WO2017006997A1 - Mixture for resin reinforcement, fiber-reinforced resin mixture, fiber-reinforced resin, and method for producing same - Google Patents

Abstract

Provided is a mixture for resin reinforcement (X1) containing a blocked isocyanate compound (A) and cellulose fibers (B). Also provided is a mixture for resin reinforcement (X1) containing a blocked isocyanate compound (A) or polyurethane compound (D), cellulose fibers (B), and an anionic surfactant (E) or silicone-based or acetylene-based nonionic surfactant (F).

Description

Resin-reinforcing mixture, fiber-reinforced resin mixture, fiber-reinforced resin, and method for producing the same Cross-reference of related applications

This application claims priority of Japanese Patent Application No. 2015-136227 filed on July 7, 2015 and Japanese Patent Application No. 2016-1115881 filed on June 10, 2016, the contents of which are incorporated by reference. It is incorporated in the description herein.

The present invention relates to a resin reinforcing mixture, a fiber reinforced resin mixture, a fiber reinforced resin, and a method for producing the same.

Conventionally, a fiber reinforced resin in which the strength of the thermoplastic resin is improved by adding cellulose fibers to the thermoplastic resin has been used.

As this type of fiber reinforced resin, for example, a fiber reinforced resin obtained by impregnating a sheet-like cellulose fiber with a thermoplastic resin and melting and curing the thermoplastic resin using two different types of solvents. It has been proposed (see Patent Document 1). Further, a fiber reinforced resin (see Patent Document 2) obtained by melting and kneading a thermoplastic resin and cellulose fibers subjected to a specific surface treatment has been proposed.

Japanese Unexamined Patent Publication No. 2005-42283 Japanese Unexamined Patent Publication No. 2006-241450

However, in the fiber reinforced resin described in Patent Document 1, it is necessary to use two specific types of solvents in order to obtain a fiber reinforced resin, and in the fiber reinforced resin described in Patent Document 2, Since it is necessary to perform a specific surface treatment on the cellulose fiber in order to obtain the resin, it is difficult to say that the fiber reinforced resin can be easily produced.
Moreover, in the fiber reinforced resin described in Patent Documents 1 and 2, it is difficult to say that the strength of the cured body is sufficiently increased.

In view of the above circumstances, a resin reinforcing mixture and a fiber reinforced resin mixture that can easily form a fiber reinforced resin with sufficiently increased strength of the cured body, and the strength of the cured body can be sufficiently increased, and easily It is an object of the present invention to provide a formed fiber reinforced resin and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have used a blocked isocyanate compound (A), a cellulose fiber (B), and a thermoplastic resin (X2) as a fiber reinforced resin (Y). It has been found that the strength of the cured body of the fiber reinforced resin (Y) can be sufficiently increased by producing the present invention, and the present invention has been completed.

That is, the resin reinforcing mixture (X1) according to the present invention is:
A block isocyanate compound (A) and a cellulose fiber (B) are contained.

Here, the “resin reinforcing mixture” means that the blocked isocyanate compound (A) and the cellulose fiber (B) are mixed in a state where the isocyanate group of the blocked isocyanate compound (A) is not dissociated. To do.

In the resin reinforcing mixture (X1) having the above-described configuration,
The blocked isocyanate compound (A) preferably has a hydrophilic group.

Here, the “hydrophilic group” of the blocked isocyanate compound means an anionic group, a cationic group, or a nonionic group. Examples of the anionic group include a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, and the like, and a carboxylate group in which a part or all of them are neutralized with a basic compound or the like, Also included are sulfonate groups, sulfate ester bases, phosphate ester bases and the like.
Examples of the cationic group include a tertiary amino group, and an acid neutralized salt of a tertiary amino group or a quaternary amino group quaternized with a quaternizing agent.
Examples of nonionic groups include polyethylene glycol chains.

In the resin reinforcing mixture (X1) having the above-described configuration,
The content of the hydrophilic group in the blocked isocyanate compound (A) is preferably 0.07 to 2.10 mmol / g.

In the resin reinforcing mixture (X1) having the above-described configuration,
The blocked isocyanate compound (A) is an oxime block agent, a phenol block agent, a lactam block agent, an alcohol block agent, an active methylene block agent, an amine block agent, a pyrazole block agent, a bisulfite block. The isocyanate group of the polyisocyanate compound may be blocked by at least one selected from the group consisting of an agent and an imidazole blocking agent.

In the resin reinforcing mixture (X1) having the above-described configuration,
Furthermore, water (C) may be contained.

The fiber-reinforced resin mixture (X) of the present invention is
The resin reinforcing mixture (X1) and the thermoplastic resin (X2) are contained.

Here, the “fiber reinforced resin mixture” means that the blocked isocyanate compound (A), the cellulose fiber (B), and the thermoplastic resin (X2) are dissociated from the blocked group of the blocked isocyanate compound and are thermoplastic. This means that the resin (X2) is mixed before being heated and mixed at a temperature equal to or higher than the melting temperature.

The fiber-reinforced resin mixture (X) of the present invention is obtained by mixing the water-containing resin reinforcing mixture (X1) and the thermoplastic resin (X2) and drying the mixture.

The fiber reinforced resin (Y) of the present invention is
The fiber reinforced resin mixture (X) is mixed in a state where the block group of the blocked isocyanate compound (A) is dissociated and heated to a temperature at which the thermoplastic resin (X2) melts.

