method (13C-CP / MAS method) described later completely disappears. Means. The use of such chemically modified cellulose as a raw material for nonwoven fabrics may be effective for improving the strength of nonwoven fabrics containing cellulose, and in some cases, inherent properties of cellulose such as hygroscopicity. Can also be a method of improvement when it becomes a weak point in the use of the complex.
Cellulose-Structural and Functional Aspects, Editted by JF Kennedy, GOPhilips and PAWilliams, John Wiley & Sons, p87-92, 1989

  With the film thickness of the nonwoven fabric (a) containing cellulose in the present invention, the nonwoven fabric is cut into a 10 cm square, and using a point contact type film thickness meter (Mitutoyo Co., Ltd., Code: 547-401), Five points were measured for various positions of the nonwoven fabric, and the average value was defined as the film thickness d (μm).

Further, (a) the porosity of the nonwoven fabric containing cellulose is the porosity Pr (%) using the following formula from the 10 cm square film thickness d (μm) and the weight W (g) of the nonwoven fabric. Is calculated.
Pr = (d−W × 67.14) × 100 / d

The composite of the present invention comprises a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose. The weight composition of component (a) / component (b) is 0.1 wt% or more and 99 wt%. % / 1% to 99.9%, preferably 1% to 90% / 10% to 99%, more preferably 5% to 60% / 40% It is 95 weight% or less. It is necessary that the weight content of the component (a) is 0.1% by weight or more because the low linear expansion coefficient in the present invention is manifested, and that the content is 99% by weight or less. It is necessary to obtain a highly transparent composite. Furthermore, when the weight content of the component (b) is 1% by weight or more, it is suitable for increasing the transparency of the composite, and when the content is 99.9% by weight or less, the physical properties of cellulose are reduced. It is necessary for expression.
Next, (a) the porosity of the nonwoven fabric containing cellulose, which is the raw material of the composite of the present invention, is the impregnation property of the resin other than cellulose into the nonwoven fabric containing cellulose, and the transparency of the obtained composite From the viewpoints of properties and moldability, it is preferably 35% or more. Moreover, it is preferable that it is 95% or less from a viewpoint of the linear expansion coefficient of a composite_body | complex, intensity | strength, and heat resistance. More preferably, the porosity is 50% or more and 95% or less, and particularly preferably, the porosity is 70% or more and 95% or less. When the porosity is 50% or more, since the impregnation rate of the component (b) into the component (a) is high, the winding speed of the roll can be increased and the productivity is improved. Also, bubbles due to insufficient impregnation do not remain in the composite, and a composite having excellent transparency and low water absorption can be obtained continuously. Further, when the porosity is 95% or less, the strength is high, and it is difficult to break in the production process. Therefore, a composite having high strength and heat resistance and low linear expansion can be obtained continuously. In other words, when a nonwoven fabric containing (a) cellulose having a porosity of 50% or more and 95% or less is used, a composite excellent in balance of transparency, water absorption, heat resistance, strength, and linear expansion coefficient is industrially produced. From the point of view, it can be obtained realistically (eg, continuous production).
In addition, a nonwoven fabric containing cellulose by using a highly viscous resin as a resin (b) other than cellulose, by reducing the pressing pressure during composite production, or by laminating a composite film and other resin films In addition to the pore portion of (a), a phase of the resin alone can be provided, and the weight composition of the component (a) / (b) can be adjusted depending on the required physical properties. Heat resistance can be judged from the relationship of storage elastic modulus in dynamic viscoelasticity measurement. When the storage elastic modulus of the composite at 30 ° C. is E ′ ₃₀ , the storage elastic modulus of the composite at 150 ° C. is E ′ ₁₅₀ , and the storage elastic modulus of the composite at 250 ° C. is E ′ ₂₅₀ , E ′ ₁₅₀ and E 'A higher value of ₂₅₀ is considered to have higher heat resistance, enabling high-temperature processing in the production process, and higher heat resistance in the use environment. The 'storage modulus values of the complexes in ₁₅₀ and 250 ° C. E' storage modulus value E of the complex at 150 ° C. ₂₅₀ of not less than 100 MPa, also complex storage modulus at 30 ° C. and 150 ° C. The ratio E _'30 / E' _150, a value of 1000 or less, more preferably, if the value of the storage modulus ratio E _'30 / E' ₂₅₀ complex at 30 ° C. and 250 ° C. is 1000 or less, (b) Since the decrease in elastic modulus in the glass transition temperature region and rubbery flat region of the component resin is extremely small, physical properties such as strength at high temperatures are unlikely to decrease, and at the same time, the process of returning to room temperature after the high temperature treatment step in the manufacturing process The elastic modulus change in the process of temperature change under the usage environment is small, and it is preferable that warpage, disconnection of the aluminum wiring, peeling of the surface coating film, etc. do not occur.

In the present invention, natural cellulose is preferably used as the cellulose fiber in the nonwoven fabric (a) containing cellulose, as described above. Among them, it is preferable to use a raw material having a high degree of crystallinity. More specifically, the degree of crystallinity obtained by the solid state NMR method is preferably 50% or more from the viewpoint of linear expansion coefficient and heat resistance, and is 99% or less from the viewpoint of imparting flexibility of the composite. It is preferable. More preferably, it is 55% or more and 95% or less, and particularly preferably 60% or more and 80% or less. Since all the cellulose obtained from BC, seaweeds and cotton has a crystallinity of 60% or more, it can be particularly preferably used as a raw material for the cellulose fiber of the present invention. Here, the solid NMR method means a method for calculating the crystallinity from the peak intensity ratio of the spectrum obtained by solid high-resolution NMR (CP / MAS method) for 13C nuclei. More specifically, depending on the intensity ratio of two types of peaks (groups) belonging to the C4 position of the cellulose molecular chain skeleton appearing in the vicinity of 80 ppm-90 ppm in the spectrum (the carbon peak of glycine is set as 176 ppm as a standard substance). It is defined as follows.
Crystallinity = Intensity of peak 1 / ((Intensity of peak 1) + (Intensity of peak 2) (3)
In the formula (3), peak 1 means a peak centered at 89 ppm in the spectrum, and as described in Non-Patent Document 4 above, C4-O3-H existing in a crystalline region at a high density. Assigned to the C4 carbon that participates in the hydrogen bond of O5 ′, peak 2 means a peak centered at 84 ppm, and is assigned to the C4 carbon that does not participate in the hydrogen bond mode described above, which is mainly amorphous. It exists in the area.

Next, the nonwoven fabric (a) containing cellulose used in the present invention is an average defined by the following formula (1) obtained by vertically scanning light at 850 nm with respect to the nonwoven fabric in a state of being immersed in toluene. The transmittance T _{r, av} is preferably 0.70 or more, more preferably 0.75, particularly preferably 0.80 or more. Within this range, it is possible to provide a composite having high transparency and excellent uniformity. That is, from the viewpoint of the transparency, uniformity, and linear expansion coefficient of the composite, _{Tr and av} are preferably 0.70 or more. This is due to the following reason. Non-woven fabric containing cellulose having a slight refractive index difference with respect to toluene having a refractive index of 1.496 at 20 ° C. (According to Patent Document 5, the refractive index is 1.51 depending on the type of cellulose and the orientation of the sample. -1.62 range), when the fibers constituting the nonwoven fabric contain a large number of fibers having a fiber diameter not sufficiently smaller than the visible wavelength of about 400 nm, the scattering at the interface causes the light of the nonwoven fabric film. Since it acts as a permeation inhibiting factor, the average transmittance value under the above conditions is a physical property value reflecting the fineness of the constituent fibers of the nonwoven fabric or the fineness of the network structure of the nonwoven fabric. In the present invention, since the space in the nonwoven fabric containing cellulose is filled with a resin to form a composite, the average transmittance _{Tr, av} obtained under the above conditions is naturally correlated with the transparency of the obtained composite. To do.
“PolymerHandbook 3rd Edition”, Ed. By J. Brandrup and EHImmergut, John Wiley & Sons, New York, 1989

Here, in the present invention, Turbiscan ^™ MA-2000 (Eihiro Seiki Co., Ltd.) is used in the measurement of _{Tr and av} . This device was originally developed to evaluate the aging stability of solutions and dispersions, but the nonwoven fabrics that are the subject of the present invention were immersed in toluene and the measurements described below were performed. The inventors are extremely sensitive to information on the diameter of the fibers constituting the nonwoven fabric and information on the fineness of the network structure in the nonwoven fabric, and are extremely effective for the purpose of clarifying the differentiation between samples. Was found by.

The measurement of _{Tr and av} of a nonwoven fabric is performed as follows using the said apparatus. First, a target nonwoven fabric sample is cut into a 10 mm × 50 mm rectangle, immersed in a sample tube filled with toluene, and subjected to vacuum defoaming for the purpose of removing bubbles inside the nonwoven fabric. Next, the long axis of the nonwoven fabric sample impregnated with toluene is placed at a position where toluene is poured into a glass test tube attached to the apparatus so as to have a height of 5 cm and is in contact with the bottom cover of the test tube. Install in close contact with the inner wall of the test tube so that it is in the length direction of the test tube. At this time, the laser beam is installed perpendicularly to the vicinity of the center of the nonwoven fabric sample and at a position where the laser beam strikes the nonwoven fabric from the near wall surface. This state is shown in FIG. Next, according to the usual usage of the apparatus, a laser beam of 850 nm is scanned in the length direction of the test tube. The apparatus detects the transmittance _Tr in the test tube length direction within a total range of 60 mm every 40 μm by a conventional method, but this profile is confirmed, and the center 30 mm of the portion considered to be hit by the nonwoven fabric is obtained. Cut (target), and calculate the average value T _{r, 1} of the transmittance T _r of a total of 750 points (FIG. 4). Next, the same measurement is performed in a state where only 5 cm of toluene is injected into the same test tube as the above measurement (no nonwoven fabric is installed), and the average value of the transmittance T _r of 750 points in total, T _{r, 2} is also obtained. calculate. Using T _{r, 1} and T _{r, 2} obtained in this way, the transmittance of the nonwoven fabric under toluene impregnation, T _{r, av,} is obtained by equation (1).
T _{r, av} = T _{r, 1} / T _{r, 2} (1)

Next, in the above measurement, when the standard deviation of _Tr measurement in the presence of the nonwoven fabric is _{Tr, sd1} , and the standard deviation of _Tr measurement with only toluene is _{Tr, sd2} , the nonwoven fabric impregnated with toluene. The standard deviation _{Tr, sd} of the membrane transmittance distribution is
T _{r, sd} = T _{r, sd1} −T _{r, sd2}
Using this, the film quality uniformity parameter H is defined as follows as a measure of film quality uniformity in the toluene-impregnated state.
H = T _{r, sd} / T _{r, av} (2)

At this time, the non-woven fabric containing cellulose used in the present invention is as described above, but the average transmittance T _{r, av} is 0.70 or more and at the same time the H value is 0.018 or less. In addition, the composite of the present invention can be provided. Preferably, it is 0.012 or less, more preferably 0.008 or less, and the composite of the present invention having extremely excellent uniformity can be provided. It is preferable to use a non-woven fabric having a value of H of 0.018 or less from the viewpoint of variation in the density of cellulose existing in the portion when the composite is formed. If there is variation in the density of cellulose, low density places become structural defects, and as a result, the strength of the composite as a whole is reduced, which is not appropriate. In order to provide a nonwoven fabric excellent in transparency under toluene impregnation and satisfying such conditions of _{Tr, av} and H, and excellent in film quality uniformity, it is necessary to pay attention to the following points. First, it is preferable to use a fiber having the smallest possible fiber diameter. Specifically, the maximum fiber diameter is preferably 1500 nm or less, more preferably 1000 nm or less, and most of the fibers formed at the same time are preferably composed of fibers of 500 nm or less, more preferably 400 nm or less. More specifically, it is preferable that 50% or more of the fibers in the nonwoven fabric confirmed by SEM are fibers of 500 nm or less. Next, when forming the film, it is extremely important to prepare a dispersion with as high uniformity as possible regardless of whether it is a papermaking method or a coating method. Although this condition (dispersing means and the like) will be described later, an appropriate dispersing means is selected according to the selected film forming method. Furthermore, by following the contents based on the nonwoven fabric production method disclosed in the present invention as described later (for example, in the case of the papermaking method, using a filter cloth under appropriate conditions), _{Tr, av} and H are The film | membrane controlled by the said range can be provided suitably.

