JP6197300B2 - Fiber resin composite material - Google Patents

Description

The present invention relates to a fiber resin composite material containing cellulose fibers and a resin and a method for producing the same, and more specifically to a fiber resin composite material used as a substrate for a reinforced resin material or an electronic material and a method for producing the same.
The present invention also relates to a cellulose fiber dispersion and a dispersion for forming a fiber resin composite material that are suitably used for the production of the fiber resin composite material.

  In recent years, active research has been conducted on fiber resin composite materials using fine cellulose fibers. It is known that cellulose has a low linear thermal expansion coefficient, a high elastic modulus, and a high strength when combined with a resin because of its extended chain crystal. Further, it has been attracting attention as a material exhibiting high transparency when it is miniaturized to be combined with a resin to form a composite material.

  Examples of applications of cellulose fiber composite materials having such a high transparency and low linear thermal expansion coefficient include transparent substrate materials for electrical and electronic devices such as flat panel displays, organic LED lighting, and photovoltaic power generation panels. In these device manufacturing steps, heat treatment may be required. In particular, the heat-resistant temperature required as an optical substrate material in the future is said to be 250 ° C., and in these applications, materials that cause coloration by heat treatment are not preferable.

  However, it is known that cellulose is gradually pyrolyzed when exposed to a high temperature of 200 ° C. or higher. In order to solve this problem, Patent Document 1 discloses that cellulose is treated with an appropriate amount of boric acid so that a hydroxyl group on the surface of the cellulose and boric acid form an ester bond, and the reducing end is fixed at about 300 ° C. It has been disclosed that depolymerization against heating up to can be suppressed. However, boric acid esters are easily decomposed by moisture, so there is little effect of suppressing thermal decomposition, and there are problems such as promoting the coloring of cellulose because it works as an acid when boric acid is too much. .

  Moreover, the method of suppressing the heat coloring of a cellulose by heat-processing a cellulose with a solvent at high temperature is also known. For example, in Patent Document 2, it is possible to suppress coloring at high temperature by heating cellulose in the presence of an alcohol having no acetal structure having 1 to 20 carbon atoms and reacting the reducing terminal of the cellulose with the alcohol. It is disclosed. However, this method needs to be processed at a high temperature of 170 ° C. or higher, which is disadvantageous from the viewpoint of manufacturing cost. Furthermore, there is no description about the case where it is combined with a resin, and the heat-resistant coloring suppression effect after the combination is unknown.

  Further, Patent Document 3 discloses a method for suppressing coloring due to heating by heat-treating refined cellulose fibers in the presence of a solvent, but in this method, heating coloring at 200 ° C. is suppressed. However, it was insufficient to suppress coloring due to thermal decomposition of cellulose when heated to 250 ° C.

JP 2008-163053 A JP 2010-159364 A JP 2011-144363 A

  This invention makes it a subject to provide the fiber resin composite material with little coloring even when it passes through a heating process in the composite material of a cellulose fiber and resin.

  As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by including a compound having a cyclic ether structure or a compound having a (meth) acryloyl group and a hydroxyl group in the fiber resin composite material. The invention has been reached.

That is, the present invention relates to cellulose fibers having a number average fiber diameter of 2 to 400 nm, resins, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, acrylic Acid 1-hydroxy-2- (acryloyloxy) ethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, And a fiber resin composite material containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter referred to as “the specific compound of the present invention”), and having a weight ratio Then, the specific compound of the present invention is added to the resin 1 It exists in the fiber resin composite material characterized by containing 0.01 times or more and 1 time or less.
The present invention also provides
Cellulose fibers having a number average fiber diameter of 2 to 400 nm, resins and / or resin precursors, and glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, acrylic Acid 1-hydroxy-2- (acryloyloxy) ethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, And a cellulose fiber dispersion containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter referred to as “the specific compound of the present invention”), and having a weight ratio With respect to the resin and / or resin precursor 1 A cellulose fiber dispersion characterized by containing the specific compound of the present invention 0.01 times or more and 1 time or less,
A method for producing a fiber-resin composite material comprising a cellulose nonwoven fabric and a resin, wherein the resin and / or resin precursor, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 2 -Hydroxyethyl, 1-hydroxy-2- (acryloyloxy) ethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryl Formation of fiber resin composite material containing at least one compound selected from the group consisting of leuoxypropyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter referred to as “specific compound of the present invention”). Dispersion for the resin, wherein the resin and And / or the fiber resin composite material-forming dispersion containing the specific compound of the present invention 0.01 times or more and 1 time or less with respect to the resin precursor 1 includes cellulose fibers having a number average fiber diameter of 2 to 400 nm. A method for producing a fiber resin composite material comprising the step of impregnating a cellulose nonwoven fabric or applying the dispersion for forming a fiber resin composite material to the cellulose nonwoven fabric,
And a method for producing a fiber-resin composite material containing cellulose fiber and resin, wherein the number-average fiber diameter is 2 to 400 nm, cellulose fiber, resin and / or resin precursor, and glycidyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 1-hydroxy-2- (acryloyloxy) ethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin One or more compounds selected from the group consisting of di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter “the specific compound of the present invention”) ).) A step of curing a cellulose fiber dispersion containing 0.01 to 1 to 1 time of the specific compound of the present invention with respect to the resin and / or the resin precursor 1 by weight ratio. A method for producing a fiber-resin composite material, comprising:
Exist.

  ADVANTAGE OF THE INVENTION According to this invention, even when it passes through a heating process in the composite material of a cellulose fiber and resin, the fiber resin composite material with little coloring can be provided.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content of is not specified.

[Fiber resin composite material]
The fiber resin composite material of the present invention is
(1) Cellulose fiber,
(2) resin,
And
(3) It contains a compound selected from the group consisting of a compound having a cyclic ether structure and a compound having a (meth) acryloyl group and a hydroxyl group.

In the following, “a compound selected from the group consisting of a compound having a cyclic ether structure and a compound having a (meth) acryloyl group and a hydroxyl group” will be referred to as “the specific compound of the present invention” and “the compound having a cyclic ether structure”. Is referred to as “cyclic ether compound”, and “compound having (meth) acryloyl group and hydroxyl group” is sometimes referred to as “(meth) acryloyl / hydroxyl group-containing compound”.
In the present invention, “(meth) acryloyl group” means “methacryloyl group” and / or “acryloyl group”. The same applies to “(meth) acrylate” and “(meth) acryl”.

  In the fiber resin composite material of the present invention, by containing the specific compound of the present invention, the cellulose in the composite material can be prevented from being thermally decomposed and colored when heated to a high temperature of 200 ° C. or higher. Although the details of the action mechanism of this coloring suppression effect are not clear, the specific compound of the present invention does not react when the fiber resin composite material is cured, and has a functional group that reacts with the hydroxyl group of cellulose at a high temperature. This is thought to be due to being a compound.

{Specific compounds of the present invention}
First, the specific compound of the present invention selected from the group consisting of a cyclic ether compound and a (meth) acryloyl / hydroxyl group-containing compound, which is a feature of the present invention, will be described. In addition, as a specific compound of this invention, 1 type (s) or 2 or more types of a cyclic ether compound may be used, and 1 type (s) or 2 or more types of a (meth) acryloyl / hydroxyl group containing compound may be used. Moreover, you may use together 1 type (s) or 2 or more types of a cyclic ether compound, and 1 type (s) or 2 or more types of a (meth) acryloyl / hydroxyl group containing compound.

  The specific compound of the present invention has a molecular weight of usually 100,000 or less, preferably 10,000 or less, more preferably 1000 or less, and usually 44 or more, preferably 88 or more. When the molecular weight of the specific compound of the present invention is within this range, the specific compound of the present invention is preferable because it is easily blended into the fiber resin composite material, hardly volatilizes, and has no problem in terms of environmental safety.

<Cyclic ether compound>
The cyclic ether compound is a compound having a cyclic ether structure in the molecule, and the cyclic ether structure may exist as a group linked to the main chain or ring of the molecule, or a part of the main chain or ring may be present. It may be configured.

  Examples of the cyclic ether structure contained in the cyclic ether compound include usually a 3-membered to 6-membered ether structure, preferably a 3-membered to 5-membered ring, more preferably a 3-membered or 4-membered ether. Structure. Examples of the 3-membered cyclic ether structure include an oxirane ring, and examples of the 4-membered cyclic ether structure include an oxetane ring.

  The cyclic ether compound may have one or more cyclic ether structures in the molecule, but is preferably 3 or less, more preferably 2 or less.