The method for producing the fiber reinforced resin (Y) of the present invention is as follows.
The fiber-reinforced resin mixture (X) containing the blocked isocyanate compound (A), the cellulose fiber (B), and the thermoplastic resin (X2) is separated from the blocked group of the blocked isocyanate compound (A) and the heat A step of mixing is performed in a state of being heated to a temperature equal to or higher than a temperature at which the plastic resin (X2) melts.

In the manufacturing method of the fiber reinforced resin (Y) having the above-described configuration,
The fiber reinforced resin mixture (X) may further contain water (C).

On the other hand, as a result of intensive studies to solve the above problems, the present inventors have obtained an isocyanate compound (A) or a polyurethane compound (D), a cellulose fiber (B), an anionic surfactant (E), Alternatively, by producing a fiber reinforced resin (Y) using a silicone-based or acetylene-based nonionic surfactant (F) and a thermoplastic resin (X2), a cured product of the fiber-reinforced resin (Y) The inventors have found that the strength can be sufficiently increased and have completed the present invention.

That is, the other resin reinforcing mixture (X1) according to the present invention is:
A blocked isocyanate compound (A) or a polyurethane compound (D);
Cellulose fibers (B);
It contains an anionic surfactant (E) or a silicone-based or acetylene-based nonionic surfactant (F).

Here, when the resin reinforcing mixture (X1) contains the blocked isocyanate compound (A), the “resin reinforcing mixture” is a state in which the blocking group of the blocked isocyanate compound (A) is not dissociated, It means that the blocked isocyanate compound (A), the cellulose fiber (B), and the surfactant (E) or the surfactant (F) are mixed.
In the case where the resin reinforcing mixture (X1) contains the polyurethane compound (D), the “resin reinforcing mixture” means that the polyurethane compound (D) and cellulose are in a state where the polyurethane compound is not fused. It means that the fiber (B) and the surfactant (E) or surfactant (F) are mixed.
Further, the “polyurethane compound (D)” includes those having a substituent other than an isocyanate group, such as a hydroxyl group and / or an amino group, at the terminal, and those in which the isocyanate group of the polyurethane compound is blocked. I can't. Such a blocked product is included in the “block isocyanate compound (A)”.

In the resin reinforcing mixture (X1) having the above structure,
The blocked isocyanate compound (A) or the polyurethane compound (D) may have a hydrophilic group.

Here, “the blocked isocyanate compound (A) or the polyurethane compound (D) has a hydrophilic group” means “the blocked isocyanate compound (A) has a hydrophilic group or the polyurethane compound (D ) Has a hydrophilic group. The “hydrophilic group” means an anionic group, a cationic group, or a nonionic group.
Examples of the anionic group include a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, and the like, and a carboxylate group in which a part or all of them are neutralized with a basic compound or the like, Also included are sulfonate groups, sulfate ester bases, phosphate ester bases and the like.
Examples of the cationic group include a tertiary amino group, and an acid neutralized salt of a tertiary amino group or a quaternary amino group quaternized with a quaternizing agent.
Examples of nonionic groups include polyethylene glycol chains.

In the resin reinforcing mixture (X1) having the above-described configuration,
Furthermore, water (C) may be contained.

The other fiber reinforced resin mixture (X) of the present invention is:
The resin reinforcing mixture (X1) and the thermoplastic resin (X2) are contained.

Here, when the resin reinforcing mixture (X1) contains the blocked isocyanate compound (A), the “fiber reinforced resin mixture” means the blocked isocyanate compound (A), the cellulose fiber (B), and the interface. The activator (E) or the surfactant (F) is mixed before being heated and mixed above the temperature at which the blocking group of the blocked isocyanate compound (A) is dissociated and the thermoplastic resin (X2) melts. Means what
When the resin reinforcing mixture (X1) contains the polyurethane compound (D), the “fiber reinforced resin mixture” means the polyurethane compound (D), the cellulose fiber (B), and the surfactant ( E) or surfactant (F) means that the polyurethane compound (D) is fused and mixed before being heated and mixed at a temperature higher than the temperature at which the thermoplastic resin (X2) melts. .

The other fiber reinforced resin mixture (X) of the present invention is:
The resin reinforcing mixture (X1) containing the water (C) and the thermoplastic resin (X2) are mixed and dried.

The other fiber reinforced resin (Y) of the present invention is
The fiber reinforced resin mixture (X) is mixed while being heated to a temperature higher than the temperature at which the thermoplastic resin (X2) melts.

For example, when the fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A), the fiber reinforced resin (Y) has a blocked group of the blocked isocyanate compound (A). A mode of mixing in a state where the thermoplastic resin (X2) is dissociated and heated at a temperature equal to or higher than the melting temperature may be employed.
For example, when the fiber reinforced resin mixture (X) contains the polyurethane compound (D), the fiber reinforced resin (Y) is fused with the fiber reinforced resin mixture (X) and the polyurethane compound (D). And the aspect formed by mixing in the state heated more than the temperature which a thermoplastic resin (X2) fuse | melts may be employ | adopted.

The method for producing another fiber reinforced resin (Y) of the present invention includes:
Block isocyanate compound (A) or polyurethane compound (D), cellulose fiber (B), anionic surfactant (E), silicone-based or acetylene-based nonionic surfactant (F), and thermoplasticity A step of mixing the fiber reinforced resin mixture (X) containing the resin (X2) in a state of being heated to a temperature equal to or higher than a temperature at which the thermoplastic resin (X2) is melted.