  In the present invention, it is preferable that a dispersion in which cellulose fibers are dispersed in water, an organic solvent or a mixed solvent thereof is first prepared, and then the dispersion is formed into a film by a papermaking method or a film is formed by a coating method. The nonwoven fabric (a) containing cellulose that can be used in the invention can be produced. However, in the present invention, since fine cellulose fibers are used as described above, it is extremely important to prepare a dispersion controlled to an appropriate dispersion state.

  In the coating method, after coating, the dispersion medium is dried to form a film. Therefore, it is desirable to disperse the cellulose fibers as high as possible in the dispersion used. On the other hand, in the papermaking method in which the dispersion liquid is usually cast on a metal wire and then the dispersion medium is filtered, the dispersion liquid is not highly dispersed and the fibers are appropriately associated without agglomeration. Need to produce. These states are controlled by selection of a disperser, dispersion conditions, addition of a mixed medium such as an organic solvent into the dispersion, a dispersion aid, and the like.

  In the present invention, cellulose fibers having a fine diameter are used, but as an effective disperser for enhancing the dispersion state, a blender type disperser or a high-pressure homogenizer is effective. In the case of a coating method, an ultra-high pressure homogenizer is also effective. is there. Further, since such a dispersion works so that the fine cellulose fibers themselves stabilize the dispersion of the cellulose fibers, a stable dispersion can be obtained at a higher concentration. In particular, in the coating method in which the drying process is performed as it is from the state of the applied dispersion, it is desirable to set the concentration of cellulose fibers in the dispersion higher, preferably 0.3% by weight to 3.0% by weight More preferably, it is 0.4 wt% or more and 2.5 wt% or less, and particularly preferably 0.5 wt% or more and 2.0 wt% or less. Since the viscosity of the dispersion can vary greatly depending on the presence or absence of the dispersion medium and additives, the concentration of the cellulose fibers is appropriately set so that the viscosity is appropriate for the coating step. If it is 0.3% by weight or more, it is advantageous from the viewpoint of industrial production because a large amount of energy is not required to remove the dispersion medium such as water, and any blending is possible at a fiber concentration lower than 3.0% by weight. The composition is preferable in terms of operation without the viscosity being too high. The dispersion is mixed with an inorganic substance such as silica, fibers other than cellulose (thermoplastic resin fibers, glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers), etc., as long as the present invention is not impaired. The nonwoven fabric (a) containing can be manufactured. Thus, when using fibers other than cellulose, the maximum fiber thickness is not particularly limited, but is preferably 1500 nm or less, more preferably 1000 nm or less, and particularly preferably 500 nm or less. It is possible to obtain a highly transparent material by using.

Next, the manufacturing method which forms into a film by the papermaking method the nonwoven fabric containing the cellulose used in manufacture of the composite_body | complex of this invention is described. A dispersion for papermaking of cellulose fibers having a maximum fiber thickness of 1500 nm or less, a dispersion average diameter of fine cellulose fibers of 1 μm to 300 μm, and a fine cellulose fiber concentration of 0.01% by weight to 1.0% by weight Prepare as is. Dispersion average diameter (hereinafter referred to as R _v) of fine cellulose fibers in papermaking dispersion, the water permeability is required than 1μm in terms of efficiency of the paper, 300 [mu] m or less from the viewpoint of uniformity of the nonwoven fabric It is necessary to be. The dispersion average diameter (R _v ) referred to here means that the dispersion for papermaking is a laser scattering particle size distribution measuring device (Horiba, Ltd., laser diffraction / scattering particle size distribution measuring device LA-920, the lower limit detection value is 0.02 μm), which means a volume average arithmetic average diameter obtained by measurement at room temperature. In this measurement, the arithmetic average diameter related to the volume distribution is used according to Mie's scattering theory, and the relative refractive index of the cellulose used in this case with respect to the refractive index of water is 1.20.
M. Kerker, “The Scattering of Light”, USA, Academic Press, New York, NY, 1969, Cap. 5.

R _v of papermaking dispersion, preferably 3μm or more 200μm or less, more preferably to be in the 100μm below the range of 5 [mu] m, it is possible to provide a nonwoven fabric of the present invention having more excellent uniformity.
The concentration of fine cellulose fibers in the papermaking dispersion during papermaking is 0.01 wt% or more and 1.0 wt% or less, preferably 0.05 wt% or less and 0.5 wt% or less, more preferably It is 0.1 wt% or more and 0.4 wt% or less. From the viewpoint of ensuring the stability of the dispersion, the fine cellulose fiber concentration in the papermaking dispersion is preferably 0.01% by weight or more. It is preferable that the fine cellulose fiber concentration is 0.1% by weight or more because the fine cellulose fiber layer and the water separation layer are difficult to separate in the dispersion. The fine cellulose fiber concentration is preferably 1.0% by weight or less from the viewpoint of the viscosity of the dispersion. When the content is 1.0% by weight or less, the viscosity of the dispersion is not too high, and uniform papermaking can be performed.

Next, as a filter cloth at the time of papermaking, from the viewpoint of avoiding a decrease in yield of the nonwoven fabric due to the passage of fine cellulose fibers through the filter cloth and avoiding a decrease in productivity due to a decrease in water permeability, a dispersion for papermaking A filter cloth having the ability to filter 95% or more of fine cellulose fibers by filtration at 25 ° C. under atmospheric pressure and having a water permeation amount of 0.005 cc / cm ² · s or more at 25 ° C. under atmospheric pressure. Is preferably used. The filter cloth is placed on the wire of the paper making apparatus, and the paper dispersion is filtered on the filter cloth to deposit fine cellulose fibers on the filter cloth for paper making. A wet nonwoven fabric (wet paper) First make. In particular, the strength of the wet paper is important in terms of paper feeding in the continuous film forming process. Therefore, it is important to control the solid content concentration in the wet paper that most affects the wet paper strength to an appropriate range. is there. The solid content concentration of fine cellulose fibers in the wet paper is preferably 4% by weight to 30% by weight, more preferably 8% by weight to 25% by weight, and particularly preferably 10% by weight to 20% by weight. A wet nonwoven fabric (wet paper) is produced. In this case, the solid content concentration of the wet paper is preferably 40% by weight or less from the viewpoint of controlling the porosity in the drying step. It is also possible to continuously wind up the nonwoven fabric of the present invention in the form of a roll by peeling the nonwoven fabric from the filter cloth described above before or after the drying step.
Here, the filter cloth having the ability to filter out 95% or more by filtration at 25 ° C. under atmospheric pressure satisfies the following conditions. That is, on a coarse cylindrical funnel type or buchner funnel glass filter (for example, Buchner funnel glass filter, 25G manufactured by Shibata Kagaku Co., Ltd.) having a pore size of 100 μm or more and an outer diameter in the range of 100 to 125 μm. The filter cloth to be applied is attached in a wet state, and a filtration test under atmospheric pressure of the paper dispersion of the present invention is performed. At this time, the content of fine cellulose fibers contained in the filtrate is measured by a drying method or the like, and as a filtration rate,
(Fine cellulose content before filtration in the papermaking dispersion used in the filtration experiment−Fine cellulose content contained in the filtrate) × 100 / (Fine cellulose before filtration in the papermaking dispersion used in the filtration experiment) Content)(%)
When this value is calculated, it means a film, a nonwoven fabric, a woven fabric, a glass nonwoven fabric, a metal mesh or the like having a value of 95% or more, preferably 98% or more.

Moreover, it is preferable that this filter cloth can pass water easily at the time of the filtration test on the conditions mentioned above. That is, it is preferable permeation amount of water under 25 ° C. atmospheric pressure is less than 0.005cc / cm ² · s or more 0.300cc / cm ² · s. If the amount of transmitted 0.005cc / cm ² · s or more 0.300cc / cm ² · s or less of water, the resistance is extremely small when the dispersion medium passes through the filter cloth, it takes much time for paper making It is preferable from the viewpoint of productivity. This is particularly important during continuous papermaking as described below.

  Among filter cloths satisfying such conditions, the filter cloth used in the present invention is preferably a nonwoven fabric or woven fabric made of organic polymer fibers, or a porous film made of organic polymers. Furthermore, in the kind of organic polymer, polyolefins such as polyethylene terephthalate, polyethylene, and polypropylene, polyvinyl chloride, polyvinylidene chloride, and polyvinyl fluoride are used in comparison with the same kind of fine cellulose fibers used in the present invention such as cellulose. Non-cellulosic general-purpose organic polymers such as vinylidene chloride and nylon-6,6, nylon-6 are preferred.

  The shape of the filter cloth may be a non-woven fabric, a woven fabric, or a porous membrane as long as it satisfies the above filterability conditions. Since these selections are related to the peelability from the filter cloth when the non-woven fabric containing microporous cellulose is peeled from the filter cloth after papermaking, it greatly contributes to the uniformity of the thickness distribution of the product. is important. For example, when the non-woven cloth containing the microporous cellulose of the present invention is peeled off from the filter cloth after drying, the ease of peeling of the cellulose from the filter cloth becomes a problem.

  As described above, since the performance required for the filter cloth used in the present invention is filterability (fine cellulose fiber) and permeability (dispersion medium), the pore diameter (through hole diameter) of the filter cloth is an important factor. However, there are various shapes that can be used as a filter cloth, and in addition, since part of the filter cloth material swells in a dispersion medium environment centering on the aqueous system used in the present invention, the pore diameter of the filter cloth measured under drying and Often different from the actual pore size. Since various materials can be allowed, it is not possible to simply limit the appropriate pore size.

Examples of the filter cloth that can be used in the present invention include a 460 mesh fabric made of polyethylene terephthalate. The pore diameter is approximately 20 μm × 20 μm. The filter cloth has a filtration rate of almost 100% fine cellulose fibers in some dispersions even though fibers smaller than 20 μm are also included in the dispersion in R _v smaller than 20 μm. . This is considered to be due to the fact that fibers having a small particle size are absorbed by the fiber assembly during the paper making process, and the concentration thereof is increased by filtration while growing.

  Furthermore, the nonwoven fabric containing the cellulose used by this invention can control the porosity of the nonwoven fabric obtained by selecting a drying method suitably with respect to the wet paper obtained at the said process, for example. Although this invention does not specifically limit the drying method of the wet paper obtained at the said process, the following method can be mentioned as an example. When wet paper containing water as a dispersion medium is directly attached to a metal surface like a drum dryer and dried, a nonwoven fabric containing cellulose having a porosity of about 35% to about 65% is obtained. Can do. By replacing the water in the wet paper with an organic solvent or an organic solvent / water mixed solution and then drying, a nonwoven fabric having a higher porosity than that obtained by drying with a drum dryer can be obtained. Although it depends on the conditions, according to the drying method, a nonwoven fabric having a porosity of about 60% or more and about 95% or less can be obtained. Furthermore, a nonwoven fabric having a high porosity of about 70% or more and about 95% or less can also be obtained by freeze-drying wet paper using water as a medium. By appropriately selecting these drying methods and more detailed conditions (drying temperature, type of organic solvent to be substituted, etc.), the porosity can be designed within the preferred range of the present invention. Moreover, as an organic solvent used in this case, an organic solvent having a relative dielectric constant of 3 or less, which is a low polarity hydrophobic solvent such as an aliphatic hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, or a halogenated hydrocarbon. It can be suitably used. More specifically, cyclohexane, toluene, carbon tetrachloride and the like are extremely effective and suitable for making a microporous nonwoven fabric having a certain range of air permeability provided by the present invention. In particular, when the solvent contained in the wet paper is water and is replaced with an organic solvent that does not dissolve in water such as cyclohexane or toluene, for example, water such as acetone, methyl ethyl ketone, iso-propyl alcohol, or iso-butyl alcohol is used. A two-stage substitution method is also effective in which substitution is first performed with a dissolving organic solvent and then substitution is performed with a water-insoluble solvent such as cyclohexane or toluene. The solvent used at this time may be a mixed solvent with water or a mixed solvent of organic solvents. Moreover, a high-porosity nonwoven fabric can also be obtained by substituting with one kind of organic solvent having a certain degree of solubility in water.