  Since the cyclic ether compound further has a (meth) acryloyl group in the molecule, the precipitation and volatilization of molecules are suppressed in the heating step and the decompression step after molding, so that coloring during heating can be further suppressed. This is preferable.

  The cyclic ether compound may have at least one (meth) acryloyl group, preferably 6 or less, more preferably 4 or less.

  When the cyclic ether compound has a (meth) acryloyl group, the ratio of the cyclic ether structure to the (meth) acryloyl group in the cyclic ether compound is preferably 1: 1 to 1: 5, and particularly 1: 1 to It is preferably 1: 2.

  The cyclic ether compound is expected to reduce coloring during heating in the fiber resin composite material due to the action of a cyclic ether structure such as an oxirane ring or an oxetane ring suppressing the thermal decomposition of cellulose in the heating step.

  Specifically, the cyclic ether compound is preferably a compound having an oxirane ring or an oxetane ring.

  Examples of the compound having an oxirane ring include a compound having a glycidyl group and a compound in which a part of the ring is constituted by an oxirane ring (a compound in which the oxirane ring is added as a condensed ring to the ring of the basic skeleton).

  Examples of the compound having a glycidyl group include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol Examples include tetraglycidyl ether. Hydrogenated bisphenol A type liquid epoxy resin can also be used.

  Examples of the compound in which a part of the ring is an oxirane ring include cyclohexene oxide, cyclopentene oxide, 3 ', 4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl, and the like.

  Examples of the cyclic ether compound further having a (meth) acryloyl group in the molecule include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.

Examples of the compound having one or more oxetane rings in the molecule include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 3-ethyl- (2-ethylhexyloxymethyl). Oxetane, 3-ethyl {[-3- (triethoxylyl) propoxy] methyl} oxetane, 3-ethyl-3-methacryloxymethyloxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 1,4- And bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, and the like.
For example, commercially available compounds having an oxetane ring include Aron Oxetane OXT-101, OXT-121, OPXT-211, OXT-212, OXT-610, OXT-213 (manufactured by Toa Gosei Co., Ltd.), ETERNACOOL OXETENE EHO, OXBP, OXMA, OXTP (manufactured by Ube Industries, Ltd.) and the like can be mentioned.

<(Meth) acryloyl / hydroxyl-containing compound>
The (meth) acryloyl / hydroxyl group-containing compound may have at least one (meth) acryloyl group and one hydroxyl group in the molecule. The (meth) acryloyl / hydroxyl group-containing compound may have at least one (meth) acryloyl group, but is preferably 6 or less, more preferably 4 or less. Further, the (meth) acryloyl / hydroxyl group-containing compound may have 1 or more hydroxyl groups, but is preferably 4 or less, more preferably 2 or less.
The ratio of (meth) acryloyl groups to hydroxyl groups in the (meth) acryloyl / hydroxyl group-containing compound is preferably 1: 5 to 5: 1. Specifically, {number of (meth) acryloyl groups} / ( The number of hydroxyl groups) is preferably 1/5 or more, more preferably 1/2 or more, preferably 5 or less, and more preferably 2 or less.

  The (meth) acryloyl / hydroxyl group-containing compound is expected to reduce coloring during heating in the fiber resin composite material by the action of the hydroxyl group of the (meth) acryloyl / hydroxyl group-containing compound suppressing the thermal decomposition of cellulose in the heating step. Is done.

  Specific examples of the (meth) acryloyl / hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 1-hydroxy-2- (acryloyloxy) ethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolethane monoacrylate, 2-acryloyloxy Ethyl-2-hydroxyethylphthalic acid, pentaerythritol triacrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, pentaerythritol tri (meth) acrylate Relate, dipentaerythritol penta (meth) acrylate, bisacrylic acid [hexamethylenebisoxybis (2-hydroxy-3,1-propanediyl)], bisacrylic acid 2,2,6-tris (acryloyloxymethyl)- 6- (Hydroxymethyl) -4-oxaheptane-1,7-diyl, 2- (acryloyloxymethyl) -2-hydroxypropane-1,3-diyl bisacrylate, 3,3,7-tris bisacrylate (Acryloyloxymethyl) -7- (hydroxymethyl) -2,5-dioxaoctane-1,8-diyl, 1,3-bis [2- (acryloyloxy) ethyl] -5- (2-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1- [2- (acryloyloxy) ethyl] -3,5-bis (2-hydroxyethyl) -1, 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

{Cellulose fiber}
Next, the cellulose fiber (hereinafter sometimes referred to as “the cellulose fiber of the present invention”) contained in the fiber resin composite material of the present invention will be described.

  The cellulose fiber of the present invention may be any of the cellulose-containing material described later, a cellulose fiber raw material obtained by refining the cellulose-containing material, and a fine cellulose fiber obtained by defibrating the cellulose fiber raw material. Preferably, the cellulose fiber raw material is defibrated. It is a fine cellulose fiber.

<Number average fiber diameter of cellulose fibers>
The cellulose fiber of the present invention is not particularly limited, but is preferably a cellulose fiber having a number average fiber diameter of 2 to 400 nm.

  The cellulose fibers in this range are usually obtained by defibrating the cellulose fiber raw material described in detail below, and the number average fiber diameter is preferably 200 nm or less, and 150 nm or less. Is more preferably 100 nm or less, particularly preferably 80 nm or less, particularly preferably 50 nm or less, and most preferably 30 nm or less. The number average fiber diameter of the cellulose fibers is preferably as small as possible. However, in order to develop a low linear thermal expansion coefficient and a high elastic modulus, it is important to maintain the crystallinity of cellulose, usually 2 nm or more, preferably 4 nm. That's it.

  In addition, the fiber diameter of a cellulose fiber is a scanning electron microscope (henceforth SEM), a transmission electron microscope (henceforth TEM), and the cellulose nonwoven fabric obtained by drying and removing the dispersion medium in the fine cellulose fiber dispersion liquid explained in full detail below. ), And by observing with an atomic force microscope (hereinafter AFM) or the like. Specifically, it is usually observed with SEM, TEM, AFM, etc., a line is drawn on the diagonal line of the photograph, 12 fibers are randomly extracted in the vicinity, and the thickest fiber and the thinnest fiber are removed 10 The fiber diameter of the point is measured, and the value obtained by averaging the measured values is taken as the number average fiber diameter.

<Method for producing cellulose fiber>
Hereinafter, the manufacturing method of the cellulose fiber of this invention is demonstrated concretely. In addition, about the manufacturing method of the cellulose fiber of this invention, it is not limited to the following method.
In order to produce the cellulose fiber of the present invention, it is preferable to use a cellulose-containing material obtained by removing impurities from a cellulose-containing material as shown below through a general purification step.

(Cellulose-containing material)
Examples of cellulose-containing materials include woods such as conifers and hardwoods (wood flour, etc.), cotton such as cotton linter and cotton lint, pomace such as sugar cane and sugar radish, bast fibers such as flax, ramie, jute and kenaf Vegetal vein fibers such as sisal and pineapple, petiole fibers such as abaca and banana, fruit fibers such as coconut palm, stem-derived fibers such as bamboo, bacterial cellulose produced by bacteria, seaweed and squirts such as valonia and falcon Natural cellulose such as encapsulates. These natural celluloses are preferable because of their high crystallinity and low linear expansion and high elastic modulus. In particular, cellulose fibers obtained from plant-derived materials are preferred.

  Bacterial cellulose is preferred in that it can be easily obtained with a fine fiber diameter. Cotton is also preferable in that it is easy to obtain a fine fiber diameter, and more preferable in terms of easy acquisition of raw materials.

  In addition, wood of conifers and hardwoods with fine fiber diameters can be obtained, and it is the largest amount of biological resources on the planet. It is a sustainable resource that produces about 70 billion tons per year. Therefore, it contributes greatly to the reduction of carbon dioxide that affects global warming, which is advantageous from an economic point of view. When wood is used as the cellulose fiber raw material of the present invention, it is preferably used after being crushed into a state such as wood chips or wood flour.

(Cellulose fiber raw material)
The cellulose fiber raw material is obtained by refining the above cellulose-containing material by a usual method.
For example, it can be obtained by degreasing the above cellulose-containing material with benzene-ethanol or an aqueous sodium carbonate solution, followed by delignification treatment with chlorite (Wise method) and dehemicellulose treatment with alkali. In addition to the Wise method, a method using peracetic acid (pa method), a method using a peracetic acid persulfuric acid mixture (pxa method), and the like are also used as purification methods. Moreover, you may perform a bleaching process etc. further suitably.