For example, when the fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A), in the heating and mixing step, the fiber reinforced resin mixture (X) is converted into the blocked isocyanate compound (A). A mode of mixing in a state where the block group is dissociated and heated at a temperature equal to or higher than the temperature at which the thermoplastic resin (X2) melts may be employed.
For example, when the fiber reinforced resin mixture (X) contains the polyurethane compound (D), in the step of heating and mixing, the fiber reinforced resin mixture (X) is converted into the polyurethane compound (D). Can be adopted in which the mixture is heated and heated at a temperature equal to or higher than the temperature at which the thermoplastic resin (X2) melts.

In the manufacturing method of the fiber reinforced resin (Y) having the above-described configuration,
The fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A),
The fiber-reinforced resin mixture (X) may be mixed in a state where the fiber-reinforced resin mixture (X) is heated to a temperature at which the blocking group of the blocked isocyanate compound (A) is dissociated and the thermoplastic resin (X2) is melted. .

In the manufacturing method of the fiber reinforced resin (Y) having the above-described configuration,
The fiber reinforced resin mixture (X) contains the polyurethane compound (D),
You may provide the process of mixing the said fiber reinforced resin mixture (X) in the state heated more than the temperature which the said polyurethane compound (D) fuse | melts and the said thermoplastic resin (X2) fuse | melts.
In addition, that a polyurethane compound (D) fuse | melts means that polyurethane compounds (D) mutually fuse | fuse, and also means that a polyurethane compound (D) will be in a fusion | melting state in other words.

In the manufacturing method of the fiber reinforced resin (Y) having the above-described configuration,
The fiber reinforced resin mixture (X) may further contain water (C).

Hereinafter, a first embodiment of the present invention will be described.

The resin reinforcing mixture (X1) of this embodiment is
A block isocyanate compound (A) and a cellulose fiber (B) are contained.

The blocked isocyanate compound (A) is obtained by reacting an isocyanate group of a polyisocyanate compound with a blocking agent, and regenerates the isocyanate group by heating.

The resin reinforcing mixture (X1) contains the blocked isocyanate compound (A) and the cellulose fiber (B), whereby the resin reinforcing mixture (X1) is used as a raw material for the fiber reinforced resin (Y). Can be used as
At this time, when the fiber reinforced resin (Y) is produced, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are dissociated from the blocked group of the blocked isocyanate compound, and the thermoplastic resin (X2 ) Is heated at a temperature equal to or higher than the melting temperature and mixed, so that the blocked isocyanate compound (A) relaxes the interaction due to hydrogen bonds in the cellulose fiber (B), so that the cellulose fiber (B) is refined. The dispersion is promoted.
Thereby, a cellulose fiber is fully loosened and fully disperse | distributed.
Further, since the blocking group of the blocked isocyanate compound (A) is dissociated, the isocyanate group is regenerated, and polymerization is performed so as to take in the cellulose fiber (B), the resin component and cellulose in the fiber reinforced resin (Y). Adhesion with the fiber (B) is improved.
Thus, since a cellulose fiber (B) is disperse | distributed to a thermoplastic resin (X2) via a blocked isocyanate compound (A), the intensity | strength of the hardening body of fiber reinforced resin (Y) is fully raised.
In addition, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased as described above can be easily obtained even if the cellulose fiber is not subjected to a surface treatment step or a plurality of types of solvents are used. It is formed.

The polyisocyanate compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Moreover, as this polyisocyanate compound, the isocyanate group terminal urethane prepolymer obtained by making this isocyanate compound and a polyol compound react is also mentioned. These may be used alone or in combination of two or more.

The aliphatic polyisocyanate is not particularly limited, and examples thereof include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine. Examples thereof include diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

The alicyclic polyisocyanate is not particularly limited. For example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

The aromatic polyisocyanate is not particularly limited. For example, tolylene diisocyanate (TDI), 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.

The aromatic aliphatic polyisocyanate is not particularly limited, and examples thereof include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate.

Also, examples of the polyisocyanate compound include dimers or trimers of the above polyisocyanates, modified products such as burette isocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), and the like.

The polyisocyanate compound is preferably an isocyanate group-terminated urethane prepolymer obtained by reacting TDI, MDI, hexamethylene diisocyanate, or a modified product thereof with a polyol compound, from the viewpoint of strength and elastic modulus. An isocyanate group-terminated urethane prepolymer obtained by reacting with a polyol compound is more preferred.

The polyol compound used in the isocyanate group-terminated urethane prepolymer is not particularly limited. For example, a low molecular weight polyol having a molecular weight of 400 or less, a polyester polyol, a polyether polyol, a castor oil-based polyol, a polycarbonate polyol, or a hydrocarbon polyol. Is mentioned. These may be used alone or in combination of two or more.

The low molecular weight polyol is not particularly limited as long as it has a molecular weight of 400 or less. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1 , 3-butanediol, 1,4-butanediol, 3-methylpentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, bisphenol F, cyclohexane dimethanol, glycerin, trimethylolpropane, etc. are mentioned. Of these, trimethylolpropane is preferable.

The polyester polyol is not particularly limited, and examples thereof include a hydroxyl-terminated esterified condensate obtained by reacting the low molecular weight polyol and a polyvalent carboxylic acid. The polyvalent carboxylic acid is not particularly limited. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrofuran acid, endomethine tetrahydrofuran acid, or hexa And hydrophthalic acid. Of these, phthalic acid, isophthalic acid and terephthalic acid having an aromatic cyclic structure are preferred from the viewpoint of strength and elastic modulus.