Examples of such organic solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and other alkyl alcohols having 1 to 4 carbon atoms, dimethylformamide, dimethyl Amide solvents such as acetamide, ketones such as acetone, methyl ethyl ketone, diacetone alcohol or keto alcohols, ethers such as tetrahydrofuran, dioxane, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexane Alkylene glycols containing 2-6 carbon atoms, such as triol, thiodiglycol, hexylene glycol, diethylene glycol, ethylene glycol Cellosolves such as monomethyl ether and ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol n-butyl ether, carbitols such as triethylene glycol n-butyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Other glycol derivatives such as 2-isopropoxyethanol, 2-butoxyethanol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 1,2-hexanediol, 1,2-octanediol, etc. 1,2-alkyldiols, and further, polyethylene glycol, polypropylene glycol, glycerin and derivatives thereof, 3-methoxy-1-propanol, 3-methoxy-1-butanol, N-methyl-2-pyrrolidone, 2-pyrrolidone 1,3-dimethyl-2-imidazolidinone, and the like, but are not limited thereto.
In addition, for example, a microporous cellulose nonwoven fabric can be obtained by using an organic solvent as described above or a mixed solution of an organic solvent and water as described above as a dispersion medium in a papermaking dispersion. . If the organic solvent as described above is contained in the nonwoven fabric containing the medium immediately before drying, a nonwoven fabric having a high porosity can be obtained. What is necessary is just to select the timing of injection | throwing-in of the organic solvent in a manufacturing process according to the objective.

  The resin (b) other than cellulose in the present invention is at least one resin selected from a thermoplastic resin, a thermosetting resin, a photocurable resin, and a cured resin. As thermoplastic resins, styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic olefin resins, polyamide resins Examples thereof include resins, polyphenylene ether resins, thermoplastic polyimide resins, polyacetal resins, polysulfone resins, and amorphous fluorine resins.

Styrenic resin refers to homopolymers of vinyl aromatic monomers or copolymers with other monomers, and examples of vinyl aromatic monomers include styrene, α-methylstyrene, paramethylstyrene, and the like. Among them, a styrene homopolymer or a copolymer with another monomer is preferable. In the case of a homopolymer, it may be one having a stereoregularity in the chain (isotropy, syndiotactic) or one (atactic). Examples of other copolymerizable monomers include acrylonitrile, methacrylonitrile, isoprene, butadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and vinyl acetate. For example, acrylonitrile-styrene copolymer Polymers, styrene-methacrylic acid copolymers and the like are preferable because the refractive index of the resin can be adjusted by the copolymerization ratio. For example, when a monomer of polystyrene (refractive index, about 1.59) and a monomer of polyacrylonitrile (refractive index of about 1.52) are copolymerized at 71:21, a resin having a refractive index of about 1.57 is obtained. And can be suitably used as a resin (b) other than cellulose of the present invention.
Examples of the copolymerization form include block copolymerization, random copolymerization, and graft copolymerization.

  Acrylic resins include methacrylic acid esters such as cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, and methyl methacrylate, and acrylics such as methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, and 2-ethylhexyl acrylate. One or more monomers selected from acid esters are polymerized. Of these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable. Examples of monomers copolymerizable with methyl methacrylate include other alkyl methallylic esters, alkyl acrylates, aromatic vinyl compounds such as styrene, vinyl toluene and α-methyl styrene, acrylonitrile, methacrylonitrile and the like. Mention may be made of vinyl cyanides, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, unsaturated carboxylic acid anhydrides such as maleic anhydride, and unsaturated acids such as acrylic acid, methacrylic acid and maleic acid. Moreover, alicyclic acrylic resins, such as tricyclodecyl methacrylate, are also mentioned.

  The aromatic polycarbonate resin is an aromatic polycarbonate derived from an aromatic dihydroxy compound. Examples of the aromatic dihydroxy compound include 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2, Bis (hydroxyaryl) alkanes such as 2-bis (4-hydroxyphenyl) propane, bis (1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. Hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4 ' -Dihydroxy-3,3'-dimethyl Dihydroxyaryl sulfides such as phenyl sulfide, dihydroxyaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethylphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4 , 4'-dihydroxy-3,3'-dimethylphenylsulfone, and the like. Among these, 2,2-bis (4-hydroxyphenyl) propane (common name, bisphenol A) is particularly preferable. These aromatic dihydroxy compounds can be used alone or in combination of two or more.

  The aromatic polyester-based resin is not particularly limited, but specific examples include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polyarylate, and the like.

  Examples of the aliphatic polyester resin include a polymer mainly composed of aliphatic hydroxycarboxylic acid and a polymer mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol. Specifically, polymers having aliphatic hydroxycarboxylic acid as a main component include polyglycolic acid, polylactic acid, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-4-hydroxyvaleric acid, poly-3- Hydroxyhexanoic acid or polycaprolactone, etc., and examples of the polymer mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol include polyethylene adipate, polyethylene succinate, polybutylene adipate, or polybutylene succinate. Is mentioned.

  Aliphatic polyolefin resins include polyethylene, polypropylene, ethylene propylene copolymer, polymethylpentene, polybutene, ethylene vinyl acetate copolymer, ionomer (ethylene acrylic acid polymer salt, styrene sulfonate, etc.) resin, and Examples thereof include copolymers thereof and modified products of maleic acid.

  The cyclic olefin-based resin is a polymer containing a cyclic olefin skeleton in a polymer chain, such as nobornene or cyclohexadiene, or a copolymer containing these, and the production method thereof is not particularly limited. Examples of the cyclic olefin-based resin include norbornene-based resins composed of a repeating unit of a norbornene skeleton or a copolymer of a norbornene skeleton and a methylene skeleton. “Arton” manufactured by JSR, “ZEONEX” manufactured by Nippon Zeon, “Zeonoa”, “Appel” manufactured by Mitsui Chemicals, and “Topas” manufactured by Chicona. Specific examples include JP-A-62-252406, JP-A-62-2252407, JP-A-2-133413, JP-A-63-145324, JP-A-63-264626, Japanese Laid-Open Patent Publication No. 1-2240517, Japanese Patent Publication No. 57-8815, Japanese Laid-Open Patent Publication No. 5-39403, Japanese Laid-Open Patent Publication No. 5-43663, Japanese Laid-Open Patent Publication No. 5-43834, Japanese Laid-Open Patent Publication No. 5-70655, Japanese Laid-open Patent Publication No. -279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, JP-A-9-241484, and the like.

  The polyamide resin is not particularly limited as long as it is a known polyamide resin. For example, polycaprolactam (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612) ), Polyundecamethylene adipamide (nylon 116), polyundecalactam (nylon 11), polydodecalactam (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I) ), Polynonanemethylene terephthalamide (9T), polyhexamethylene terephthalamide (6T), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-amino) Chlorhexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), polydodecane terephthalamide (nylon 12T), and these Of these, polyamide copolymers containing at least two different polyamide-forming components, and mixtures thereof.

  Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). -Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and further copolymers of 2,6-dimethylphenol and other phenols (for example, And polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol as described in JP-B-52-17880. Can be mentioned. Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture. In addition, the polyphenylene ether resin that can be used in the present invention may be a polyphenylene ether modified in whole or in part. The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure. The polyphenylene ether modified with at least one modifying compound having a group. Since the polyphenylene ether resin has high heat resistance and excellent electrical characteristics, it can be suitably used for high heat resistance applications and electronic parts.

The monomer in the present invention refers to a monomer constituting these thermoplastic resins.
The number average molecular weight of these thermoplastic resins is generally 1000 or more, preferably 5000 or more and 5 million or less, and more preferably 10,000 or more and 1 million or less.

  These thermoplastic resins can be used alone or in admixture of two or more. In the case of using a mixture of two or more thermoplastic resins, it is preferable because the refractive index of the resin can be adjusted by the mixing ratio. For example, when polymethyl methacrylate (refractive index: about 1.49) and acrylonitrile styrene (acrylonitrile content: about 21%, refractive index: about 1.57) are mixed at 50:50, a resin having a refractive index of about 1.53 is obtained. The resin (b) other than cellulose of the present invention can be suitably used.

  The thermosetting resin and photocurable resin used in the present invention mean a relatively low molecular weight substance that is liquid, semi-solid or solid at room temperature and exhibits fluidity at room temperature or under heating. To do. These can be an insoluble and infusible resin formed by forming a network-like three-dimensional structure while increasing the molecular weight by causing a curing reaction or a crosslinking reaction by the action of a curing agent, a catalyst, heat or light. In addition, the cured resin in the present invention means a resin obtained by curing the thermosetting resin or the photocurable resin.

  The thermosetting resin used in the present invention is not particularly limited, but specific examples include epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, Silicon resins, benzoxazine resins, phenol resins, unsaturated polyester resins, bismaleimide triazine resins, alkyd resins, furan resins, melamine resins, polyurethane resins, aniline resins, and other industrially used resins and these resins of 2 or more The resin obtained by mixing is mentioned. Among these, epoxy resins, allyl resins, unsaturated polyester resins, vinyl ester resins, thermosetting polyimide resins, and the like are suitable for use as optical materials because they have transparency.

  The epoxy resin refers to an organic compound having at least one epoxy group. The number of epoxy groups in the epoxy resin is preferably 1 or more and 7 or less per molecule, and more preferably 2 or more per molecule. Here, the number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin. It does not specifically limit as said epoxy resin, A conventionally well-known epoxy resin can be used, For example, the epoxy resin etc. which were shown below are mentioned. These epoxy resins may be used independently and 2 or more types may be used together. These epoxy resins are thermosetting resin precursor epoxy compounds, and by using a curing agent, a cured epoxy resin that is a cured product of the epoxy resin can be obtained. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, phenol novolac type epoxy resin, novolak type epoxy resin such as cresol novolak type epoxy resin, Aromatic epoxy resins such as trisphenol methane triglycidyl ether and their water additives and bromides can be mentioned. Also, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, bis (3,4 -Epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3 , 4-epoxycyclohexanone-meta-dioxane, alicyclic epoxy resins such as bis (2,3-epoxycyclopentyl) ether, etc. Also, 1,4-butanediol diglycidyl ether, 1,6-to Diglycidyl ether of xanediol, Triglycidyl ether of serine, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyoxyalkylene glycol containing an alkylene group having 2 to 9 carbon atoms (preferably 2 to 4 carbon atoms) And aliphatic epoxy resins such as polyglycidyl ether of a long-chain polyol containing polytetramethylene ether glycol, etc. In addition, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Glycidyl ester-type epoxy resins such as diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, dimer acid glycidyl ester, and water thereof In addition, triglycidyl isocyanurate, N, N′-diglycidyl derivative of cyclic alkylene urea, N, N, O-triglycidyl derivative of p-aminophenol, N, N, O of m-aminophenol -Glycidylamine type epoxy resins such as triglycidyl derivatives and their hydrogenated products, etc. Also, glycidyl (meth) acrylate and radical polymerizable monomers such as ethylene, vinyl acetate, (meth) acrylic acid ester, etc. In the present invention, (meth) acryl means acryl or methacryl, and a polymer mainly composed of a conjugated diene compound such as epoxidized polybutadiene or a partially hydrogenated product thereof. And an epoxidized unsaturated carbon double bond in the polymer. Also, a polymer block mainly composed of a vinyl aromatic compound, such as epoxidized SBS, and a polymer block mainly composed of a conjugated diene compound or a partially hydrogenated polymer block thereof are contained in the same molecule. Examples of the block copolymer include epoxidized unsaturated carbon double bonds of a conjugated diene compound. Moreover, the polyester resin etc. which have 1 or more per molecule, Preferably 2 or more epoxy groups are mentioned. Examples thereof include urethane-modified epoxy resins and polycaprolactone-modified epoxy resins in which urethane bonds and polycaprolactone bonds are introduced into the structure of the epoxy resin. Examples of the modified epoxy resin include a rubber modified epoxy resin in which a rubber component such as NBR, CTBN, polybutadiene, and acrylic rubber is contained in the epoxy resin. In addition to the epoxy resin, a resin or oligomer having at least one oxirane ring may be added. Moreover, the thermosetting resin and composition containing a fluorene group, such as a fluorene containing epoxy resin, a fluorene containing acrylate resin, a fluorene containing epoxy acrylate resin, or its hardened | cured material is also mentioned. These fluorene-containing epoxy resins are suitably used because they contain a fluorene group in the molecule and thus have a high refractive index and high heat resistance. The curing agent used for the curing reaction of the epoxy resin is not particularly limited, and conventionally known curing agents for epoxy resins can be used. For example, amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, A tertiary amine compound, an imidazole compound, a hydrazide compound, a melamine compound, an acid anhydride, a phenol compound, a thermal latent cationic polymerization catalyst, a photolatent cationic polymerization initiator, dicyanamide, and derivatives thereof may be mentioned. These hardening | curing agents may be used independently and 2 or more types may be used together.