  In the purification treatment, water is generally used as a dispersion medium. However, an aqueous solution of an acid or base or other treatment agent may be used, and in this case, it may be finally washed with water.

The cellulose fiber raw material may be obtained by a general method for producing chemical pulp, for example, a method for producing kraft pulp, salified pulp, alkali pulp, or nitrate pulp.
That is, as a cellulose fiber raw material, you may use hardwood kraft pulp, softwood kraft pulp, hardwood sulfite pulp, softwood sulfite pulp, hardwood bleached kraft pulp, softwood bleached kraft pulp, linter pulp and the like.

  In addition, as a raw material for cellulose fiber, CGP (Chemical Groundwood Pulp) or the like which is subjected to light chemical treatment with ground pulp, such as SGW (Stone Groundwood) or sodium sulfite, and then crushed, can be used. Groundwood pulp is preferably used.

  In addition, the cellulose-containing material may be crushed into a state such as wood chips or wood powder, and this crushing may be performed at any timing before, during or after the purification treatment.

  The degree of purification of the cellulose fiber raw material obtained by refining the cellulose-containing material is not particularly defined, but it is preferable that the fat content of the cellulose fiber raw material is less because the fat and oil and lignin are less and the cellulose component content is higher. The cellulose component content of the cellulose fiber raw material is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more.

  The cellulose component of the cellulose fiber raw material can be classified into a crystalline α-cellulose component and an amorphous hemicellulose component. It is preferable that the content of crystalline α-cellulose is large because the effects of low linear thermal expansion coefficient, high elastic modulus, and high strength are easily obtained when a fiber resin composite material is used. The α-cellulose content of the cellulose fiber raw material is preferably 90% by weight or more, more preferably 95% by weight or more, and more preferably 97% by weight or more.

  Although the fiber diameter of the cellulose fiber raw material is not particularly limited, the number average fiber diameter is usually 1 μm to 1 mm. In addition, the number average fiber diameter of the cellulose fiber raw material which passed through general refinement | purification is about 50 micrometers normally.

(Defibrillation treatment of cellulose fiber raw material)
The cellulose fiber raw material is normally defibrated in a cellulose fiber raw material dispersion (cellulose fiber raw material dispersion). This cellulose fiber raw material dispersion has a solid content concentration of 0.1% by weight or more, preferably 0.2% by weight or more, particularly 0.3% by weight or more, and 10% by weight or less, particularly 6% by weight as a cellulose fiber raw material. % Or less cellulose fiber raw material dispersion. If the solid content concentration in the cellulose fiber raw material dispersion to be subjected to the defibrating process is too low, the amount of liquid will be too large for the amount of cellulose to be processed, and the efficiency will be poor, and if the solid content concentration is too high, the fluidity will be poor. The concentration of the cellulose fiber raw material dispersion to be subjected to the defibration treatment is preferably adjusted by adding water as appropriate.

  As the dispersion medium, an organic solvent, water, or a mixed solution of an organic solvent and water can be used. Examples of organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, ethylene glycol and ethylene glycol mono-t-butyl ether, ketones such as acetone and methyl ethyl ketone, and other water-soluble organic compounds. One kind or two or more kinds of solvents can be used. The dispersion medium is preferably a mixed liquid of an organic solvent and water or water, and particularly preferably water.

  There are no particular restrictions on the method of defibrating the cellulose fiber raw material, but for example, ceramic beads having a diameter of about 1 mm are placed in the cellulose fiber raw material dispersion, and vibration is applied using a paint shaker or bead mill. , A method of defibrating cellulose fiber raw material, a method of defibrating by using shearing force through a cellulose fiber raw material dispersion between a blender type disperser and a slit rotating at high speed (high-speed rotating homogenizer method), and from high pressure A method in which shearing force is generated between cellulose fibers by suddenly reducing the pressure (high pressure homogenizer method), a method using an opposing collision type disperser (Masuko Sangyo) such as “Masscomizer X”, etc. Is mentioned. In particular, the high-speed rotating homogenizer and the high-pressure homogenizer treatment improve the efficiency of defibration. Note that a miniaturization process combined with an ultrasonic process may be performed after the above process.

  After the defibrating treatment, centrifugal separation may be performed to separate and remove cellulose fibers with poor defibration. By centrifuging, a more uniform and fine cellulose fiber supernatant is obtained. The conditions for the centrifugation are not particularly limited because they depend on the applied defibrating treatment and the required degree of refinement. For example, it is preferable to apply a centrifugal force of 3000 G or more, preferably 10,000 G or more. Moreover, as processing time, it is preferable to apply centrifugal force, for example for 1 minute or more, Preferably it is 5 minutes or more. If the centrifugal force is too small or the treatment time is too short, separation / removal of cellulose fibers with poor defibration becomes insufficient, which is not preferable.

In addition, when the centrifugal separation is performed, it is not preferable that the viscosity of the dispersion liquid including the cellulose fiber to which the centrifugal force is applied is high because the separation efficiency is lowered. As the viscosity of this dispersion, the viscosity at a shear rate of 10 s ⁻¹ measured at 25 ° C. is preferably 500 mPa · s or less, particularly preferably 100 mPa · s or less.

  A fine cellulose fiber dispersion containing fine cellulose fibers can be obtained by performing such defibrating treatment and, if necessary, centrifugal separation.

In addition, as described later, the above-described defibrating treatment may be performed on a dispersion containing the cellulose fiber raw material and the specific compound of the present invention, whereby the book containing the cellulose fiber and the specific compound of the present invention. The cellulose fiber dispersion of the invention can be produced.
The defibrating treatment may be performed on a dispersion containing a cellulose fiber raw material and a resin and / or resin precursor described below. The cellulose fiber raw material, the resin and / or the resin precursor, and the You may carry out with respect to the dispersion liquid containing a specific compound.

(Chemical modification treatment / oxidation treatment)
The cellulose fiber of the present invention may be one derivatized by chemical modification (chemically modified cellulose fiber) or one having a carboxy group introduced by oxidation treatment. The chemical modification is one in which a hydroxyl group in cellulose is chemically modified by reacting with a chemical modifying agent (another substituent is introduced).

  These treatments may be performed before or after the above-described purification treatment, or may be performed on a cellulose nonwoven fabric described later. Further, it may be performed after the cellulose fibers are defibrated by the above-described defibrating treatment or after the defibrating treatment.

  The group introduced into the hydroxyl group of cellulose by these chemical modification treatment / oxidation treatment is not particularly limited. For example, acetyl group, acryloyl group, methacryloyl group, propionyl group, propioyl group, butyryl group, 2-butyryl group, pentanoyl group, Hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, myristoyl, palmitoyl, stearoyl, pivaloyl, benzoyl, naphthoyl, nicotinoyl, isonicotinoyl, furoyl, cinnamoyl Such as an acyl group, an isocyanate group such as a 2-methacryloyloxyethylisocyanoyl group, a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, a 2-butyl group, a tert-butyl group, a pentyl group, Alkyl groups such as xyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, palmityl group, stearyl group, oxirane group, oxetane group, thiirane group, thietane group, phosphate group, A carboxy group etc. are mentioned. A hydrogen atom in these substituents may be substituted with a functional group such as a hydroxyl group or a carboxy group. Further, a part of the alkyl group may be an unsaturated bond.

  The chemical modification method is not particularly limited, but there is a method of reacting cellulose with the following chemical modifier. Although there are no particular limitations on the reaction conditions, a solvent, a catalyst, or the like may be used, or heating, decompression, or the like may be performed as necessary.

  As a kind of chemical modifier, 1 type, or 2 or more types chosen from the group which consists of cyclic ethers, such as an acid, an acid anhydride, alcohol, a halogenating reagent, isocyanate, alkoxysilane, and an oxirane (epoxy), are mentioned.

  Examples of the acid include acetic acid, acrylic acid, methacrylic acid, propanoic acid, butanoic acid, 2-butanoic acid, and pentanoic acid.

Examples of the acid anhydride include acetic anhydride, acrylic anhydride, methacrylic anhydride, propanoic anhydride, butanoic anhydride, 2-butanoic anhydride, and pentanoic anhydride.
Examples of the alcohol include methanol, ethanol, propanol, and 2-propanol.
Examples of the halogenating reagent include acetyl halide, acryloyl halide, methacryloyl halide, propanoyl halide, butanoyl halide, 2-butanoyl halide, pentanoyl halide, benzoyl halide, naphthoyl halide, and the like.
Examples of the isocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, and the like.
Examples of the alkoxysilane include methoxysilane and ethoxysilane.
Examples of cyclic ethers such as oxirane (epoxy) include ethyl oxirane and ethyl oxetane.