The polyether polyol is not particularly limited, and examples thereof include low molecular weight polyols such as bisphenol A and bisphenol F, pentaerythritol, sorbitol, sucrose and the like obtained by addition polymerization of alkylene oxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. Among these, from the viewpoint of strength and elastic modulus, those having an aromatic cyclic structure, that is, those obtained by addition polymerization of alkylene oxide to bisphenol A and bisphenol F are preferred, and ethylene oxide and / or propylene oxide is added to bisphenol A. Those obtained by addition polymerization are more preferred.

The castor oil-based polyol is not particularly limited, and examples thereof include castor oil, hydrogenated castor oil hydrogenated to castor oil, castor oil fatty acid, or polyol produced using hydrogenated castor oil fatty acid hydrogenated thereto. Also included are transesterification products of castor oil and other natural fats and oils, reaction products of castor oil and polyhydric alcohols, esterification reaction products of castor oil fatty acid and polyhydric alcohols, or polyols obtained by addition polymerization of these with alkylene oxide. It is done.

The polycarbonate polyol is not particularly limited, and includes conventionally known polycarbonate polyols. Such a polycarbonate polyol is obtained, for example, by a reaction between the low molecular weight polyol and diphenyl carbonate, or a reaction between the low molecular weight polyol and phosgene.

The hydrocarbon polyol is not particularly limited, and examples thereof include polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, and hydrogenated polyisoprene polyol.

The blocking agent is not particularly limited and includes conventionally known blocking agents. For example, oxime block agent, phenol block agent, lactam block agent, alcohol block agent, active methylene block agent, amine block agent, pyrazole block agent, bisulfite block agent, imidazole block agent, etc. Is mentioned. Such blocking agents can be used alone or in combination of two or more.

The oxime blocking agent is not particularly limited, and examples thereof include formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketone oxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime. Among these, methyl ethyl ketone oxime and cyclohexanone oxime are preferable from the viewpoint of strength and elastic modulus. When such a blocking agent is used, the dissociation temperature of the blocking group is 130 to 190 ° C.

The phenolic blocking agent is not particularly limited, and examples thereof include phenol, cresol, xylenol, and ethylphenol. Among these, ortho-secondary butylphenol is preferable from the viewpoint of strength and elastic modulus. When such a blocking agent is used, the dissociation temperature of the blocking group is 120 to 180 ° C.

The lactam blocking agent is not particularly limited, and examples thereof include caprolactam, valerolactam, butyrolactam, and propiolactam. Among these, caprolactam is preferable from the viewpoint of strength and elastic modulus. When such a blocking agent is used, the dissociation temperature of the blocking group is 130 to 200 ° C.

The alcohol blocking agent is not particularly limited, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Among these, methanol and ethanol are preferable from the viewpoints of strength and elastic modulus. When such a blocking agent is used, the dissociation temperature of the blocking group is 150 to 210 ° C.

The active methylene blocking agent is not particularly limited, and examples thereof include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. When such a blocking agent is used, the dissociation temperature of the blocking group is 80 to 160 ° C.

The amine blocking agent is not particularly limited, and examples thereof include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, and dicyclohexylamine. When such a blocking agent is used, the dissociation temperature of the blocking group is 140 to 220 ° C.

The pyrazole block agent is not particularly limited, and examples thereof include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and the like. Among these, 3,5-dimethylpyrazole is preferable from the viewpoint of strength and elastic modulus. When such a blocking agent is used, the dissociation temperature of the blocking group is 110 to 180 ° C.

The bisulfite block agent is not particularly limited, and examples thereof include sodium bisulfite. When these blocking agents are used, the dissociation temperature of the blocking group is 80 to 170 ° C.

The imidazole blocking agent is not particularly limited, and examples thereof include 2-methylimidazole 2-ethyl-4-methylimidazole. When such a blocking agent is used, the dissociation temperature of the blocking group is 80 to 150 ° C.

Among these blocking agents, from the viewpoint of strength and elastic modulus, from the group consisting of an oxime blocking agent, a phenol blocking agent, a lactam blocking agent, a pyrazole blocking agent, an imidazole blocking agent, and an alcohol blocking agent. At least one selected is preferable, and an oxime blocking agent, a phenol blocking agent, a lactam blocking agent, a pyrazole blocking agent, and an imidazole blocking agent are more preferable.

Thus, in the resin reinforcing mixture (X1) of the present embodiment,
The blocked isocyanate compound (A) is an oxime block agent, a phenol block agent, a lactam block agent, an alcohol block agent, an active methylene block agent, an amine block agent, a pyrazole block agent, a bisulfite block. The isocyanate group of the polyisocyanate compound may be blocked by at least one selected from the group consisting of an agent and an imidazole blocking agent.

When the blocked isocyanate compound (A) is at least one selected from the above group, there is an advantage that the strength and elastic modulus of the resin can be increased when the fiber reinforced resin (Y) is produced.

The dissociation temperature of the blocking group of the blocked isocyanate compound (A) is preferably 70 ° C. to 210 ° C., more preferably 80 ° C. to 190 ° C. from the viewpoint of strength and elastic modulus. Examples of the blocking agent in which the dissociation temperature of the blocking group falls within this range include methyl ethyl ketone oxime, ortho-secondary butylphenol, caprolactam, sodium bisulfite, 3,5-dimethylpyrazole, 2-methylimidazole and the like.