  Moreover, as a photocurable resin used in this invention, the epoxy resin containing a latent photocationic polymerization initiator etc. are mentioned, for example. These thermosetting resins or photocurable resins may be used alone or in combination of two or more. In addition, when hardening the said photocurable resin, you may apply heat simultaneously with light irradiation. In the present invention, the curing agent and curing catalyst used in combination with the thermosetting resin and the photocurable resin are not particularly limited as long as they are used for curing the thermosetting resin and the photocurable resin. Specific examples of the curing agent include polyfunctional amines, polyamides, acid anhydrides, and phenol resins. Specific examples of the curing catalyst include imidazole. These may be used alone or as a mixture of two or more. it can.

  The polyimide resin in the present invention is not particularly limited, but is a resin containing an imide group in the main chain skeleton, and any of thermoplastic and thermosetting polyimide resins can be used. Specifically, polyimide, polyamide imide, polyether imide, polyester imide, polysiloxane imide and the like can be mentioned, and specific examples include Japanese Patent No. 2218568, Japanese Patent No. 2129731, Japanese Patent No. 2738453, Japanese Patent No. 2746555, Japanese Patent No. 2909844, Japanese Patent No. 3034838, Japanese Patent No. 1531563, Japanese Patent No. 1836437, Japanese Patent No. 2597214, Japanese Patent No. 2597215, Japanese Patent No. 2671162, Japanese Patent No. 1954076, Japanese Patent No. 2034676, Japanese Patent No. 2514313, It is described in Japanese Patent No. 2587810, Japanese Patent No. 2523682, Japanese Patent No. 2566250, Japanese Patent No. 2566251, and the like.

  Moreover, resin obtained by mixing 2 or more types of thermoplastic resins, thermosetting resins, photocurable resins, and resin cured products can also be used.

  In this invention, (a) component is 0.1 weight% or more and 99 weight% or less, and (b) component is 1 weight% or more and 99.9 weight% or less. From the viewpoint of water absorption, the component (a) must be 99% by weight or less, and the component (b) must be 1% by weight or more. From the viewpoint of linear expansion coefficient and heat resistance, the component (a) is 0.1% by weight or more It is necessary that the component (b) is 99.9% by weight or less. A preferred range is that the component (a) is 0.2 wt% or more and 80 wt% or less, and the component (b) is 20 wt% or more and 99.8 wt% or less. More preferable range is that the component (a) is 10% or more and less than 60% by weight, and the component (b) is more than 40% by weight and 90% by weight or less. Particularly preferable ranges are (a) component of more than 10% by weight and 50% by weight or less, and (b) component of 50% by weight or more and less than 90% by weight. The resin content can be obtained from the weight of the cellulose nonwoven fabric before impregnation with the resin and the weight of the composite after impregnation, and can also be obtained from the weight of the remaining cellulose nonwoven fabric by removing only the resin with a soluble solvent. As other methods, there are a method of obtaining from the specific gravity of the resin and the specific gravity of cellulose, and a method of obtaining by quantitatively determining the functional groups of the resin and cellulose using NMR and IR.

  Further, the glass transition temperature of the resin (b) other than cellulose is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher. From the viewpoint of heat resistance of the composite, the glass transition temperature is desirably 50 ° C. or higher.

  In the present invention, it is preferable that the total light transmittance of a 100 μm molded product of the resin (b) other than cellulose is 70% or more. When it is 70% or more, the transparency of the composite is improved, which is preferable. More preferably, it is 80% or more, and particularly preferably 85%.

  In the present invention, the refractive index of the resin (b) other than cellulose is preferably more than 1.49 and less than 1.59. More preferably, it is 1.50 or more and 1.58 or less, and particularly preferably 1.53 or more and 1.57 or less. Within this range, the difference from the refractive index of the cellulose used as component (a) is small, so the transparency of the composite is further improved, which is preferable. In order to make the refractive index of the resin (b) other than cellulose close to the refractive index of cellulose as the component (a), two or more kinds of resin monomers are copolymerized, and the refractive index is adjusted and used. It is also very effective to adjust the refractive index by blending two or more kinds of resins. In addition, it is preferable that two or more types of resins to be used are compatible because transparency is improved. The combination of compatible resins is not particularly limited, and examples thereof include a polymethyl methacrylate / styrene-acrylonitrile copolymer blend. In addition, as the component (b), it is very effective to control the refractive index by a combination of a thermosetting resin and a photocurable resin, a curing agent, and a curing accelerator. In this case, two or more kinds of resins, curing agents, and curing accelerators can be used. For example, although not particularly limited, it is effective to adjust the refractive index by mixing a bisphenol A type epoxy resin and a hydrogenated bisphenol A type epoxy resin. As the component (b), an organic-inorganic hybrid material obtained by hybridizing a thermosetting resin and a photocurable resin with a metal alkoxide such as silica, titanium, or zinc is also very effective for controlling the refractive index.

In the present invention, the Abbe number of the resin (b) other than cellulose is preferably 30 or more and 70 or less, more preferably 40 or more and 60 or less. If it is within this range, the refractive index wavelength dependency of the resin (b) other than cellulose is reduced, which is preferable because the transparency of the composite is further improved. The Abbe number (υd) here indicates the wavelength dependence of the refractive index, that is, the degree of dispersion, and can be obtained by υd = (nD−1) / (nF−nC). Here, nC, nD, and nF are refractive indices with respect to the C-line (wavelength 656 nm), D-line (589 nm), and F-line (486 nm) of the Brownhofer line, respectively. The refractive index of a material having a small Abbe number varies greatly depending on the wavelength.
A preferable in-plane retardation (Re) value of the composite obtained in the present invention is 50 nm or less, more preferably 40 nm or less, and particularly preferably 30 nm or less. By controlling Re within a preferred range, the viewing angle characteristics are excellent when used in a liquid crystal display device or the like. At present, polycarbonate films and polyphenylene ether films, which are plastic films that have been studied, have a problem in that the range of use is limited because the in-plane retardation tends to increase at the film forming stage. In the composite of the present invention, by using a nonwoven fabric (a) containing cellulose in which cellulose fibers having a fiber diameter of up to 1500 nm or less are irregularly arranged in the plane direction and impregnating a resin (b) other than cellulose. In order to manufacture, in-plane retardation (Re) can be controlled in a preferable range.
The photoelastic coefficient is described in various documents (see, for example, Non-Patent Document 7) and is defined by the following equation.
| CR | = | Δn | / σR | Δn | = | n1-n2 |
(Where: | CR |: absolute value of photoelastic coefficient, σR: stretching stress, | Δn |: absolute value of birefringence, n1: refractive index in stretching direction, n2: refractive index perpendicular to stretching direction)
The closer the value of the photoelastic coefficient is to zero, the smaller the change in birefringence due to external force, which means that the change in birefringence designed for each application is small. The composite obtained by the present invention preferably has an absolute value of the photoelastic coefficient of 80 × 10 ⁻¹² / Pa or less. More preferably, it is 50 * 10 < ^-12 > / Pa or less, More preferably, it is 20 * 10 < ^-12 > / Pa or less. If the photoelastic coefficient is within this range, the change in birefringence due to stress is small, so that the contrast and the uniformity of the screen are excellent when used in a liquid crystal display device or the like. The polycarbonate film (photoelastic coefficient 90 × 10 ⁻¹² / Pa), which is currently being investigated, has a large photoelastic coefficient, so that the birefringence tends to increase due to the addition of stress during use. There was a problem that it was. In the composite of the present invention, the nonwoven fabric (a) containing cellulose, in which cellulose fibers having a fiber diameter of up to 1500 nm or less are irregularly arranged in the plane direction, and the absolute value of the photoelastic coefficient of a single resin is The composite value of the resin (b) other than cellulose, which is the preferred range, can control the absolute value of the photoelastic coefficient within the preferred range.
Chemical Review, No. 39, 1998 (published by Academic Publishing Center)

  The thickness of the composite in the present invention is preferably 5 μm or more and 5000 μm or less, and the composite having a thickness of 5 μm or more and 5000 μm or less can maintain strength and heat resistance. It is preferable because the thickness and weight of the display used can be reduced. More preferably, they are 20 micrometers or more and 1000 micrometers or less, Most preferably, they are 30 micrometers or more and 400 micrometers or less.

  In the present invention, a plurality of composites can be stacked to obtain a composite laminate. The laminate can be thickened by subjecting it to a heat press treatment, and a composite of the present invention having a thickness of 10 μm or more and 5000 μm or less can be obtained. The laminate thus obtained has high strength, is preferable, and is more preferable for transparency, heat resistance, water absorption, and linear expansion because the resin is more easily penetrated than a single-layer body having the same thickness. The number of laminated layers is preferably 2 or more and 30 or less, and more preferably 2 or more and 20 or less. Particularly preferably, the number is 2 or more and 10 or less. When it is 30 or less, a flexible composite can be obtained.

In the present invention, it is preferable that the relationship of the storage elastic modulus in the dynamic viscoelasticity measurement of the composite satisfies the following formula. The storage elastic modulus here means using RSAII manufactured by Rheometrics, the distance between chucks is about 20 to 30 mm, the sample width is about 2 to 4 mm, the measurement frequency is 1 Hz, the amount of strain is 0.05%, and in the tensile mode, This is the storage elastic modulus E ′ of the composite obtained when the temperature is raised from room temperature to 300 ° C. at a rate of 5 ° C. per minute.
_{E '30 / E' 150 ≦} 1000
Tg: Glass transition temperature of resin (b) other than cellulose E ′ ₃₀ : Storage elastic modulus of the composite at 30 ° C. E ′ ₁₅₀ : Storage elastic modulus of the composite at 150 ° C. More preferably, E ′ ₃₀ / E ′ ₁₅₀ ≦ 100, particularly preferably E ′ ₃₀ / E ′ ₁₅₀ <25. The composite of the present invention satisfies the above formula. When it is in this range, it is preferable from the viewpoint of heat resistance, and can be preferably used for an alternative to glass.
Further, it is more preferable that the storage elastic modulus is less decreased even at 250 ° C., and it is more preferable that the following formula is satisfied.
_{E '30 / E' 250 ≦} 1000
E ′ ₂₅₀ : Storage elastic modulus of the composite at 250 ° C. More preferably, E ′ ₃₀ / E ′ ₂₅₀ ≦ 100, and particularly preferably E ′ ₃₀ / E ′ ₂₅₀ <25.

In the present invention, in the measurement of the dynamic viscoelasticity of the composite, the storage elastic modulus E ′ _{150 at} 150 ° C. is preferably 100 MPa or more and 30000 MPa or less. More preferably, it is 400 MPa or more and 20000 MPa or less, Most preferably, it is 1000 MPa or more and 10,000 MPa or less. When it is 100 MPa or more and 50000 MPa or less, it is preferable from a viewpoint of heat resistance and a softness | flexibility, and it can use preferably for the use of glass substitution.
Further, the storage elastic modulus E ′ _{250 at} 250 ° C. is more preferably 100 MPa or more and 30000 MPa or less. More preferably, it is 400 MPa or more and 20000 MPa or less, Most preferably, it is 1000 MPa or more and 10,000 MPa or less.
The composite of the present invention satisfies the above values.

  “Preferable from the viewpoint of heat resistance” means that the difference in elastic modulus at high temperature and room temperature is small, or that the elastic modulus at high temperature is high. It is preferable because functionalization such as imparting electrical conductivity or imparting gas barrier properties is possible in a simple surface treatment process.

  In the present invention, the linear expansion coefficient of the composite is preferably 0.5 or more and 60 ppm / ° C. or less. More preferably, it is 1 or more and 50 ppm / ° C or less, and particularly preferably 2 or more and 20 ppm / ° C or less. (Evaluation methods are described in detail in the Examples) By making this range, it can be preferably used for glass substitute applications. The reason why low linear expansion coefficient is required for resin in glass replacement applications is that the surface-treated conductive function and gas barrier function are destroyed in the process of cooling from the required surface treatment process temperature to room temperature. This is necessary to prevent warpage and deformation due to temperature differences that occur during use. Further, in applications such as a flexible substrate and an electronic substrate that are bonded to a metal, the linear expansion coefficient is preferably the same as that of the metal to be bonded, and is preferably 10 to 20 ppm / ° C.