Among these, acetic anhydride, acrylic acid anhydride, methacrylic acid anhydride, benzoyl halide, and naphthoyl halide are particularly preferable.
These chemical modifiers may be used alone or in combination of two or more.

  In the present invention, the chemical modification rate of cellulose fibers is preferably 3 mol% or more, more preferably 8 mol% or more, based on the total hydroxyl groups of cellulose. The chemical modification rate is 65 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less, based on the total hydroxyl groups of cellulose.

  The higher this chemical modification rate tends to be excellent in the effect of suppressing coloration by heating in the resulting fiber resin composite material, and the higher the chemical modification rate, the lower the hydrophilicity of the cellulose fiber, and the water absorption rate. However, if the chemical modification rate is too high, the cellulose structure is destroyed and the crystallinity is lowered, so that there is a problem that the linear expansion coefficient of the obtained fiber resin composite material is increased, which is not preferable. . In particular, when wood is used as the cellulose fiber raw material, there is a problem of coloring due to heating even if the chemical modification rate is low or high. Therefore, it is preferable to appropriately adjust the chemical modification.

  In addition, the chemical modification rate here shows the ratio of what was chemically modified among all the hydroxyl groups in a cellulose, and a chemical modification rate can be measured with the following titration method.

これを解いていくと、以下の通りである。

0.05 g of dried cellulose fiber or 0.05 g of dried cellulose nonwoven fabric described later is precisely weighed, and 1.5 ml of ethanol and 0.5 ml of distilled water are added thereto. This is left to stand in a hot water bath at 60 to 70 ° C. for 30 minutes, and then 2 ml of 0.5 M aqueous sodium hydroxide solution is added. After leaving this in a 60-70 degreeC hot water bath for 3 hours, it ultrasonically shakes for 30 minutes with an ultrasonic cleaner. This is titrated with 0.2 M hydrochloric acid standard solution using phenolphthalein as an indicator.
Here, from the amount Z (ml) of 0.2 M hydrochloric acid aqueous solution required for titration and the amount Z ₀ (ml) of 0.2 N hydrochloric acid aqueous solution required for titration of the blank sample (= sample without dry cellulose), The amount of substituent Q (mol) introduced by chemical modification is determined by the formula.
Q (mol) = (Z ₀ −Z) × 0.2 / 1000
The relationship between the number of moles Q of the substituent and the chemical modification rate X (mol%) is calculated by the following formula (cellulose = (C ₆ O ₅ H ₁₀ ) _n = (162.14) _n , repetition Number of hydroxyl groups per unit = 3, molecular weight of OH = 17). In the following, T is the molecular weight of a substituent introduced by chemical modification.

Solving this, it is as follows.

<Cellulose nonwoven fabric>
In the fiber resin composite material of the present invention, the cellulose fiber may be contained as a cellulose nonwoven fabric in the fiber resin composite material.

  A cellulose nonwoven fabric is a nonwoven fabric of cellulose fibers, which is manufactured by filtering a dispersion of cellulose fibers, etc., but is manufactured using cellulose fibers that have been refined by defibration rather than using cellulose fibers before defibration. This is preferable because a fiber resin composite material having high transparency, low linear thermal expansion coefficient, and high elastic modulus can be obtained using this. That is, the cellulose nonwoven fabric is preferably produced as a sheet by filtering the fine cellulose fiber dispersion obtained by the defibrating process or by applying it to a suitable base material.

  When a cellulose nonwoven fabric is produced by filtering a fine cellulose fiber dispersion, the fine cellulose fiber concentration of the dispersion subjected to filtration is usually 0.01% by weight or more, preferably 0.05% by weight or more. Preferably it is 0.1 weight% or more. If the concentration of the fine cellulose fibers in the dispersion is too low, filtration takes an enormous amount of time, which is not preferable. The concentration of fine cellulose fibers in the dispersion is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1.5% by weight or less, and particularly preferably 1.2% by weight. % Or less, most preferably 1.0% by weight or less. If the concentration of the fine cellulose fibers in the dispersion is too high, a uniform sheet cannot be obtained, which is not preferable.

  When filtering the fine cellulose fiber dispersion, it is important that the fine cellulose fibers do not pass through and the filtration speed is not too slow as a filter cloth at the time of filtration. As such a filter cloth, a sheet made of an organic polymer, a woven fabric, and a porous membrane are preferable. The organic polymer is preferably a non-cellulose organic polymer such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or the like. More specifically, a porous film of polytetrafluoroethylene having a pore diameter of 0.1 to 20 μm, for example, 1 μm, polyethylene terephthalate or polyethylene fabric having a pore diameter of 0.1 to 20 μm, for example, 1 μm, and the like can be given.

  In addition, a paper base material made of cellulose which is a natural fiber can be used as a filter medium. The paper base material is preferable because it can easily produce a wide or long paper material, and can control the amount of water passing through the paper by changing the type of pulp as the raw material or the beating degree of the pulp. In addition, it is possible to easily impart water resistance to the substrate with a water-proofing agent or a hydrophobizing agent.

  The cellulose nonwoven fabric obtained by the filtration is then dried, but in some cases, it may proceed to the next step without drying. For example, when the heat-treated fine cellulose fiber dispersion is filtered, it can be used as it is in the next step without passing through the drying step.

  However, it is preferable to perform drying also in the sense of controlling the porosity, film thickness, and strengthening the structure of the nonwoven fabric. This drying may be air drying, vacuum drying, pressure drying, or freeze drying. Moreover, you may heat-dry.

  When carrying out heat drying, the heating temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, 250 ° C. or lower, more preferably 150 ° C. or lower. If the heating temperature is too low, drying may take time or drying may be insufficient, and if the heating temperature is too high, the cellulose nonwoven fabric may be colored or cellulose may be decomposed. Moreover, when pressurizing, 0.01 MPa or more is preferable, 0.1 MPa or more is more preferable, 5 MPa or less is preferable, and 1 MPa or less is more preferable. If the applied pressure is too low, drying may be insufficient. If the applied pressure is too high, the cellulose nonwoven fabric may be crushed or cellulose may be decomposed.

  Moreover, you may manufacture a cellulose nonwoven fabric as a sheet-like material by apply | coating a fine cellulose fiber dispersion liquid to a suitable base material. In this case, usually, the dispersion is applied onto a predetermined substrate, and the dispersion medium is evaporated to a specific amount and removed. The coating method is not particularly limited, and examples thereof include spin coating, blade coating, wire bar coating, spray coating, and slit coating. In particular, the spin coating method is preferable in that a thin film having a uniform thickness can be obtained.

  In addition, it does not specifically limit as a board | substrate, A glass substrate, a plastic substrate, etc. are mentioned.

  The cellulose nonwoven fabric used in the present invention is usually composed only of cellulose fibers, but may contain other compounding agents and fibers as necessary.

  In addition, the preferable fiber diameter of the cellulose fiber contained in a cellulose nonwoven fabric is the same as the number average fiber diameter of the above-mentioned cellulose fiber of this invention.

  Moreover, since it will become difficult to impregnate resin when the porosity of a cellulose nonwoven fabric is small, it is preferable that there exists a certain amount of porosity. The porosity in this case is usually 10% by volume or more, preferably 20% by volume or more. However, when the porosity is excessively large, the linear thermal expansion coefficient is increased when the cellulose fiber composite material is formed, and therefore, the porosity of the cellulose nonwoven fabric is preferably 60% by volume or less.

The porosity of a cellulose nonwoven fabric here can be calculated | required easily by a following formula.
Porosity (volume%) = {(1-B / (M × A × t)} × 100
Here, A is the area (cm ² ) of the cellulose nonwoven fabric, t is the thickness (cm), B is the weight (g) of the cellulose nonwoven fabric, M is the density of cellulose, and in the present invention, M = 1.5 g / cm ³ Assume that The film thickness of a cellulose nonwoven fabric measures 10 points | pieces about the various positions of a cellulose nonwoven fabric using a film thickness meter (PDN-20 made from PEACOK), and employ | adopts the average value.

  Although there is no limitation in particular in the thickness of a cellulose nonwoven fabric, Preferably it is 1 micrometer or more, More preferably, it is 5 micrometers or more. Moreover, it is 1000 micrometers or less normally, Preferably it is 250 micrometers or less. The thickness of the cellulose nonwoven fabric is preferably not less than the above lower limit from the viewpoint of production stability and strength, and is preferably not more than the above upper limit from the viewpoint of productivity, uniformity, and resin impregnation.