The blocked isocyanate compound (A) preferably has a hydrophilic group from the viewpoint of strength such as bending strength and bending elastic modulus of the cured product of the fiber reinforced resin (Y). The reason why the blocked isocyanate compound (A) having a hydrophilic group is excellent in bending strength and flexural modulus is not clear, but the interaction due to hydrogen bonding between the cellulose fibers (B) is alleviated, and the blocked isocyanate compound (A). This is presumably due to the effect of promoting the dispersion of cellulose fibers therein.

Thus, in the resin reinforcing mixture (X1) of the present embodiment,
The blocked isocyanate compound (A) preferably has a hydrophilic group.

As described above, the blocked isocyanate compound (A) has a hydrophilic group so that when the fiber reinforced resin (Y) is produced, the blocked isocyanate compound (A) is formed by hydrogen bonds in the cellulose fiber (B). In order to further relax the interaction, the dispersion of the cellulose fiber (B) is further promoted.
Thereby, a cellulose fiber is more fully disperse | distributed in a thermoplastic resin (X2).
Therefore, the strength of the cured body of the fiber reinforced resin (Y) is more sufficiently increased.

The hydrophilic group may be any of the above anionic group, cationic group, or nonionic group, and is not particularly limited. Among these, from the viewpoint of strength such as bending strength and bending elastic modulus, the anionic group Or a cationic group is preferable.

The hydrophilic group compound for introducing the blocked isocyanate compound (A) by incorporating a hydrophilic group is not particularly limited. For example, (di) alkanol carboxylic acid or sulfonic acid tertiary amine or alkali metal Examples thereof include Japanese products, (methoxy) polyalkylene oxides, (di) alkanolamine organic / inorganic acid neutralized products, and quaternary ammonium salts obtained by reacting these with alkyl halides or dialkyl sulfuric acid. Of these, (di) neutralized products of alkanol carboxylic acids or sulfonic acids with tertiary amines or alkali metals, (di) neutralized products of alkanolamines with organic / inorganic acids, and reaction with alkyl halides or dialkyl sulfate Quaternary ammonium salts are preferred.
The (methoxy) polyalkylene oxide may contain at least ethylene oxide as the alkylene oxide, and may contain other alkylene oxides such as propylene oxide and butylene oxide. In the case of using a (methoxy) polyalkylene oxide containing a plurality of types of alkylene oxide, the addition form (form of introducing a hydrophilic group) may be either a block addition form or a random addition form. There may be.

Examples of compounds that can introduce these hydrophilic groups include the following.
Examples of the compound capable of introducing a hydrophilic group include carboxylic acid compounds such as dimethylolpropionic acid, dimethylolbutanoic acid, lactic acid, and glycine, or polyester diol composed of aminoethylsulfonic acid, sulfoisophthalic acid and diol, and the like. Examples of the anionic type include salts obtained by neutralizing a sulfonic acid compound with a tertiary alkanolamine such as triethylamine, NaOH, or dimethylaminoethanol. Of these, dimethylolpropionic acid, glycine, and a sodium salt of aminoethylsulfonic acid are preferred from the viewpoints of the bending strength and flexural modulus of the composite material.

Further, as a compound capable of introducing a hydrophilic group, for example, an alkanolamine such as dimethylaminoethanol and methyldiethanolamine is neutralized with an organic carboxylic acid such as formic acid and acetic acid, or an inorganic acid such as hydrochloric acid and sulfuric acid. And quaternized with alkyl halides such as methyl chloride and methyl bromide or dialkyl sulfuric acid such as dimethyl sulfate. Of these, a combination of methyldiethanolamine and an organic carboxylic acid and a combination of methyldiethanolamine and dimethylsulfuric acid are preferred because they are easy to produce industrially.

The content of the hydrophilic group in the blocked isocyanate compound (A) is not particularly limited. For example, the content is preferably 0.07 to 2.10 mmol / g, more preferably 0.12 to 1.80 mmol / g, and 0.17 to 1.60 mmol / g. Is more preferable.
When the content of the hydrophilic group is 0.07 to 2.10 mmol / g, when the fiber reinforced resin (Y) is produced, the cellulose fibers are more sufficiently bonded via the blocked isocyanate compound (A). And is further dispersed.
Therefore, the strength (for example, strength such as bending strength and bending elastic modulus) of the cured body of the fiber reinforced resin (Y) is further increased.
The content of such a hydrophilic group is a value measured by a measurement method described in Examples described later.

The blocked isocyanate compound (A) preferably has an aromatic cyclic structure from the viewpoint of strength such as bending strength and bending elastic modulus of the cured product of the fiber reinforced resin (Y). The content of the aromatic cyclic structure in the blocked isocyanate compound (A) is preferably 4% by mass to 80% by mass, and more preferably 8% by mass to 70% by mass.
In addition, as shown in the Example mentioned later, content of the said aromatic cyclic structure is the ratio of the aromatic cyclic structure contained in the said block isocyanate compound with respect to the total mass of the said blocked isocyanate compound (A). Show. That is, the content is the total mass of all raw materials such as polyol and polyisocyanate used for the production of the blocked isocyanate compound, and the aromatic cyclic structure-containing polyol or aromatic used for the production of the blocked isocyanate compound. It is a value calculated based on the content of the aromatic cyclic structure possessed by the aromatic cyclic structure content such as the polycyclic isocyanate containing the aromatic cyclic structure. Examples of the aromatic cyclic structure include a phenyl group and a naphthalene group.