  In the present invention, the total light transmittance of the composite is preferably 60% or more, more preferably 75% or more, and particularly preferably 85% or more. In order to obtain a composite having a total light transmittance of 60% or more, for example, a resin other than cellulose having a total light transmittance of 60% or more and a refractive index of 1.45 to 1.65 is used. This can be achieved by using a nonwoven fabric (a) containing cellulose having a fiber diameter of 1500 nm or less. When the total light transmittance of the composite is in this range, it can be preferably used as an optical material such as a display display substrate.

In the present invention, the haze value of the composite is preferably 80 or less. More preferably, the haze value is 60 or less, and particularly preferably, the haze value is 50 or less. For example, the average transmittance _{Tr, av in} the above-mentioned toluene of the nonwoven fabric (a) containing cellulose is 0.70 or more, the film quality uniformity parameter H is 0.018 or less, and the maximum fiber diameter of the cellulose is 1500 nm. When the refractive index of the component (b) is 1.45 or more and 1.65 or less, the haze value can be made 80 or less. Within this range, it can be preferably used as an optical material such as a display display substrate.
In the present invention, the retardation of the complex is preferably 350 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less. Within this range, it can be preferably used as an optical material such as a display display substrate.

In the present invention, for the nonwoven fabric (a) containing cellulose,
(1) A method in which a monomer is impregnated and polymerized,
(2) A method of impregnating and curing a thermosetting resin precursor or a photocurable resin precursor,
(3) A method of drying after impregnating a solution of resin (b) other than cellulose,
(4) A method of producing a composite by any one of the methods of impregnating a thermoplastic resin melt other than cellulose (b) and cooling after defoaming can be used.
(1) The method of impregnating and polymerizing a monomer means that a monomer such as methyl methacrylate, which is a monomer constituting a thermoplastic resin, is impregnated in a nonwoven fabric (a) containing cellulose, and the monomer is subjected to heat treatment or the like. It is a production method for obtaining a composite comprising a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose by polymerization, and is used for polymerization of organic peroxides such as peroxides or monomers in general. The polymerization catalyst obtained can be used as a polymerization initiator. When it is assumed that the polymerization catalyst impairs the performance of the composite as an impurity, impregnate a high-purity monomer that does not contain any polymerization inhibitor such as quinones, and perform thermal polymerization without using a polymerization initiator. It is also effective.

  In addition, (2) a method of impregnating and curing a thermosetting resin precursor or a photocurable resin precursor is a method of curing a thermosetting resin precursor such as an epoxy resin or a mixture of a photocurable resin precursor and a curing agent. Non-cellulose (a) containing cellulose by impregnating non-woven fabric (a) containing cellulose and curing the thermosetting resin precursor or photocurable resin precursor by heat treatment or light irradiation, etc. It is a manufacturing method which obtains the composite_body | complex which consists of hardened | cured material of thermosetting resins, such as cured epoxy resin which is resin (b), or hardened | cured material of photocurable resin. When a thermosetting resin precursor such as an epoxy resin or a photocurable resin precursor is solid at room temperature and difficult to impregnate the nonwoven fabric (a) containing cellulose, the precursor is heat-treated in advance and melted. It is also possible to impregnate a solution obtained by dissolving the precursor in a soluble solvent. In order to increase the smoothness of the surface, it is also effective to allow the reaction to proceed further under heat press treatment when the curing reaction has progressed to some extent. It is also effective at the time of thickening the film (described above) to stack several composites that have undergone a curing reaction to some extent during the heat treatment.

  Moreover, (3) The method of drying after impregnating the solution of resin (b) other than cellulose is a non-woven fabric containing cellulose by dissolving a thermoplastic resin (b) other than cellulose in a dissolvable solvent ( It is a production method for obtaining a composite comprising a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose by impregnating and drying a).

  In addition, (4) a method of impregnating a melt of a thermoplastic resin that is a resin other than cellulose (b) and cooling after defoaming is a method of cooling the thermoplastic resin that is a resin other than cellulose (b) above the glass transition temperature or higher. A composite comprising a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose by melting by heating at a melting point or higher, impregnating the nonwoven fabric (a) containing cellulose, and cooling after defoaming. It is a manufacturing method to obtain. The heat treatment is desirably performed under pressure, and the use of equipment having a vacuum heating press function is effective.

  In the present invention, a continuous nonwoven fabric having a thickness of 5 μm or more and 500 μm or less obtained by an artificial film forming method such as a papermaking method or a coating method can be used as the nonwoven fabric (a) containing cellulose. Here, thickness is 5 micrometers or more from a viewpoint of nonwoven fabric strength, Preferably it is 10 micrometers or more, More preferably, it is 20 micrometers. Moreover, it is 500 micrometers or less from the surface of productivity or process control, Preferably it is 300 micrometers, More preferably, it is 200 micrometers or less.

  In order to produce a continuous nonwoven fabric, it is essential to perform continuous papermaking or film formation by continuous coating under the above-described conditions. In the case of continuous application, film formation is performed by a continuous film formation process of an application method. For example, a cellulose fiber dispersion is applied onto a traveling support (belt or the like), and this is continuously applied until a drying step. And after drying, the nonwoven fabric is peeled off from the support. The porosity of the nonwoven fabric is controlled by the dispersion medium of the dispersion and the composition of the additive.

  In the case of continuous papermaking, the rate of occurrence of paper breakage can be reduced to zero by providing a continuous support between the papermaking process / drying process or between the papermaking process / replacement process / drying process. It is effective. The filter cloth mentioned above can be used effectively as a continuous support here. Moreover, the transfer part of each process can also be transferred to the next process using press transfer or a pick-up roll. The support is necessary up to the entry side of the drying process. After drying, the nonwoven fabric is peeled off and wound up. In this case, it is important that the peeling is good. Select the material. Further, it is possible to substitute a filter cloth used in the paper making process as the support. In this case, as described above, after the drying step, the non-woven fabric is peeled off from the papermaking filter cloth as a support and wound. At this time, the good peelability of the filter cloth is important because it greatly affects the quality of the nonwoven fabric. In addition, when the nonwoven fabric and the support are used separately, it is necessary to transfer the wet paper from the filter cloth to the support after performing post-paper pressing, etc. It is good to use.

  In the present invention, by using the above-mentioned continuous nonwoven fabric and further impregnating with a monomer, a molten resin or a resin solution in a continuous process, and then polymerizing, curing, or drying, it is also produced as a continuous molded product usually called a roll product. Can do. Obtaining a continuous molded body in this way leads to an improvement in the productivity of the composite, and at the same time it can be adapted to the so-called semi-continuous display device manufacturing process of Rollto Roll, which is extremely meaningful in the industry. .

  Further, by stacking a plurality of layers of the composite of the present invention, which is a continuous molded body, and continuously or semi-continuously heat-pressing it, it is possible to obtain a continuous molded body laminate having a thickness of 10 μm or more and 5000 μm or less. it can.

The composite in the present invention is excellent in optical properties such as low linear expansion coefficient, heat resistance, transparency, low haze value, and low retardation, such as liquid crystal display, plasma display, organic EL display, field emission display, rear projection television, etc. It can be used for displays, touch panels, solar cell substrates, front plates, color filter substrates, and the like. In particular, the composite of the present invention can be substituted for the glass application used in these displays and solar cells, and effects such as weight reduction, flexibility, and resistance to cracking can be obtained. The composite of the present invention can be subjected to surface functionalization treatment such as transparent conductive treatment, electromagnetic wave shielding treatment, gas barrier treatment, and antifouling treatment, and antireflection treatment, for example. For example, when a conductive metal oxide is subjected to a conductive treatment by a method such as vapor deposition or sputtering or metal mesh wiring, metal paste, etc., on the composite of the present invention, it can be used as an electromagnetic shield on the front surface of a plasma display. What was laminated | stacked by vapor deposition, sputtering, the oxidation of polysilazane, and polysilane, and gave the gas barrier process can be used for various display substrates. In addition, a transparent conductive film can be obtained by laminating conductive metal oxides such as ITO and conductive zinc oxide by techniques such as vapor deposition and sputtering, and can be used for touch panels, various display substrates, and solar cell substrates. . As a method for surface treatment of such a composite, the method described in Non-Patent Document 8 can be used. Also by this method, the composite of the present invention can be used as a TFT liquid crystal substrate.
A. Asano, T. Kinoshita, SID Digest2002, 1196 (2002)

The conductive substrate for transparent electrodes that can be used as a touch panel, various display substrates, or a solar cell substrate using the composite of the present invention can be obtained, for example, as follows. First, a semiconductor film such as an oxide film of indium oxide, tin oxide, tin-indium alloy, zinc oxide-gallium, zinc oxide-aluminum, or a metal film such as gold, silver, palladium, or an alloy thereof on the surface of the transparent substrate A combination of a semiconductor film and a metal film is formed by a known physical deposition method such as a vacuum evaporation method, a sputtering method, or an ion plating method. In order to prevent the performance deterioration of the liquid crystal element, the organic EL element and the like due to the water vapor or oxygen permeating through the transparent substrate as necessary, vapor deposition of a gas barrier layer made of SiO ₂ or the like, or a polysilazane / organic solvent solution, Application of other coating silica materials such as alkoxysilane / organic solvent solution and formation of a barrier layer based on a three-dimensional reaction by heating, application of a polymer having a relatively high gas barrier property such as vinylidene chloride polymer or vinyl alcohol polymer Thus, a gas barrier layer can be provided.

  In the present invention, any additive can be blended according to various purposes within a range that does not significantly impair the effects of the present invention. The type of additive is not particularly limited as long as it is generally used for blending resins and rubber-like polymers. Inorganic fillers, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, lubricants, mold release agents, paraffinic process oil, naphthenic process oil, Softeners and plasticizers such as aromatic process oil, paraffin, organic polysiloxane, mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazoles Examples include ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, reinforcing agents such as metal whiskers, colorants, other additives, or mixtures thereof.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention.

  Hereinafter, the manufacture example of resin (b) other than the nonwoven fabric (a) containing cellulose used for the Example and cellulose is demonstrated.

[Production Example 1]
Polysaccharide-production medium (Polysaccharide-production-medium, Akihiko Shimada, VivaOrigino, 23, 1, 52-53, 1995) supplemented with 2.0% glucose was autoclaved and 1000L of the fermentation medium with an internal capacity of 3000L Place in a tank, inoculate CJF-002 strain at 10 ⁴ CFU / ml, perform agitation culture under aeration at 30 ° C. for 2 days under aeration, and a dispersion containing a large amount of bacterial cellulose (BC) Got. Then, after filtering, washing with water and pressing with a screen mesh, it was immersed in a 1% NaOH solution, sterilized, neutralized, washed with water, and pressed again. Further, the washing and pressing steps were repeated three times to obtain a purified cotton-like BC / water dispersion (cellulose content: 11.6% by weight, hereinafter referred to as M1).

Next, after diluting M1 with water so that the cellulose concentration becomes 1.0% by weight and pre-dispersing with a home mixer for 10 minutes, using a high-pressure homogenizer (NS3015H manufactured by Niro Soabi (Italy)), Four dispersion treatments were performed under an operating pressure of 80 MPa. Next, this dispersion liquid having a cellulose concentration of 1.0% by weight is further diluted with water so that the cellulose concentration becomes 0.40% by weight, and again subjected to a dispersion treatment with a home mixer for 5 minutes. Used as a papermaking dispersion. Measurement of the average dispersed diameter R _v of the papermaking dispersion, was 75 [mu] m.
Next, a square-shaped metal using a PET woven fabric (fiber thickness: about 40 μm, 460 mesh) having a filtration rate of 99% or more of cellulose (BC) evaluated using the papermaking dispersion as follows. Paper cut was performed using a batch type paper machine (automatic square sheet machine manufactured by Kumagai Rikkoku Kogyo Co., Ltd.) using a filter cloth that was cut to the size of a wire made (25 cm × 25 cm). The above-mentioned PET fabric is placed on a rectangular metal wire (25 cm × 25 cm, filtration rate of cellulose when using the paper dispersion; less than 30%) incorporated in the paper machine, and from above Only 580 g of the papermaking dispersion was poured into the papermaking machine, and papermaking was performed using a suction (decompression device). The obtained wet paper was further covered with the same filter cloth, dehydrated with a metal roller, and adjusted so that the cellulose concentration was 12 to 13% by weight. The obtained wet paper was first immersed in acetone without peeling off the PET fabric, and was subjected to a substitution treatment for about 10 minutes while occasionally rinsing the whole, followed by mixing of toluene / acetone = 50/50 (g / g). It was immersed in the solution, and the replacement treatment was performed for about 10 minutes while occasionally rinsing the whole lightly. Immediately after that, a wet paper sandwiched between filter cloths was placed on a metal plate, and a weight was placed on the wet paper so that it was dried at a constant length, set in a drying oven, and dried at 100 ° C. for 50 minutes. . After drying, the non-woven fabric was peeled off from the filter fabric to obtain a white cellulose non-woven fabric. The resulting cellulose nonwoven fabric (a) (hereinafter BC-1) had a porosity of 75% and a film thickness of 100 μm.