{Production method of fiber resin composite material}
Although the manufacturing method of the fiber resin composite material of this invention is demonstrated below, the manufacturing method of the fiber resin composite material of this invention is not limited to the following methods at all.

<Method 1 for producing fiber resin composite material>
The manufacturing method of the 1st fiber resin composite material of this invention makes the above-mentioned cellulose nonwoven fabric into the dispersion for fiber resin composite material formation of this invention containing resin and / or a resin precursor, and the specific compound of this invention. It is a method for producing a fiber resin composite material of the present invention comprising a cellulose nonwoven fabric, a resin and a specific compound of the present invention by impregnation or by applying the dispersion for forming a fiber resin composite material to a cellulose nonwoven fabric. .

(Dispersion for forming fiber resin composite material)
Hereinafter, the dispersion for forming a fiber resin composite material of the present invention containing a resin and / or a resin precursor and the specific compound of the present invention will be described.

  Suitable resins and / or resin precursors contained in this dispersion for forming a fiber resin composite material are thermoplastic resins that become fluid when heated, thermosetting resins that polymerize when heated, It is at least one resin (polymer material) or a precursor thereof selected from active energy ray-curable resins that are polymerized and cured by irradiation with active energy rays such as ultraviolet rays and electron beams.

In the present invention, the precursor of the resin (polymer material) is a so-called monomer or oligomer.
Further, the thermoplastic resin, thermosetting resin, and light (active energy ray) curable resin in the present invention may be used alone or in combination of two or more.

The resin used in the present invention (in the case of a precursor, the polymerized resin) is a synthetic polymer that is amorphous and has a high glass transition temperature (Tg), and is a highly durable fiber resin excellent in transparency. Preferred for obtaining a composite material, of which the degree of amorphousness is preferably 10% or less, particularly 5% or less in terms of crystallinity, and Tg is 110 ° C. or more, particularly 120 ° C. or more, The thing of 130 degreeC or more is preferable. If the Tg of the resin used is low, the manufactured fiber resin composite material may be deformed when it is exposed to, for example, hot water, which causes a practical problem.
Moreover, in order to obtain a low water-absorbing fiber resin composite material, it is preferable to select a material having few hydrophilic functional groups such as a hydroxy group, a carboxy group, and an amino group.

  Tg can be obtained by a general method. For example, it can be determined by measurement using a DSC (Differential Scanning Calorimetry) method. The degree of crystallinity can be calculated from the density of the amorphous part and the crystalline part, and can also be calculated from tan δ, which is the ratio of the elastic modulus to the viscosity, by dynamic viscoelasticity measurement.

  Below, the specific example of resin which can be used by this invention, and its precursor is demonstrated.

<Thermoplastic resin>
Although it does not specifically limit as a thermoplastic resin and its precursor, A styrene resin, an acrylic resin, an aromatic polycarbonate resin, an aliphatic polycarbonate resin, an aromatic polyester resin, an aliphatic polyester resin , Aliphatic polyolefin resins, cyclic olefin resins, polyamide resins, polyphenylene ether resins, thermoplastic polyimide resins, polyacetal resins, polysulfone resins, amorphous fluorine resins, and precursors thereof. .

<Thermosetting resin>
As the thermosetting resin and its precursor, is not particularly limited, A acrylic resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicone resin, polyurethane resin, diallyl phthalate resin, or the like, And precursors thereof.

<Photocurable resin>
The photocurable resin and its precursor, is not particularly limited, A acrylic resins, etc., and their precursors thereof.

  Specific examples of the thermoplastic resin, the thermosetting resin, and the photocurable resin include those described in JP-A-2009-299043.

  In addition, you may mix | blend a polymerization initiator, a hardening | curing agent, a chain transfer agent, a ultraviolet absorber, a filler, a silane coupling agent etc. suitably with the dispersion for fiber resin composite material formation as needed.

<Content of resin and / or resin precursor and specific compound of the present invention>
The content of the resin and / or resin precursor in the dispersion for forming a fiber resin composite material is usually 1% by weight or more, preferably 20% by weight or more, more preferably 50% by weight or more, and usually 99% by weight or less, preferably Is 97% by weight or less, more preferably 95% by weight or less. If the content of the resin and / or resin precursor is below the lower limit, the resulting composite material may have a low degree of cure and may be easily cracked. If the content exceeds the upper limit, the content of the specific compound of the present invention is relatively small. Thus, there is a risk that it is difficult to obtain the effect of suppressing heat coloring.

  The content of the specific compound of the present invention in the dispersion for forming fiber resin composite material is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, usually 99% by weight or less, preferably Is 80% by weight or less, more preferably 50% by weight or less. If the content of the specific compound of the present invention is less than the above lower limit, the effect of suppressing heat coloring may be difficult to obtain, and if it exceeds the above upper limit, the content of the resin and / or resin precursor is relatively reduced. The fiber-resin composite material obtained in this way has a low degree of curing and may be easily broken.

  Since the content ratio of the resin and / or resin precursor contained in the dispersion for forming a fiber resin composite material and the specific compound of the present invention has a good balance between curability and heat coloring suppression effect, And / or relative to the resin precursor 1, the specific compound of the present invention is preferably 0.01 times or more, more preferably 0.02 times or more, and preferably 1 time or less, 0 More preferably, it is 7 times or less.

(Dispersion medium)
The dispersion for forming a fiber resin composite material of the present invention usually contains water and / or an organic solvent as a dispersion medium. Organic solvents include methanol, ethanol, propyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, cyclohexane, hexane, heptane, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethylene Examples thereof include one or more of glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy 2-propanol, propylene glycol monomethyl ether acetate, tetrahydrofuran, diethyl ether and the like.

  The content of the dispersion medium in the dispersion for forming a fiber resin composite material is usually 1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, and usually 99% by weight or less, preferably 98% by weight or less, More preferably, it is 97 weight% or less. If the content of the dispersion medium is less than the above lower limit, the fluidity of the dispersion may be impaired and workability may be deteriorated. If the content exceeds the above upper limit, the solvent removal step may be expensive.

(Impregnation / application method)
As a method for manufacturing the fiber resin composite material of the present invention by impregnating the above-mentioned cellulose nonwoven fabric into the fiber resin composite material-forming dispersion, or applying the fiber resin composite material-forming dispersion to the cellulose nonwoven fabric. The following methods can be mentioned.
(A) Method of impregnating a cellulose nonwoven fabric with a dispersion for forming a fiber resin composite material containing a liquid thermoplastic resin precursor and polymerizing the cellulose nonwoven fabric (b) A thermosetting resin precursor or a photocurable resin precursor on a cellulose nonwoven fabric A method of impregnating a dispersion for forming a fiber resin composite material containing a body and polymerizing and curing (c) A solution of a dispersion for forming a fiber resin composite material on a cellulose nonwoven fabric (thermoplastic resin, thermoplastic resin precursor, thermosetting After impregnating one or more selected from a resin precursor and a photo-curable resin precursor and a solution containing the specific compound of the present invention as a solute) and drying, it is brought into close contact with a heating press or the like, and polymerized and cured as necessary. Method (d) Method of impregnating cellulose nonwoven fabric with melt of dispersion for forming fiber resin composite material containing thermoplastic resin, and adhering with a hot press or the like (e) Cellulose nonwoven fabric A method of applying a liquid fiber resin composite material dispersion containing a thermoplastic resin precursor, a thermosetting resin precursor or a photocurable resin precursor to the surface or both surfaces and polymerizing and curing (f) On one or both sides, a dispersion solution for forming a fiber resin composite material (one or more selected from thermoplastic resins, thermoplastic resin precursors, thermosetting resin precursors, and photocurable resin precursors) and the specific compound of the present invention Is applied as a solute), and after removing the solvent, it is polymerized and cured as necessary.

  After impregnation or coating as described above and curing as necessary, post-treatment such as drying may be further performed as desired.

  The fiber resin composite material of the present invention may include one cellulose nonwoven fabric or a plurality of cellulose nonwoven fabrics. A fiber resin composite material including a plurality of cellulose nonwoven fabrics may be used. In order to manufacture, after manufacturing the fiber resin composite material containing one cellulose nonwoven fabric by said method, you may laminate | stack and integrate several sheets of the obtained fiber resin composite material.

<Method 2 for producing fiber resin composite material>
The manufacturing method of the 2nd fiber resin composite material of this invention is a cellulose fiber by hardening the cellulose fiber dispersion of this invention containing a cellulose fiber, resin, and / or a resin precursor, and the specific compound of this invention. And a resin and a specific compound of the present invention.