It is also a preferable aspect that the blocked isocyanate compound (A) has a short-chain polyol group (a short-chain polyol group is introduced). By having a short-chain polyol group, when the blocked isocyanate compound (A) is a water body, urethane bonds are localized in the blocked isocyanate compound (A) and a branched structure is introduced into the molecule. obtain. The short-chain polyol group for localizing the urethane bond is not particularly limited, and examples thereof include ethylene glycol and 1,4-butanediol. Although it does not specifically limit as a short chain polyol for introduce | transducing a branched structure, For example, a trimethylol propane, glycerol, etc. are mentioned. These can be used as one kind or a mixture of two or more kinds.

It is also a preferable aspect that a chain extender is introduced into the blocked isocyanate compound (A). By introducing the chain extender, when the blocked isocyanate compound (A) is an aqueous dispersion as described later, the molecular weight thereof can be increased. The chain extender is not particularly limited, and examples thereof include water, diamines such as ethylenediamine, trimethylenediamine, piperazine, and isophoronediamine, and polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine. These can be used as one kind or a mixture of two or more kinds.

Even if the blocked isocyanate compound (A) is contained in the resin reinforcing mixture (X1) without being dispersed in water, the resin reinforcing mixture (X1) is used as an aqueous dispersion dispersed in water (C). It may be contained in.
Thus, the resin reinforcing mixture (X1) may contain the blocked isocyanate compound (A), the cellulose fiber (B), and water (C).
Thus, by containing water, when the fiber reinforced resin (Y) is produced, the cellulose fibers are more easily dispersed.
Thereby, the intensity | strength of the hardening body of fiber reinforced resin (Y) is raised more fully.

The blocked isocyanate compound (A) may be contained in the resin reinforcing mixture (X1) by being mixed with the cellulose fiber (B) as an aqueous dispersion dispersed in water and then dried. Good.
That is, the resin reinforcing mixture (X1) may be dried after the blocked isocyanate compound (A), the cellulose fiber (B), and water (C) are mixed.
Thus, when fiber-reinforced resin (Y) is produced by containing water, a cellulose fiber is disperse | distributed more fully.
Thereby, the intensity | strength of the hardening body of fiber reinforced resin (Y) is raised more fully.

The form of the resin reinforcing mixture (X1) is not particularly limited as long as it contains the blocked isocyanate compound (A) and the cellulose fiber (B).

In a preferred embodiment, when the blocked isocyanate compound (A) is contained in the resin reinforcing mixture (X1) as an aqueous dispersion, a surfactant is used to disperse the blocked isocyanate compound in water. is there. Examples of the surfactant include nonionic surfactants and anionic surfactants.

The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene alkylphenol ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and polyoxyethylene sorbitol tetraoleate.
The anionic surfactant is not particularly limited. For example, fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkane sulfonate sodium salts, alkyl diphenyl ethers. Examples include sodium sulfonate, polyoxyethylene alkylphenyl sulfate, and polyoxyethylene alkylsulfate.
Of these, nonionic surfactants are preferably used.

The addition amount of the surfactant is preferably an addition amount within a range that does not adversely affect the strength such as bending strength and bending elastic modulus of the fiber reinforced resin (Y) to be obtained, and the solid content of the blocked isocyanate compound (A) is 100. It can be added in an amount of 20 parts by mass or less, preferably 15 parts by mass or less with respect to parts by mass.

When the blocked isocyanate compound (A) is an aqueous dispersion, from the viewpoint of the strength, the average particle size of the blocked isocyanate compound (A) is preferably 0.3 μm or less, and is 0.15 μm or less. It is more preferable.
This average particle diameter is a value measured by the method described in the examples described later.

Although it does not specifically limit as said cellulose fiber (B), For example, the pulp obtained from natural plant raw materials, such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, cloth, paper; rayon, cellophane Regenerated cellulose fibers and the like. Of these, pulp is preferred. Although it does not specifically limit as said wood, For example, Sitka spruce, cedar, cypress, eucalyptus, acacia etc. are mentioned. The paper is not particularly limited, and examples thereof include deinked waste paper, corrugated waste paper, magazines, and copy paper.

The pulp includes chemical pulp (kraft pulp (KP), sulfite pulp (SP)), semi-chemical pulp (SCP) obtained by pulping plant raw materials chemically or mechanically, or a combination of both. ), Chemi-Grand Pulp (CGP), Chemi-Mechanical Pulp (CMP), Groundwood Pulp (GP), Refiner Mechanical Pulp (RMP), Thermomechanical Pulp (TMP), Chemi-thermomechanical Pulp (CTMP), and these pulps Examples include deinked waste paper pulp, corrugated waste paper pulp, and magazine waste paper pulp. These raw materials may be subjected to delignification treatment as necessary, or may be those in which the amount of lignin in the pulp is adjusted by bleaching.

Among these pulps, various kraft pulps derived from conifers with strong fiber strength (coniferous unbleached kraft pulps (hereinafter sometimes referred to as NUKP), softwood oxygen-bleached unbleached kraft pulps (hereinafter sometimes referred to as NOKPs), Softwood bleached kraft pulp (hereinafter sometimes referred to as NBKP)) is particularly preferred.

The pulp is mainly composed of cellulose, hemicellulose, and lignin. The lignin content in the pulp is not particularly limited, but is usually about 0 to 40% by weight, preferably about 0 to 10% by weight. The lignin content is measured by the Klason method.