Next, a BC / water dispersion (R _v : 77 μm) having a cellulose concentration of 0.10 wt% was prepared in the same manner as described above using the same BC aqueous dispersion, M1, and the amount of the dispersion was 1050 g. As above, batch-type papermaking and substitution with an organic solvent and drying were carried out in the same manner to obtain a cellulose nonwoven fabric (a) (hereinafter BC-2) having a porosity of 77% and a film thickness of 49 μm. Both BC-1 and BC-2 had a crystallinity of 83% determined by a solid state NMR method. In the SEM image, only very thin fibers having a fiber diameter of 100 nm or less were confirmed. Further, by measuring the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} is 0.87 for BC-1 and 0.93 for BC-2, and the value of the film quality uniformity parameter H. The BC-1 was 0.0040 and the BC-2 was 0.0032.

[Production Example 2]
A BC / water dispersion (R _v : 77 μm) having a cellulose concentration of 0.10% by weight was obtained in the same manner as described above using an aqueous dispersion of BC and M1. Paper making was performed in the same manner as described above with an amount of the dispersion of 1150 g, to obtain a wet paper having a solid content of about 10% by weight. In a state where both sides of the wet paper were sandwiched between filter cloths made of PET, the wet paper was stuck on a drum dryer whose surface temperature was set to 100 ° C., and dried for a drying time of 180 seconds. After drying, the PET filter cloth on both sides of the cellulose nonwoven fabric was peeled off to obtain a translucent white cellulose nonwoven fabric (a) (hereinafter BC-3) having a film thickness of 25 μm and a porosity of 51%. The crystallinity determined by the solid-state NMR method of BC-3 was 83%, and only very thin fibers having a fiber diameter of 100 nm or less were confirmed in the SEM images. Further, from the measurement of the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} was 0.91, and the value of the film quality uniformity parameter H was 0.0045.

[Production Example 3]
Instead of M1, a dice piece of Nata de Coco (manufactured by Fujicco Co., Ltd., solid content: 0.5% by weight), which is a water-containing BC gel used as a foodstuff, was thoroughly washed (water under water flow) A BC / water dispersion having a solid content of 12% by weight was prepared. Water was added to the dispersion, diluted with water so that the cellulose concentration became 1.0% by weight, pre-dispersed with a home mixer for 10 minutes, and then a high-pressure homogenizer (NS3015H manufactured by Niro Soabi (I)) was added. The dispersion process was performed 4 times under an operating pressure of 80 MPa. Next, this dispersion liquid having a cellulose concentration of 1.0% by weight is further diluted with water so that the cellulose concentration becomes 0.10% by weight, and again subjected to a dispersion treatment with a home mixer for 5 minutes. Used as a papermaking dispersion. Measurement of the average dispersed diameter R _v of the papermaking dispersion was 55 .mu.m.

Next, a plain fabric made of PET / nylon blend having a filtration rate of 99% or more evaluated using the papermaking dispersion (NT20, manufactured by Shikishima Kanbus Co., Ltd.) is used as follows. Paper making was performed using the same batch type paper machine as in Production Example 1 using a filter cloth that was cut to a size of metal wire (25 cm × 25 cm). Only 1330 g of the papermaking dispersion was passed through the papermaking machine, and papermaking was performed using a suction (decompression unit). The obtained wet paper was further covered with the same filter cloth, dehydrated with a metal roller, and adjusted so that the cellulose concentration was 12 to 13% by weight. The obtained wet paper was immersed in iso-butanol without removing the filter cloth and subjected to a substitution treatment for about 20 minutes while occasionally rinsing the whole, and then the wet paper having both sides sandwiched by the filter cloth was placed on the metal plate. The weight was placed thereon, and a weight was placed thereon to be dried at a constant length, which was set in a drying oven and dried at 100 ° C. for 50 minutes. After drying, the nonwoven fabric was peeled off from the filter cloth to obtain a white cellulose nonwoven fabric (film thickness: 65 μm, porosity: 78%, hereinafter BC-4). The degree of crystallinity obtained by the solid state NMR method of BC-4 was 82%, and only very thin fibers having a fiber diameter of 100 nm or less were confirmed in the SEM images. Further, from the measurement of the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} was 0.91, and the value of the film quality uniformity parameter H was 0.0040.

[Production Example 4]
Dispersion M1 obtained in Production Example 1 was diluted with water to obtain a cellulose concentration of 1.0% by weight, and a Disperser for papermaking (manufactured by Kumagai Riki Kogyo Co., Ltd., No. 2500-I, KRK high concentration). After performing continuous dispersion treatment equivalent to 15 times with a disc refiner and refiner plate (Type-D is used), using a high-pressure homogenizer (NS3015H manufactured by Niro Soavi (Italy)) 4 times under an operating pressure of 100 MPa. The distributed processing was implemented. Next, this dispersion liquid having a cellulose concentration of 0.5% by weight is further diluted with water so that the cellulose concentration becomes 0.25% by weight, and again subjected to continuous dispersion treatment corresponding to 10 times with a disc refiner. Was used as a papermaking dispersion. Measurement of the average dispersed diameter R _v of the papermaking dispersion was 65 .mu.m.

Next, using a 0.65 m wide inclined wire type continuous paper making machine (manufactured by Saito Iron Works Co., Ltd.) set at an inclination angle of 5 °, a polyolefin wire used as standard in the apparatus (this example) The PET / nylon plain woven fabric (width 0.76 m × length 100 m) used in Production Example 3 on the filtration rate of cellulose when the papermaking dispersion used in the above was used; 64%) It is continuously installed as a filter cloth, the paper dispersion obtained above is continuously supplied at a supply speed of 6.5 L / min, the paper travel speed is 6 m / min, and the degree of vacuum is 8.90 kPa. The continuous suction papermaking was carried out by operating the dry suction with a wet suction (inclined part) and a reduced pressure of 46.7 kPa. A dehydration step using a metal roll was provided immediately after papermaking, and the cellulose concentration of the wet paper immediately after this step was 11% by weight. The wet paper / filter cloth is immersed in a substitution bath filled with a large excess of iso-butanol in two layers, and prepared so that the immersion time is 20 minutes. A filter cloth is continuously applied to the upper part of the filter to form a three-layer structure of filter cloth / nonwoven fabric / filter cloth, and then dried with a drum dryer whose surface temperature is set to 100 ° C. A continuous nonwoven fabric of cellulose (hereinafter referred to as BC-5) was obtained by peeling the nonwoven fabric. BC-5 had a porosity of 85% and a film thickness of 26 μm. The crystallinity obtained by the solid-state NMR method of BC-5 was 83%, and only very thin fibers having a fiber diameter of 100 nm or less were confirmed in the SEM images. Further, from the measurement of the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} was 0.95, and the value of the film quality uniformity parameter H was 0.0025.

[Production Example 5]
A high-pressure homogenizer (Niro Soabi (Italy) manufactured by dispersing purified cotton linters in water to 1.0% by weight and treating with a beater (manufactured by Kumagai Riki Kogyo Co., Ltd., 23L) for 2 hours. NS3015H) was used to carry out the miniaturization treatment 20 times under an operating pressure of 100 MPa. Next, this dispersion liquid having a cellulose concentration of 1.0% by weight is further diluted with water so that the cellulose concentration becomes 0.20% by weight, and subjected to a dispersion treatment for 10 minutes with a home mixer. Was used as a papermaking dispersion. The dispersion average diameter Rv of this papermaking dispersion was measured and found to be 9.2 μm.
Cellulose nonwoven fabric, CL-1, was obtained from 350 g of the dispersion using the same batch papermaking and organic solvent substitution and drying conditions as in Production Example 3. The porosity of CL-1 was 85% and the film thickness was 50 μm. The crystallinity obtained by the solid-state NMR method of CL-1 was 76%. From the SEM image, it was confirmed that CL-1 is mainly composed of fibers with a thin fiber diameter of several tens to 100 nm, but some fibers of several hundred nm are also mixed. No fiber with a diameter exceeding 1000 μm was present. Further, from the measurement of the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} was 0.86, and the value of the film quality uniformity parameter H was 0.0035.

[Production Example 6]
Acetic acid bacteria were cultured to obtain cellulose. Culture is a standard condition, using a Hestrin-Schramm medium (“Cellulose Dictionary” Cellulose Society, edited by Asakura Shoten, 2000, p44), with fructose as a carbon source at PH 6 at a temperature of 28 ° C. for 8 days, an inner diameter of 10 cm. The stationary culture was performed in the petri dish. The obtained translucent gel-like material having a thickness of about 2 mm was subjected to a lysis treatment at 120 ° C. for 1 hour in a state of being immersed in a 2 wt% aqueous sodium hydroxide solution using an autoclave apparatus. Furthermore, after the obtained wet gel was washed with water, the lysis treatment by autoclave was again performed under the same conditions as above to obtain a wet gel sheet. The gel was immersed in a sufficient amount of 4 ° C. cold water and allowed to stand for 2 hours, and then the gel was sandwiched between filter papers and pressed. The cold water immersion and pressing steps were further repeated four times under the same conditions to obtain a pressed gel-like stationary culture membrane. The stationary culture membrane containing water thus obtained was immersed in iso-butanol and subjected to substitution treatment for about 45 minutes while occasionally rinsing the whole, and then placed on a metal plate by sandwiching it with the above-mentioned PET filter cloth, A weight was placed thereon and dried in a constant length, set in a drying oven and dried at 100 ° C. for 50 minutes. After drying, by peeling the stationary culture membrane from the filter cloth,
A white cellulose nonwoven fabric obtained by stationary culture was obtained. The resulting nonwoven fabric (a) containing cellulose (a) (hereinafter BC-6) had a porosity of 78% and a film thickness of 85 μm. The crystallinity obtained by the solid-state NMR method of BC-6 was 80%, and only very thin fibers having a fiber diameter of 100 nm or less were confirmed in the SEM images. Further, from the measurement of the transmittance distribution under the toluene immersion liquid described above _, the value of _{Tr, av} was 0.93, and the value of the film quality uniformity parameter H was 0.0030.
[Production Example 7]
In Production Example 3 and Production Example 5, one of the filter cloths that was pressed with a 20 kg metal load roll on the wet paper immediately after papermaking obtained in the course of batch-type papermaking, and sandwiched between both sides immediately after solvent replacement Pressed with a felt roll from the upper part of the nonwoven fabric in a two-layered state of the nonwoven fabric / filter fabric peeled off, and dried with a drum dryer set at 100 ° C. By peeling off the filter cloth as a support from the obtained two-layer nonwoven fabric, a nonwoven fabric used in the present invention having high surface smoothness with reduced transferability due to the unevenness of the filter cloth was obtained.
BC-7 is the non-woven fabric with high surface smoothness obtained by the above process under the conditions of Production Example 3, and CL-2 is the non-woven fabric with high surface smoothness obtained by the above process under the conditions of Production Example 5.
The porosity of BC-7 was 74%, the film thickness was 50 μm, the porosity of CL-2 was 78%, and the film thickness was 37 μm. Further, when the transmittance distribution of these two nonwoven fabrics was measured under a toluene immersion liquid _, the values of _{Tr, av} were 0.92 (BC-7) and 0.88 (CL-2), The values of the film quality uniformity parameter H were 0.0037 (BC-7) and 0.0035 (CL-2).
[Production Example 8] Styrene / Acrylonitrile Copolymer A monomer mixture consisting of 72% by weight of styrene, 13% by weight of acrylonitrile, and 15% by weight of ethylbenzene was continuously fed into a fully mixed reactor equipped with a stirrer. The polymerization reaction was carried out with a residence time of 2 hours.
The obtained polymerization solution was continuously supplied to an extruder, and unreacted monomers and a solvent were recovered by the extruder to obtain pellets of a (styrene / acrylonitrile) copolymer (a-1). The styrene content was 80% by weight, the acrylonitrile content was 20% by weight, and the melt flow rate value at 220 ° C. and a load of 10 kg according to ASTM-D1238 was 13 g / 10 min.