(Cellulose fiber dispersion)
Hereinafter, the cellulose fiber-containing dispersion of the present invention containing the cellulose fiber and the specific compound of the present invention will be described. Thus, although a cellulose fiber dispersion contains a cellulose fiber and the specific compound of this invention, Preferably it contains resin and / or a resin precursor.

This cellulose fiber dispersion may be produced by mixing cellulose fibers and the specific compound of the present invention.
For example, after preparing the cellulose fiber dispersion of the present invention containing the cellulose fiber and the specific compound of the present invention, the resin and / or the resin precursor may be mixed and manufactured, or these may be mixed at once. The order of mixing the cellulose fibers, the specific compound of the present invention, and the resin and / or resin precursor is not particularly limited.

In addition, as resin and / or resin precursor contained in a cellulose fiber dispersion, what was mentioned above as resin and / or resin precursor contained in the dispersion for fiber resin composite material formation of this invention can be used.
In addition, the cellulose fiber dispersion also contains a polymerization initiator, a chain transfer agent, an ultraviolet absorber, a filler, a silane coupling agent, and the like as necessary, as with the dispersion for forming a fiber resin composite material. Also good.

As a method for producing a cellulose fiber dispersion containing cellulose fiber and the specific compound of the present invention, the specific compound of the present invention is applied to a dispersion of cellulose fiber, preferably a fine cellulose fiber dispersion obtained by the above-described defibrating treatment. The method of adding is mentioned.
In addition, the specific compound of the present invention is added to the above-mentioned cellulose fiber raw material dispersion, and the above-described defibrating treatment is performed while the specific compound of the present invention is contained, so that the fine cellulose fiber dispersion containing the specific compound of the present invention is obtained. A liquid is obtained, and this may be used as the cellulose fiber dispersion of the present invention containing the cellulose fiber and the specific compound of the present invention.
In addition, a resin and / or a resin precursor may be added to the cellulose fiber raw material dispersion described above to perform defibrating treatment, or both the specific compound of the present invention and the resin and / or resin precursor may be added. Then, the defibrating process may be performed.

(Cellulose fiber, resin and / or resin precursor, content of specific compound of the present invention)
The content of cellulose fibers in the cellulose fiber dispersion is usually 1% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, usually 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less. If the content of the cellulose fiber in the cellulose fiber dispersion is below the lower limit, the fiber resin composite material obtained may have a high linear thermal expansion coefficient or a decrease in elastic modulus or strength. The dispersion may increase in viscosity and become difficult to handle.

  The content of the specific compound of the present invention in the cellulose fiber dispersion is usually 1% by weight or more, preferably 2% by weight or more, more preferably 5% by weight or more, usually 90% by weight or less, preferably 80% by weight or less, More preferably, it is 50 weight% or less. If the content of the specific compound of the present invention in the cellulose fiber dispersion is below the lower limit, the effect of suppressing heat coloring may be reduced, and if the content exceeds the upper limit, the degree of curing of the resulting fiber resin composite material is low and easily cracked. There is a fear.

  The cellulose fiber dispersion may contain a resin and / or a resin precursor, and the content thereof is usually 1% by weight or more, preferably 5% by weight or more, more preferably 7% by weight or more, usually 99% by weight. % Or less, preferably 98% by weight or less, more preferably 97% by weight or less. If the content of the resin and / or resin precursor in the cellulose fiber dispersion is below the lower limit, the resulting fiber-resin composite material may have a low degree of curing and may be easily cracked. There is a possibility that the content of the specific compound is reduced and the effect of suppressing heating coloring is reduced.

  When the cellulose fiber dispersion contains a resin and / or a resin precursor, the content ratio of the resin and / or resin precursor contained in the cellulose fiber dispersion and the specific compound of the present invention is curable and suppresses heat coloring. Since the balance of the effect is good, the specific compound of the present invention is preferably 0.01 times or more and 0.02 times or more with respect to the resin and / or the resin precursor 1 by weight ratio. More preferably, it is preferably 1 times or less, and more preferably 0.7 times or less.

(Dispersion medium)
The cellulose fiber dispersion of the present invention usually contains water and / or an organic solvent as a dispersion medium. As an organic solvent as a dispersion medium, what was illustrated as an organic solvent which the above-mentioned dispersion for fiber resin composite material formation of this invention contains as a dispersion medium is mentioned.

  The content of the dispersion medium in the cellulose fiber dispersion is usually 1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, usually 99.5% by weight or less, preferably 99.0% by weight or less. More preferably, it is 98.5% by weight or less. If the content of the dispersion medium in the cellulose fiber dispersion is less than the above lower limit, the cellulose fibers may be aggregated. If the content exceeds the above upper limit, the solvent removal step may be expensive.

<Curing>
In any of the fiber resin composite material manufacturing methods, a curing treatment is performed to manufacture the fiber resin composite material.
As the curing treatment, for example, a heat treatment and / or an exposure treatment are performed in accordance with the resin to remove the solvent. When a resin precursor is used, the precursor is cured through this step to become a resin.

  When the heating and / or exposure treatment is performed, in the case of the production method 2, a cellulose fiber dispersion containing a resin and / or a resin precursor is applied onto a substrate such as a glass substrate or a plastic substrate to form a coating film. Alternatively, it may be poured into a mold. After applying or pouring into the mold, if necessary, a drying treatment may be applied to remove the solvent.

  The heating conditions for performing the curing process by heating are not particularly limited, and when a resin precursor is used, it may be at or above the temperature at which the precursor is cured. Among these, the heating temperature is preferably 60 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint that the solvent can be volatilized and removed. In addition, from the point which suppresses decomposition | disassembly of a cellulose fiber, 250 degreeC or less is preferable and the heating temperature has more preferable 200 degreeC or less. The heating time is preferably 60 to 180 minutes from the viewpoint of productivity.

  The heat treatment may be performed multiple times by changing the temperature and the heating time. Specifically, primary heating at 60 to 100 ° C. for 30 to 60 minutes, secondary heating at 130 to 160 ° C. for 30 to 60 minutes, and 150 to 200 ° C. which is 40 to 60 ° C. higher than the secondary heating temperature. It is preferable to carry out by a three-stage treatment with tertiary heating for ˜60 minutes in that the solvent is completely removed, the surface shape of the resulting fiber-resin composite material is reduced, and complete curing is achieved. Note that the heat treatment is preferably performed in at least two stages.

  In the exposure process in the case of performing the curing process by exposure, light such as infrared rays, visible rays, and ultraviolet rays, radiation such as electron beams, and the like are used, but light is preferable. More preferred is light having a wavelength of about 200 to 450 nm, and even more preferred is ultraviolet light having a wavelength of 300 to 400 nm.

The optimal amount of light irradiation is appropriately selected depending on the resin precursor used, the photopolymerization initiator, and the like, but ultraviolet rays having a wavelength of 300 to 450 nm are preferable, preferably 0.1 J / cm ² or more and 200 J / cm. ² the range, more preferably preferably irradiated with 1 J / cm ² or more 20 J / cm ² or less. Moreover, it is more preferable to irradiate by dividing into multiple times. That is, it is preferable to irradiate about 1/20 to 1/3 of the total irradiation amount at the first time and to irradiate the necessary remaining amount after the second time.

  Specific examples of the lamp to be used include a metal halide lamp, a high pressure mercury lamp lamp, an ultraviolet LED lamp and the like.

{Fiber resin composite material}
As described above, the fiber resin composite material of the present invention containing the cellulose fiber, the resin, and the specific compound of the present invention can be obtained. As described above, the cellulose fiber may exist as a nonwoven fabric in the fiber resin composite material or may exist in a dispersed state.

<Cellulose fiber content>
The content of the cellulose fiber in the fiber resin composite material of the present invention is not particularly limited, but is preferably 2.5% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight based on the total amount of the composite material. 99% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight or less.
When the content of the cellulose fiber in the fiber resin composite material is too small, the effect of reducing the linear thermal expansion coefficient becomes insufficient, and further, the strength and the elastic modulus tend to decrease. If there is too much cellulose fiber content in the fiber-resin composite material, adhesion between the fibers by the resin or filling of the space between the fibers will not be sufficient, the strength and transparency of the fiber-resin composite material, the surface when cured There is a possibility that the flatness of the material will be lowered.