As the cellulose fibers, those that have been defibrated can be used, but those that have not been defibrated can also be suitably used.

The content ratio of the blocked isocyanate compound (A) and the cellulose fiber (B) in the resin reinforcing mixture (X1) is not particularly limited, but the bending strength and bending elastic modulus of the cured product of the fiber reinforced resin (Y) are not limited. From the viewpoint of strength, the blocked isocyanate compound (A) is preferably 0.01 to 4.0 parts by mass, and 0.03 to 3.0 parts by mass with respect to 1 part by mass of the cellulose fiber (B). More preferred is 0.05 to 2.5 parts by mass.

The content of water (C) in the resin reinforcing mixture (X1) is preferably 1 to 99% by mass, more preferably 2 to 95% by mass. When the content of water (C) is 1 to 99% by mass, the mixing property between the resin reinforcing mixture (X1) and the thermoplastic resin (X2) becomes good.

The fiber reinforced resin mixture (X) of the present embodiment contains a resin reinforcing mixture (X1) and a thermoplastic resin (X2).

The thermoplastic resin (X2) is not particularly limited. For example, polyethylene (PE), polypropylene (PP), polybutene, polyvinyl chloride, polystyrene, polyvinylidene chloride, fluororesin, polymethyl methacrylate, polyamide resin, Examples thereof include cellulose resins such as polyester, polycarbonate, polyphenylene oxide, thermoplastic polyurethane, polyacetal, nylon resin, vinyl ether resin, polysulfone resin, triacetylated cellulose, and diacetylated cellulose. These may be used alone or in combination of two or more. Among these, polyolefins such as polyethylene, polypropylene, polybutene, and polystyrene are preferable as the wood plastic in that the strength is easily increased by mixing with a woody material such as wood powder. In addition, polypropylene, polyethylene, polylactic acid, and polyamide resin are preferable from the viewpoint of versatility such as structural members. In addition, the ABS resin (acrylonitrile, butadiene and styrene copolymer synthetic resin) is excellent in compatibility because the compatibility parameters of polyacrylonitrile, which is one component thereof, and the cellulosic material are close to each other. preferable. As the thermoplastic resin (X2), among the resins exemplified above, polypropylene, polyethylene or ABS resin is preferable, and polypropylene is more preferable.

As the polypropylene, it is preferable to use maleic acid-modified polypropylene in combination from the viewpoint of the above-mentioned strength such as bending elastic modulus and bending strength. In this case, the content of the maleic acid-modified polypropylene is preferably 5 to 40% by mass, more preferably 8 to 30% by mass with respect to the thermoplastic resin (X2). The reason why the strength such as the flexural modulus and the bending strength is sufficiently increased by the combined use of maleic acid-modified polypropylene is not clear, but is that cellulose, blocked isocyanate and maleic acid-modified polypropylene are mutually crosslinked or compatibilized. Inferred.

The average particle size of the thermoplastic resin (X2) is not particularly limited, but is preferably about 1 to 1000 μm, more preferably about 1 to 500 μm, and more preferably about 1 to 100 μm because aggregation of cellulose fibers is reduced. Is more preferable.
This average particle diameter is a value measured by the method described in the examples described later.

The blending ratio of the cellulose fiber (B) and the thermoplastic resin (X2) in the fiber reinforced resin mixture (X) is not particularly limited. For example, considering the viewpoint of excellent mechanical properties, heat resistance, surface smoothness and appearance, the blending amount of the cellulose fiber (B) is 1 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (X2). About 1 to 200 parts by mass, more preferably about 1 to 100 parts by mass.

The blending of the blocked isocyanate compound (A) and the thermoplastic resin (X2) in the fiber reinforced resin mixture (X) is not particularly limited. For example, considering the viewpoint of excellent mechanical properties, heat resistance, surface smoothness and appearance, the blending amount of the cellulose fiber (B) is 1 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (X2). About 1 to 200 parts by mass, more preferably about 1 to 100 parts by mass.

The fiber reinforced resin mixture (X) may further contain any additive. Optional additives are not particularly limited. For example, as such additives, compatibilizers; surfactants; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; colorants; Examples include plasticizers, fragrances, pigments, flow control agents, leveling agents, conductive agents, antistatic agents, ultraviolet absorbers, ultraviolet dispersants, and deodorants.

The blending ratio of such additives can be set as appropriate as long as the effect of the obtained fiber reinforced resin (Y) is not impaired. For example, the fiber reinforced resin mixture (X) is preferably about 10% by mass or less, and more preferably about 5% by mass or less.

As described above, the fiber reinforced resin mixture (X) of the present embodiment contains the above-described resin reinforcing mixture (X1) and the thermoplastic resin (X2).

Thereby, this resin reinforcement mixture (X1) can be used as a raw material for fiber reinforced resin (Y). At this time, when the fiber reinforced resin (Y) is produced, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are dissociated from the blocked group of the blocked isocyanate compound, and the thermoplastic resin (X2 ) Is heated at a temperature equal to or higher than the melting temperature and mixed, so that the blocked isocyanate compound (A) relaxes the interaction due to hydrogen bonds in the cellulose fiber (B), so that the cellulose fiber (B) is refined. The dispersion is promoted.
Thereby, a cellulose fiber is fully loosened and fully disperse | distributed.
Further, since the blocking group of the blocked isocyanate compound (A) is dissociated, the isocyanate group is regenerated, and polymerization is performed so as to take in the cellulose fiber (B), the resin component and cellulose in the fiber reinforced resin (Y). Adhesiveness with a fiber (B) is improved.
Thus, since a cellulose fiber (B) is disperse | distributed to a thermoplastic resin (X2) via a blocked isocyanate compound (A), the intensity | strength of the hardening body of fiber reinforced resin (Y) is fully raised.
Moreover, even if the surface treatment process is not performed on the cellulose fiber or a plurality of types of solvents are not used, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is formed as described above. Therefore, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is easily formed.
As described above, according to the fiber-reinforced resin mixture (X) of this embodiment, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are dissociated from the blocked group of the blocked isocyanate compound, and heated. By heating and mixing at a temperature equal to or higher than the temperature at which the plastic resin (X2) melts, the strength of the cured body is sufficiently increased with respect to the fiber reinforced resin (Y) and is easily formed. .