[Example 1]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) Two pieces of the cellulose non-woven fabric (a) BC-1 obtained in Production Example 1 were impregnated (impregnation time: within 5 minutes) and laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of a cellulose nonwoven fabric (a) and a cured epoxy resin (b) was obtained by heat curing (curing time: 1 hour) under .81 MPa. The thickness was about 240 μm.

[Example 2]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) Two pieces of the cellulose non-woven fabric (a) BC-3 obtained in Production Example 2 were impregnated (impregnation time: within 30 minutes) and laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of a cellulose nonwoven fabric (a) and a cured epoxy resin (b) was obtained by heat curing (curing time: 1 hour) under .81 MPa. The thickness was about 50 μm.

[Example 3]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) Two pieces of the cellulose non-woven fabric (a) BC-4 obtained in Production Example 3 were impregnated (impregnation time: within 5 minutes), and the mixture was laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of a cellulose nonwoven fabric (a) and a cured epoxy resin (b) was obtained by heat curing (curing time: 1 hour) under .81 MPa. The thickness was about 130 μm.

[Example 4]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) 1 liquid impregnated with the cellulose non-woven fabric (a) BC-1 obtained in Production Example 1 (impregnation time: within 5 minutes) in a press machine at a temperature of 100 ° C. and a pressure of 9.81 MPa. Under heat curing (curing time: 1 hour), a composite of cellulose nonwoven fabric (a) and cured epoxy resin (b) was obtained. The thickness was about 100 μm.

[Example 5]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) 2 pieces of the cellulose nonwoven fabric (a) CL-1 obtained in Production Example 5 were impregnated (impregnation time: within 5 minutes), and the temperature was 100 ° C. and the pressure 9 The composite of the cellulose nonwoven fabric (a) and the cured epoxy resin (b) was obtained by heat curing (curing time: 2 hours) under .81 MPa. The thickness was about 100 μm.

[Example 6]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) The cellulose non-woven fabric (a) BC-6 obtained in Production Example 6 was impregnated (impregnation time: within 5 minutes) with a temperature of 100 ° C. and a pressure of 9.81 MPa in a single press. The composite of the nonwoven fabric (a) containing cellulose and the cured epoxy resin (b) was obtained by heat curing (curing time: 2 hours). The thickness was about 85 μm.

[Example 7]
100 parts by weight of bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.), which is an epoxy compound of a thermosetting resin precursor, is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xyloseamine) Two pieces of the cellulose non-woven fabric (a) BC-5 obtained in Production Example 4 were impregnated (impregnation time: within 5 minutes), and the mixture was laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of a cellulose nonwoven fabric (a) and a cured epoxy resin (b) was obtained by heat curing (curing time: 1 hour) under .81 MPa. The thickness was about 52 μm.
[Example 8]
100 parts by weight of bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.), which is an epoxy compound of a thermosetting resin precursor, is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xyloseamine) Two pieces of the cellulose non-woven fabric (a) BC-7 obtained in Production Example 7 were impregnated (impregnation time: within 5 minutes) and laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of the cellulose nonwoven fabric (a) and the cured epoxy resin (b) was obtained by heat curing (curing time: 3 hours) under .81 MPa. The thickness was about 100 μm. Moreover, about Example 8, it measured also about the in-plane retardation (Re) and the photoelastic coefficient in the light of wavelength 550nm.
[Example 9]
100 parts by weight of bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.), which is an epoxy compound of a thermosetting resin precursor, is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xyloseamine) Two pieces of the cellulose non-woven fabric (a) CL-2 obtained in Production Example 7 were impregnated (impregnation time: within 5 minutes), and the mixture was laminated in a press machine at a temperature of 100 ° C. and a pressure of 9 The composite of the cellulose nonwoven fabric (a) and the cured epoxy resin (b) was obtained by heat curing (curing time: 3 hours) under .81 MPa. The thickness was about 75 μm.

[Example 10]
Cellulose nonwoven fabric (a) BC-2 obtained in Production Example 1 is sandwiched between two sheets of PLA film (Carloill Dow 4031D made by melt extrusion at 190 ° C., approximately 100 μm thick), 200 The composite of cellulose and resin was obtained by pressing at 9.81 MPa. The thickness was about 50 μm.

[Example 11]
To the monomer mixture consisting of 80% by weight of methyl methacrylate and 20% by weight of methyl acrylate, 2500 ppm of lauryl peroxide and 4500 ppm of n-octyl mercaptan were added and mixed uniformly. About 30 g of this mixed solution was put into a pressure vessel, and the cellulose nonwoven fabric (a) BC-1 obtained in Production Example 1 was cut into an appropriate size to enter the pressure vessel, put into the solution, and covered. . The pressure vessel was covered with a mesh wire mesh for safety. The pressure vessel was placed in an 80 ° C. water bath for 2 hours, the monomer solution was polymerized, and volatiles were removed in a 120 ° C. explosion-proof oven to obtain a bacterial cellulose nonwoven fabric-containing PMMA composite. The obtained cellulose nonwoven fabric-containing PMMA was press-molded at 250 ° C. 9.81 MPa to obtain a film that is a composite of cellulose nonwoven fabric and PMMA. The thickness was about 100 μm.

[Example 12]
Cellulose nonwoven fabric (a) BC-1 obtained in Production Example 1 is impregnated with an 8 wt% chloroform solution of polycarbonate (Panlite L-1225Y manufactured by Teijin Chemicals Ltd.). One PC solution-impregnated cellulose nonwoven fabric was dried in a vacuum dryer attached to a solvent trap, and press molded at 280 ° C. to obtain a cellulose PC composite. The thickness was about 100 μm.

[Example 13]
A composite film was continuously produced from the roll of cellulose continuous nonwoven fabric BC-5 (width 65 cm × length 100 m) obtained in Production Example 4. The feed side roll is immersed in a dip tank into which 10% by weight of polycarbonate (Panlite L-1225Y manufactured by Teijin Chemicals Ltd.) / Methylene chloride solution 40L (temperature: adjusted to 15 ° C.) is injected, and the traveling speed Is set so that the impregnation time is 20 cm / min and about 100 sec, the continuous film is pulled up to the atmospheric phase, roughly dried by running for about 180 sec, and then sent to a drying box set at 60 ° C., and for another 300 sec It dried and wound up with the winding roll. Injection and discharge of the polycarbonate solution into the dip tank were performed continuously, and all the steps were performed under a running speed of 20 cm / min and in an exhaust environment. Thereby, the continuous film which is a composite_body | complex of a cellulose nonwoven fabric and PC was obtained. The thickness was about 26 μm.
[Example 14]
Cellulose nonwoven fabric (a) BC-7 obtained in Production Example 7 is impregnated with an 8% by weight methylene chloride solution of polycarbonate (Panlite L-1225Y manufactured by Teijin Chemicals Ltd.). One piece of the PC solution-impregnated cellulose nonwoven fabric was air-dried, and when it turned into a transparent solid film, it was dried with a dryer at 60 ° C. for 2 hours to obtain a transparent cellulose PC composite. The thickness was about 50 μm.
[Example 15]
The cellulose nonwoven fabric (a) CL-2 obtained in Production Example 7 is impregnated with an 8% by weight methylene chloride solution of polycarbonate (Panlite L-1225Y manufactured by Teijin Chemicals Ltd.). One piece of the PC solution-impregnated cellulose nonwoven fabric was air-dried, and when it turned into a transparent solid film, it was dried with a dryer at 60 ° C. for 2 hours to obtain a transparent cellulose PC composite. The thickness was about 38 μm.
[Example 16]
Cellulose continuous non-woven fabric (a) CL-1 obtained in Production Example 5 is sandwiched between two sheets of polylactic acid film (prepared by melt-extrusion of 4040D made by Cargill Dow Co., Ltd. at 190 ° C., thickness of about 100 μm). The composite of cellulose and resin was obtained by pressing at 200 ° C. and 4.91 MPa. The thickness was about 40 μm.
[Example 17]
Cellulose continuous non-woven fabric (a) CL-1, obtained in Production Example 5, one sheet, polymethyl methacrylate film (produced by melt extrusion of LP-1 manufactured by Asahi Kasei Chemicals Corporation at 250 ° C., thickness of about 100 μm) The composite of cellulose and resin was obtained by sandwiching between two sheets and pressing at 240 ° C. and 4.91 MPa. The thickness was about 78 μm.
[Example 18]
Cellulose continuous non-woven fabric (a) CL-1 obtained in Production Example 5 was used as a polymethyl methacrylate / acrylonitrile-styrene copolymer (composition ratio = 50/50) alloy film (LP manufactured by Asahi Kasei Chemicals Corporation). -1 and an acrylonitrile-styrene copolymer (AS) polymerized in Production Example 9 are melted and kneaded at 250 ° C. and extruded to make about 100 μm thick) and pressed at 240 ° C. and 4.91 MPa. As a result, a composite of cellulose and resin was obtained. The thickness was about 84 μm.
[Example 19]
Cellulose continuous non-woven fabric (a) CL-1 obtained in Production Example 5 was melt-extruded at 250 ° C. with one sheet of acrylonitrile-styrene film (acrylonitrile-styrene copolymer (AS) polymerized in Production Example 9). And made between about 100 μm thick) and pressed at 240 ° C. and 4.91 MPa to obtain a composite of cellulose and resin. The thickness was about 81 μm.
[Example 20]
Cellulose continuous non-woven fabric (a) CL-1 obtained in Production Example 5 is sandwiched between two sheets of polystyrene film (PSPS, Inc., GPPS685 made by melt extrusion at 250 ° C., approximately 100 μm thick). The composite of cellulose and resin was obtained by pressing at 240 ° C. and 4.91 MPa. The thickness was about 64 μm.

[Comparative Example 1]
Cellulose nonwoven fabric (a) BC-1 obtained in Production Example 1 was used as Comparative Example 1.
[Comparative Example 2]
100 parts by weight of a bisphenol A type epoxy resin (AER-250 manufactured by Asahi Kasei Epoxy Co., Ltd.) which is an epoxy compound of a thermosetting resin precursor is melted at 120 ° C., and 18 parts by weight of a curing agent (m-xylylenediamine) The mixed epoxy resin (b) is poured into a 100 μm-thick press metal frame and thermally cured (curing time: 1 hour) at a temperature of 100 ° C. and a pressure of 9.81 MPa in a press machine. A film was obtained.

[Comparative Example 3]
Polylactic acid (hereinafter referred to as PLA) pellets (Cargill Dow 4031D) were melt-extruded at 190 ° C. using a sheet extruder (Technovel KZW15TW-25MG-NH type) to produce a film of about 100 μm.
[Comparative Example 4]
To the monomer mixture consisting of 80% by weight of methyl methacrylate and 20% by weight of methyl acrylate, 2500 ppm of lauryl peroxide and 4500 ppm of n-octyl mercaptan were added and mixed uniformly. About 30 g of this mixed solution was placed in a pressure vessel and covered. The pressure vessel was covered with a mesh wire mesh for safety. The pressure vessel was placed in an 80 ° C. water bath for 2 hours to polymerize the monomer solution, and then the volatile matter was removed in a 120 ° C. explosion-proof oven to obtain polymethyl methacrylate (hereinafter referred to as PMMA). The obtained PMMA was press-molded at 250 ° C. to obtain a single PMMA film. The thickness was about 100 μm.

[Comparative Example 5]
Polycarbonate (hereinafter referred to as PC) pellets (Panlite L-1225Y manufactured by Teijin Chemicals Ltd.) were melt-extruded at 280 ° C. using a sheet extruder (Technovel KZW15TW-25MG-NH type) to produce a film having a thickness of about 100 μm.