<Resin content>
The content of the resin in the fiber resin composite material of the present invention is not particularly limited, but is preferably 1% by weight or more, more preferably 20% by weight or more, still more preferably 30% by weight or more from the viewpoint of moldability. 5 wt% or less is preferable, 95 wt% or less is more preferable, and 90 wt% or less is more preferable. When the content of the resin in the fiber resin composite material is too large, the content of the cellulose fiber is relatively decreased, and the effect of reducing the linear thermal expansion coefficient tends to be insufficient. If there is too little resin in the fiber-resin composite material, adhesion between the fibers by the resin or filling of the space between the fibers will not be sufficient, and the strength and transparency of the fiber-resin composite material and the flatness of the surface when cured May fall.

<Content of specific compound of the present invention>
The content of the specific compound of the present invention in the fiber resin composite material of the present invention is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, usually 50% by weight or less, preferably 40% by weight. Hereinafter, it is more preferably 30% by weight or less. If the content of the specific compound of the present invention is less than the above lower limit, the effect of suppressing heat coloring may be difficult to obtain, and if the content exceeds the above upper limit, the degree of curing of the fiber resin composite material may be low and easily broken.

  The content ratio of the resin and / or resin precursor contained in the fiber resin composite material of the present invention and the specific compound of the present invention has a good balance between curability and heat coloring suppression effect. The specific compound of the present invention is preferably 0.01 times or more with respect to the resin precursor 1, more preferably 0.02 times or more, and preferably 1 time or less. More preferably, it is 7 times or less.

  The fiber resin composite material of the present invention may contain cellulose fibers, a resin, and other compounding agents of the specific compound of the present invention. For example, what was illustrated as mix | blending with the above-mentioned dispersion for fiber resin composite material formation is mentioned.

  The content of the cellulose fiber in the fiber resin composite material of the present invention can be determined, for example, from the weight of the cellulose fiber before composite and the weight of the fiber resin composite material after composite. Alternatively, the fiber resin composite material is immersed in a solvent in which the resin and the specific compound of the present invention are soluble to remove only the resin and the specific compound of the present invention, and the weight can be determined from the weight of the remaining cellulose fibers. The content of the resin in the fiber resin composite material and the specific compound of the present invention can be determined by calculation from the ratio of the resin and / or resin precursor used in the production of the fiber resin composite material and the specific compound of the present invention. . It can also be determined by quantitatively determining the functional group of the resin, the specific compound of the present invention, or the cellulose fiber using NMR, IR, or the method of determining from the specific gravity of the resin.

<Shape / Thickness>
The shape of the fiber resin composite material of the present invention is not particularly limited, and may be a plate shape or a plate shape having a curved surface. Other irregular shapes may also be used. Further, the thickness is not necessarily uniform and may be partially different.

  When the shape of the fiber resin composite material of the present invention is a plate shape (sheet shape, film shape), the thickness (average thickness) is preferably 10 μm or more and 10 cm or less. The strength as a material can be maintained. The thickness of the fiber resin composite material is more preferably 30 μm to 1 cm, and still more preferably 50 μm to 250 μm.

  In addition, in the said plate-shaped object, a film means the plate-shaped object whose thickness is generally 200 micrometers or less, and a sheet | seat means a plate-shaped object thicker than a film.

<Glass transition temperature>
The fiber resin composite material of the present invention is considered to have an effect of increasing the Tg (glass transition temperature) of the resin by uniformly dispersing the cellulose fibers in the resin. Due to this effect, a material having a high Tg suitable for the use described later can be obtained. In particular, when an epoxy resin is used as the resin, the effect becomes remarkable. In addition, in an electrical / electronic material use, it becomes a big merit that Tg of a fiber resin composite material raises 3-4 degreeC.

<YI value>
The fiber resin composite material of the present invention can suppress coloring due to thermal decomposition of cellulose by containing the specific compound of the present invention.

<Application>
The fiber resin composite material of the present invention may be used as a laminate together with a substrate such as a resin. Moreover, you may manufacture a laminated body by apply | coating the cellulose fiber dispersion of this invention on this board | substrate, and performing a heat processing and / or an exposure process etc. as mentioned above. Moreover, this laminated body may have a protective film.

  The fiber resin composite material or laminate thereof of the present invention can be used for various applications. Examples of the application include adhesives, paints, building materials for civil engineering and construction, insulating materials for electric / electronic parts, and the like. It is done. Particularly suitable for wiring boards such as multilayer electrical laminates and new-type printed wiring boards such as build-up methods and sealing materials because of its excellent heat resistance, low linear expansion, and moldability can do. Further, it can also be used for display substrates such as organic EL elements and liquid crystal display elements, flexible laminate applications, resist materials, sealing materials, and the like.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Production Example 1]
<Manufacture of cellulose nonwoven fabric>
Softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd.) was beaten using a disc refiner (manufactured by Kumagai Rika Kogyo Co., Ltd.). The beaten pulp is diluted with water to a concentration of 2% by weight, and defibrated for 2 hours at a rotational speed of 6500 rpm using a high-speed rotating homogenizer (M Technique Co., Ltd .: CLM11S). Obtained.
The obtained fine cellulose fiber dispersion was diluted with water to a concentration of 0.2% by weight and ethylene glycol mono-tert-butyl ether (24 times the amount of dry fine cellulose fiber (g)) was A4. The paper was put into a size paper making apparatus (manufactured by Oji Paper Co., Ltd.), dried with a cylinder dryer heated to 120 ° C., and an A4 size cellulose nonwoven fabric having a thickness of 70 μm and a basis weight of 35 g / m ² was obtained. The porosity of this cellulose nonwoven fabric was calculated to be 64% by volume.
In addition, the number average fiber diameter of the cellulose fiber after the defibrating treatment was 28 nm.

<Chemical modification of cellulose nonwoven fabric>
The cellulose non-woven fabric was rolled up into a cylinder by stacking 11 sheets, and placed in a container containing 20 mL of acetic anhydride so as not to come into contact with the liquid and sealed. The container was heated to 145 ° C., the temperature in the container was raised to 140 ° C., and acetic anhydride vapor was brought into contact with the cellulose nonwoven fabric for 60 minutes (treatment time) to carry out the reaction. After the reaction, it was dried with a hot air dryer at 140 ° C. to remove residual gas, thereby obtaining an acetylated cellulose nonwoven fabric. It was 11.7 mol% when the chemical modification rate of this cellulose nonwoven fabric was calculated | required with the measuring method of the above-mentioned chemical modification rate.

[Example 1]
The cellulose nonwoven fabric obtained in Production Example 1 was prepared by using 89.8% by weight of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK Ester A-DCP), glycidyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; Light Ester G) 10 0.04% by weight, impregnated with 0.2% by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF; lucillin TPO) (dispersion for forming fiber resin composite material) and under reduced pressure Let stand for 1 hour.

The impregnated cellulose non-woven fabric was sandwiched between two glass plates and irradiated with an electrodeless mercury lamp (“D bulb” manufactured by Fusion UV Systems) under an irradiation light amount of 400 mW / cm ² and a line speed of 7 m / min. . The amount of light at this time was 0.12 J / cm ² . The glass surface sandwiching the cellulose nonwoven fabric was inverted, and the back surface was irradiated again under the same conditions as described above. This was done 10 times. Next, irradiation was performed at a line speed of 2 m / min under an irradiation light amount of 1900 mW / cm ² . The amount of light at this time was 2.7 J / cm ² . In the same manner as described above, this operation was further repeated 9 times by inverting the glass surface. The total amount of irradiation light was 28.2 J / cm ² . After the ultraviolet irradiation, the glass plate was removed and heated in a nitrogen gas atmosphere at 200 ° C. for 2 hours to obtain a plate-like fiber resin composite material having a thickness of 95 μm.
In addition, the illumination intensity of the ultraviolet rays measured the range of 320-390 nm at 23 degreeC using the attachment UV-35 with the ultraviolet illuminance meter (Oak Manufacturing; UV-M02).

The yellowness (YI value) of the obtained fiber resin composite material was measured according to JIS standard K7105 using a color computer manufactured by Suga Test Instruments Co., Ltd. and found to be 8.27. Moreover, when the total light transmittance by C light was measured about the obtained fiber resin composite material according to JIS specification K7136 using the Hezometer by Suga Test Instruments, haze was 33.28%, total light transmittance. Was 86.92%.
Further, this fiber resin composite material was heated as it was for 2 hours in a nitrogen gas atmosphere at 220 ° C., and then the yellowness (YI value) was measured in the same manner as described above, which was 13.03. Furthermore, it heated for 2 hours in 250 degreeC nitrogen gas atmosphere, and it was 32.6 when yellowness (YI value) was measured similarly.
The content of cellulose fibers in the fiber resin composite material was determined to be 37% by weight from the solid content of the cellulose nonwoven fabric and the dispersion for forming the fiber resin composite material.

[Example 2]
The same as in Example 1 except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toagosei Co., Ltd .; OXT-212). Thus, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 8.23. The haze was 34.96% and the total light transmittance was 86.45%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 16.51, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 54. .05.

[Example 3]
The same as in Example 1 except that glycidyl methacrylate contained in the liquid mixture impregnated with the cellulose nonwoven fabric was changed to 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate (manufactured by Wako Pure Chemical Industries, Ltd.). Thus, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 12.84. The haze was 32.78% and the total light transmittance was 85.74%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 12.19, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 57. .6.

[Example 4]
A fiber resin composite material is obtained in the same manner as in Example 1 except that the glycidyl methacrylate contained in the liquid mixture impregnated with the cellulose nonwoven fabric is changed to a hydrogenated bisphenol A type liquid epoxy resin (Mitsubishi Chemical Corporation; YX8000). It was.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 10.16. The haze was 32.29% and the total light transmittance was 87.91%.
Further, the yellowness (YI value) after heating in a nitrogen gas atmosphere at 220 ° C. for 2 hours was 18.04, and the yellowness (YI value) after heating in a nitrogen gas atmosphere at 250 ° C. for 2 hours was 45. .39.

[Example 5]
A fiber resin composite material was obtained in the same manner as in Example 1 except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.).
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 7.94. The haze was 31.55% and the total light transmittance was 87.06%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. was 13.13, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. was 43. .41.

[Example 6]
Except for changing the content of tricyclodecane dimethanol diacrylate to 79.8% by weight and the content of 4-hydroxybutyl acrylate glycidyl ether to 20.0% by weight, contained in the mixed liquid impregnated with the cellulose nonwoven fabric, In the same manner as in Example 5, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 8.60. The haze was 33.61% and the total light transmittance was 87.06%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 15.78, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 54. .77.

[Example 7]
Except for changing the content of tricyclodecane dimethanol diacrylate to 49.9% by weight and the content of 4-hydroxybutyl acrylate glycidyl ether to 49.9% by weight, contained in the mixed liquid impregnated with the cellulose nonwoven fabric, In the same manner as in Example 5, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 10.52. The haze was 39.92% and the total light transmittance was 86.12%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 20.64, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 57. .11.

[Example 8]
A fiber resin composite material was obtained in the same manner as in Example 1 except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd .; HEMA).
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 6.61. The haze was 30.75% and the total light transmittance was 87.71%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 11.08, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 48. .98.

[Comparative Example 1]
A mixture of 99.8% by weight of tricyclodecane dimethanol diacrylate and 0.2% by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide without adding glycidyl methacrylate to the mixture impregnated with cellulose nonwoven fabric A fiber resin composite material was obtained in the same manner as in Example 1 except that.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 6.33. The haze was 30.89% and the total light transmittance was 88.00%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 10.59, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 69. 37.

[Comparative Example 2]
A fiber resin composite material was obtained in the same manner as in Example 1 except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to tricyclodecyl methacrylate (manufactured by Hitachi Chemical Co., Ltd .; FA513M).
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 6.75. The haze was 32.78% and the total light transmittance was 87.58%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 12.45, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 76. 0.03.

[Example 9]
Example 1 except that tricyclodecane dimethanol diacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to 1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical; NK ester A-DOD-N). In the same manner, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 10.28. The haze was 48.33% and the total light transmittance was 86.23%.
Further, the yellowness (YI value) after heating in a nitrogen gas atmosphere at 220 ° C. for 2 hours was 18.51, and the yellowness (YI value) after heating in a nitrogen gas atmosphere at 250 ° C. for 2 hours was 46. .49.

[Example 10]
The same as Example 9 except that glycidyl methacrylate contained in the liquid mixture impregnated with the cellulose nonwoven fabric was changed to 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toagosei Co., Ltd .; OXT-212). Thus, a fiber resin composite material was obtained.
This fiber resin composite material was measured for yellowness (YI value) in the same manner as in Example 1. As a result, it was 12.26. The haze was 62.31% and the total light transmittance was 82.73%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 22.5, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 69. .24.

[Example 11]
The same as Example 9 except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric was changed to 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate (manufactured by Wako Pure Chemical Industries, Ltd.). Thus, a fiber resin composite material was obtained.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 17.91. The haze was 59.97% and the total light transmittance was 83.73%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 25.42, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 64. .58.

[Example 12]
A fiber resin composite material is obtained in the same manner as in Example 9, except that glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric is changed to hydrogenated bisphenol A type liquid epoxy resin (Mitsubishi Chemical Corporation; YX8000). It was.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 12.94. The haze was 50.91% and the total light transmittance was 85.00%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 20.23, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 56. .48.

[Example 13]
The glycidyl methacrylate contained in the mixed liquid impregnated with the cellulose nonwoven fabric is changed to 4-hydroxybutyl acrylate glycidyl ether, and the content of 1,10-decanediol diacrylate is 49.9% by weight, 4-hydroxybutyl acrylate glycidyl ether. A fiber resin composite material was obtained in the same manner as in Example 9 except that the content of was changed to 49.9% by weight.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 12.42. The haze was 57.68% and the total light transmittance was 85.29%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 23.94, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 61. .14.

[Comparative Example 3]
No mixture of glycidyl methacrylate was added to the liquid mixture impregnated with cellulose nonwoven fabric, and 99.8% by weight of 1,10-decanediol diacrylate and 0.2% by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide were mixed. A fiber resin composite material was obtained in the same manner as in Example 9 except that the liquid was used.
With respect to this fiber resin composite material, the yellowness (YI value) was measured in the same manner as in Example 1. As a result, it was 8.33. The haze was 36.68% and the total light transmittance was 87.06%.
The yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 220 ° C. is 17.7, and the yellowness (YI value) after heating for 2 hours in a nitrogen gas atmosphere at 250 ° C. is 78. .87.

The results of Examples 1 to 13 and Comparative Examples 1 to 3 are summarized in Table 1.
From Table 1, it can be seen that the fiber resin composite material of the present invention containing the specific compound of the present invention is less colored even when subjected to a heating process.

Claims (5)

Cellulose fibers having a number average fiber diameter of 2 to 400 nm, resins, and
Glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 1-hydroxy-2- (acryloyloxy) ethyl acrylate, 2-hydroxypropyl (meth) acrylate, One or more selected from the group consisting of 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate compounds (hereinafter referred to as "specific compound of the present invention".)
A fiber-resin composite material containing the specific compound of the present invention in a weight ratio of 0.01 to 1 time with respect to the resin 1. The fiber resin composite material according to claim 1, comprising the cellulose fiber nonwoven fabric (hereinafter referred to as “cellulose nonwoven fabric”). Cellulose fibers having a number average fiber diameter of 2 to 400 nm, resins and / or resin precursors, and glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, acrylic Acid 1-hydroxy-2- (acryloyloxy) ethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, And a cellulose fiber dispersion containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter referred to as “the specific compound of the present invention”), and having a weight ratio With respect to the resin and / or resin precursor 1 A cellulose fiber dispersion comprising the specific compound of the present invention in an amount of 0.01 to 1 time. A method for producing a fiber-resin composite material comprising a cellulose nonwoven fabric and a resin,
Resin and / or resin precursor, and glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 1-hydroxy-2- (acryloyloxy) ethyl acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and 2-hydroxy-3-phenoxypropyl (meth) A dispersion for forming a fiber-resin composite material containing one or more compounds selected from the group consisting of acrylates (hereinafter referred to as “specific compounds of the present invention”), and the resin and / or resin by weight ratio. 0.01 times or more of the specific compound of the present invention relative to the precursor 1 A dispersion for forming a fiber resin composite material containing 1 or less times is impregnated with a cellulose nonwoven fabric containing cellulose fibers having a number average fiber diameter of 2 to 400 nm, or the cellulose nonwoven fabric is dispersed for forming the fiber resin composite material A method for producing a fiber-resin composite material, comprising a step of applying a body. A method for producing a fiber-resin composite material comprising cellulose fibers and a resin,
Cellulose fibers having a number average fiber diameter of 2 to 400 nm, resins and / or resin precursors, and glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, acrylic Acid 1-hydroxy-2- (acryloyloxy) ethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, And a cellulose fiber dispersion containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl (meth) acrylate (hereinafter referred to as “the specific compound of the present invention”), and having a weight ratio With respect to the resin and / or resin precursor 1 And a step of curing a cellulose fiber dispersion containing the specific compound of the present invention in an amount of 0.01 times to 1 time, and a method for producing a fiber resin composite material.