-Evaluation method About the composite body produced in the said Example and the comparative example, various characteristics were measured with the following evaluation method. The evaluation results are shown in Tables 1 and 2.
a) Resin content It calculated | required from the weight of the cellulose nonwoven fabric measured previously, and the weight of the obtained composite_body | complex.
b) Average linear expansion coefficient Change rate ΔL (%) of the sample length when the temperature was raised from 50 ° C. to 150 ° C. at a rate of 5 ° C. per minute using a TMA / SS120 type device manufactured by Seiko Instruments Inc. Was determined by the following equation. When the sample length at 50 ° C. was L ₅₀ and the sample length at 150 ° C. was L ₁₅₀ , the load was 10 g and the measurement was performed in the tensile mode.
ΔL = (L ₁₅₀ −L ₅₀ ) / L ₅₀ / (150−50)
Moreover, about the composite of the cellulose of Example 8-16 and a thermoplastic resin, and the thermoplastic resin single-piece | unit of Comparative Example 1-5, when it heated up at a rate of 5 degreeC from 30 degreeC to 100 degreeC in 1 minute The change rate ΔL (%) of the sample length was determined by the following equation. When the sample length at 30 ° C. was L ₃₀ and the sample length at 70 ° C. was L ₇₀ , the load was 10 g and the measurement was performed in the tensile mode.
ΔL = (L ₇₀ −L ₃₀ ) / L ₃₀ / (70−30)
c) Total light transmittance It measured based on JIS K7361-1 using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000.
d) Viscoelasticity Measurement Using RSAII manufactured by Rheometrics, the temperature was increased from room temperature to 300 ° C at a rate of 5 ° C per minute, and the storage elastic modulus E ′ and loss elastic modulus E ″ of the sample were measured.
The distance between chucks is about 20-30 mm, the sample width is about 2-4 mm, the measurement frequency is 1 Hz, the amount of strain is 0.05%, the tensile modulus is measured, and the storage elastic modulus at 30 ° C. is E ′ ₃₀ , 150 'the storage modulus at a _0.99, 250 ° C. E' ° C. the storage modulus E when the was _250. The storage elastic modulus at 200 ° C. was E ′ ₂₀₀ .
e) Water absorption rate After placing the test piece in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. ± 1 ° C. or ± 2 ° C. and a relative humidity (50 ± 5)% for 24 hours or more, a Karl Fischer moisture meter is used. The water absorption was titrated.
f) Molding processability The time required for impregnation with the resin was observed.
g) Refractive index of resin The refractive index of the resin in the D line (589 nm) was determined using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.
h) Parallel light transmittance of light having a wavelength of 580 nm Using a spectroscopic variable angle color difference meter GC5000 manufactured by Nippon Denshoku Industries Co., Ltd., the direction perpendicular to the sample surface is 0 degree, and the transmittance at a wavelength of 580 nm at a light receiving angle of 0 degree is parallel. It calculated | required as light transmittance.
i) In-plane retardation (Re) measurement with light having a wavelength of 550 nm At 23 ° C., using a birefringence measuring device RETS-100 manufactured by Otsuka Electronics Co., Ltd. In-plane retardation (Re) at 550 nm was measured by a rotating analyzer method.
j) Measurement of photoelastic coefficient
A birefringence measuring apparatus described in detail in Macromolecules 2004, 37, 1062-1066 was used. A film tensioning device was placed in the laser beam path, and birefringence was measured while applying a tensile stress at 23 ° C. The strain rate during stretching was 20% / min (chuck interval: 30 mm, chuck moving speed: 6 mm / min), and the test piece width was 7 mm. From the relationship between birefringence (Δn) and tensile stress (σR), the photoelastic coefficient (CR) is calculated by finding the slope of the straight line in the linear region by least square approximation, and the absolute value (| CR |) of the photoelastic coefficient is obtained. It was. The smaller the absolute value of the slope is, the closer the photoelastic coefficient is to 0, indicating a preferable optical characteristic.
| CR | = | Δn | / σR
The absolute value of birefringence (Δn) was determined as follows.
| Δn | = | n1-n2 |
(CR: photoelastic coefficient, σR: stretching stress, Δn: birefringence, n1: refractive index in the stretching direction, n2: refractive index perpendicular to the stretching direction)
k) The acrylonitrile content (styrene / acrylonitrile) copolymer was formed into a film using a hot press, and the absorbance at 1603 cm ⁻¹ and 2245 cm ⁻¹ of the film was measured using FT-410 manufactured by JASCO Corporation. Has been determined in advance, acrylonitrile content of (styrene / acrylonitrile) copolymer and ^1603cm -1, by using the relationship between the absorbance ratio of the 2245 cm ^-1, it was determined acrylonitrile amount of (styrene / acrylonitrile) copolymer .

  The composite of the present invention is applied to a plastic substrate for liquid crystal display elements, a substrate for color filters, a plastic substrate for organic EL display elements, a solar cell substrate, a touch panel substrate, a plasma display protection plate, a liquid crystal display protection plate, and a plasma display electromagnetic wave shielding substrate. It can be used suitably.

It is an example of the image when observing the surface of the nonwoven fabric obtained by making paper of the bacterial cellulose produced by CJF002 bacteria belonging to the Entrobacter family at a magnification of 10,000 using a scanning electron microscope (SEM). An image of the surface of a nonwoven fabric obtained by paper making a finer linter fiber obtained by ultra high-pressure homogenizer treatment of purified cotton linter (100MPa x 20 passes) using a scanning electron microscope (SEM). It is an example. It is explanatory drawing which shows the measuring method of transmittance | permeability _{Tr, av} of the laser beam of 850 nm under the toluene impregnation of the nonwoven fabric containing a cellulose. It is a chart figure of transmittance | permeability _Tr obtained by making a 850 nm laser beam scan in the length direction of a test tube using the method of FIG. The horizontal axis is the distance from the lowest measurement in the test tube length direction, and the vertical axis is the transmittance of the laser beam of 850 nm. It is a graph which shows the parallel light transmittance when light with a wavelength of 580 nm is applied to Examples 12-16. The horizontal axis represents the refractive index of the resin of component (b) in Examples 12-16, and the vertical axis represents the parallel light transmittance when light having a wavelength of 580 nm is applied.

Claims (20)

It consists of a nonwoven fabric (a) containing cellulose and a resin (b) other than cellulose, wherein (a) component is 5 wt% to 60 wt%, and (b) component is 40 wt% to 95 wt%. The cellulose-containing nonwoven fabric (a) has a porosity of 50% or more and 95% or less, and is obtained by vertically scanning light at 850 nm with respect to the nonwoven fabric in a state of being immersed in toluene. Contains cellulose having an average transmittance T _{r, av} defined by the following formula (1) of 0.70 or more, and a film quality uniformity parameter H defined by the following formula (2) is 0.018 or less. A composite comprising a non-woven fabric containing cellulose.
However,
_{Tr, av} is filled with toluene in a state where the nonwoven fabric is adhered to the inner surface of the test tube, irradiated with light of 850 nm from the direction perpendicular to the nonwoven fabric, and linearly along the surface of the nonwoven fabric. Obtained by carrying out the same measurement in the state where only toluene was injected except for the average value T _{r, 1 of the} transmittance obtained when scanning for a total length of 30000 μm (data points: 750) every 40 μm. The ratio of the average transmittance T _{r, 2} is defined by the following equation.
T _{r, av} = T _{r, 1} / T _{r, 2} (1)
H is filled with toluene with the nonwoven fabric attached to the inner surface of the test tube, irradiated with light of 850 nm to the test tube from a direction perpendicular to the nonwoven fabric, and linearly along the surface of the nonwoven fabric every 40 μm. The transmittance obtained by performing the same measurement in the state in which only toluene was injected except for the standard deviation _{Tr, sd1 of the} transmittance and the nonwoven fabric obtained when scanning was performed for a total length of 30000 μm (data score: 750). It is defined by the following equation using T _{r, av} obtained by equation (1) in the same measurement as T _{r, sd} defined by the difference between standard deviations T _{r, sd2} .
H = T _{r, sd} / T _{r, av} (2)
Here, _{Tr, sd} = _{Tr, sd1} - _{Tr, sd2} . The composite according to claim 1, wherein pores of the nonwoven fabric (a) containing cellulose are filled with a resin (b) other than cellulose. The composite according to claim 1 or 2, wherein a non-woven fabric containing cellulose having a porosity of 70% to 95% is used as the non-woven fabric (a) containing cellulose. As the nonwoven fabric (a) containing cellulose, a nonwoven fabric in which cellulose fibers having a maximum fiber thickness of 1500 nm or less obtained by forming a film from a dispersion containing cellulose fibers by a papermaking method or a coating method is used. The complex according to any one of claims 1 to 3, wherein: The nonwoven fabric (a) containing cellulose is a nonwoven fabric obtained by a papermaking method, and as a dispersion for papermaking, the dispersion average diameter of cellulose fibers is 1 μm or more and 300 μm or less, and the cellulose fiber concentration is 0.01% by weight or more. Using a dispersion of 1.0% by weight or less, as a filter cloth, it has the ability to filter out 95% or more of cellulose fibers in a papermaking dispersion by filtration at 25 ° C. under atmospheric pressure, and 25 under atmospheric pressure. By using a filter cloth having a water permeation amount of 0.005 cc / cm ² · s or more at 0 ° C., the filter cloth is placed on the wire of the papermaking apparatus, and the papermaking dispersion is filtered on the filter cloth, whereby cellulose Produced by depositing fibers on a filter cloth to produce a wet nonwoven fabric with a solid content of 4% by weight or more of fine cellulose fibers, and peeling the nonwoven fabric from the filter cloth before or after the drying step. A composite according to any one of claims 1 to 4, cellulosic fibers larger fiber thickness is 1500nm or less, characterized by using a nonwoven fabric formed by entangling. As the nonwoven fabric (a) containing cellulose, a cellulose fiber having a maximum fiber thickness of 1500 nm or less produced by a production method including a step of replacing the dispersion medium in the papermaking dispersion with an organic solvent before the drying step The composite according to claim 5, wherein a non-woven fabric entangled is used. The composite according to any one of claims 1 to 6, which has a linear expansion coefficient of 0.5 ppm / ° C or more and 60 ppm / ° C or less. The composite according to any one of claims 1 to 7, which has a linear expansion coefficient of 1 ppm / ° C to 50 ppm / ° C. The storage elastic modulus relationship in the dynamic viscoelasticity measurement satisfies the following formula, and the storage elastic modulus E ′ ₁₅₀ at 150 ° C. of the composite in the dynamic viscoelasticity measurement is 100 MPa or more. The composite according to Item.
_{E '30 / E' 150 ≦} 1000
E ′ ₃₀ : Storage elastic modulus of the composite at 30 ° C. E ′ ₁₅₀ : Storage elastic modulus of the composite at 150 ° C. The storage elastic modulus relationship in the dynamic viscoelasticity measurement satisfies the following formula, and the storage elastic modulus E ′ ₂₅₀ at 250 ° C. of the composite in the dynamic viscoelasticity measurement is 100 MPa or more. The composite according to Item.
_{E '30 / E' 250 ≦} 1000
E ′ ₃₀ : Storage elastic modulus of the composite at 30 ° C. E ′ ₂₅₀ : Storage elastic modulus of the composite at 250 ° C. The composite according to any one of claims 1 to 10, wherein the total light transmittance is 60% or more. For the nonwoven fabric (a) containing cellulose,
(1) A method in which a monomer is impregnated and polymerized.
(2) A method in which a thermosetting resin precursor or a photocurable resin precursor is impregnated and cured.
(3) A method of drying after impregnating a solution of a resin other than cellulose.
(4) A method of impregnating a thermoplastic resin melt and cooling after defoaming.
The method for producing a composite according to any one of claims 1 to 11, wherein the resin (b) other than cellulose is filled and composited by any one of the methods. The plastic substrate for a display which consists of a composite_body | complex of any one of Claims 1-11. A plastic substrate for a display front plate, comprising the composite according to any one of claims 1 to 11 and having a thickness of 500 µm or less. The display using the plastic substrate as described in any one of Claims 13-14. The display according to claim 15, wherein the display is a liquid crystal display. The display according to claim 15, wherein the display is an organic electroluminescence (organic EL) display.   The display of claim 15, wherein the display is a plasma display. The display of claim 15, wherein the display is a field emission display. The display of claim 15, wherein the display is a surface electric field display.

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