When the blocked isocyanate compound (A) is an aqueous dispersion, the fiber-reinforced resin mixture (X) contains the blocked isocyanate compound (A), the cellulose fiber (B), and water (C). It may be.
As described above, by containing water (C), the cellulose fibers (B) are more sufficiently dispersed in the blocked isocyanate compound (A).
Thereby, the intensity | strength of the hardening body of fiber reinforced resin (Y) can be raised more fully.

Moreover, the fiber reinforced resin mixture (X) of this embodiment is a mixture obtained by mixing and drying the resin reinforcing mixture (X1) containing the water (C) and the thermoplastic resin (X2). There may be.
For example, in the case where the blocked isocyanate compound (A) is an aqueous dispersion, the fiber-reinforced resin mixture (X) is dried by mixing the resin reinforcing mixture (X1) and the thermoplastic resin (X2). It may be made.
According to this, since it is not necessary to remove water when the fiber reinforced resin (Y) is produced, the fiber reinforced resin (Y) is more easily formed.

In the fiber reinforced resin (Y) of the present embodiment, the fiber reinforced resin mixture (X) is heated to a temperature higher than the temperature at which the thermoplastic resin (X2) melts while the blocking group of the blocked isocyanate compound (A) is dissociated. And mixed.

According to such a configuration, as described above, the fiber reinforced resin (Y) has a sufficiently high strength and is easily formed.

The manufacturing method of the fiber reinforced resin (Y) of this embodiment described above is
The fiber reinforced resin mixture (X) containing the blocked isocyanate compound (A), the cellulose fiber (B), and the thermoplastic resin (X2) is converted into the heat while the blocking group of the blocked isocyanate compound (A) is dissociated. A step (heating and mixing step) of heating and mixing above the temperature at which the plastic resin (X2) melts is provided.

According to this manufacturing method, as described above, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is easily formed.

Moreover, in the manufacturing method of the fiber reinforced resin (Y) of this embodiment, the fiber reinforced resin mixture (X) may further contain water (C).
Thus, by containing water (C), as above-mentioned, the fiber reinforced resin (Y) in which the intensity | strength of the hardening body was fully raised is formed more simply.

Although the manufacturing method of the blocked isocyanate compound (A) used by this embodiment is not specifically limited, The method of blocking the isocyanate group of the polyisocyanate compound with which the polyol compound was made to react with a blocking agent as needed may be employ | adopted.
The equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound is not particularly limited, but is preferably 1: 0.3 to 1.2. At this time, it is preferable from the viewpoint of stirring efficiency and the like that both compounds are diluted to an arbitrary solid content ratio in an organic solvent inert to the isocyanate group.
Examples of the organic solvent include aromatic solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, ketone solvents such as acetone and methyl ethyl ketone, and acetic acid. Ester solvents such as ethyl and butyl acetate, glycol ether ester solvents such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate, glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dibutyl ether and propylene glycol dibutyl ether used.
These reactions can be carried out according to normal blocking reaction conditions of 20 to 100 ° C., preferably 30 to 90 ° C. At this time, a known urethanization catalyst may be used.
The amount of blocked isocyanate groups is preferably from 0.1 mmol / g to 5 mmol / g, particularly preferably from 0.3 mmol / g to 4.7 mmol / g, from the viewpoint of the above strength.

In order for the blocked isocyanate compound (A) to contain a hydrophilic group, the hydrophilic group-containing compound may be further reacted in the above reaction system.
In order to obtain an aqueous dispersion of the blocked isocyanate compound (A), for example, after the blocked isocyanate compound (A) is produced, water is further added together with a surfactant as necessary, A solvent may be used.

Although the manufacturing method of the resin reinforcing mixture (X1) used in the present embodiment is not particularly limited, for example, a method of mixing the blocked isocyanate compound (A) and the cellulose fiber (B) by a known method may be employed. .
Moreover, the method of mixing a block isocyanate compound (A), a cellulose fiber (B), and water (C) by a well-known method may be employ | adopted.
In addition, water (C) may be added as a blocked isocyanate compound (A) water dispersion as mentioned above, and may be added separately from this.

In the heating and mixing step of the fiber reinforced resin (Y) of the present embodiment, for example, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) can be melt-kneaded.
These blending amounts may be adjusted to the blending amounts as described above.
In addition to the resin reinforcing mixture (X1) and the thermoplastic resin (X2), any additive may be blended as described above.
The temperature at the time of melt-kneading is not particularly limited as long as it is equal to or higher than the temperature at which the blocking group of the blocked isocyanate compound (A) dissociates and the thermoplastic resin (X2) melts. Dissociation of the blocking group It can be appropriately set according to the temperature and the melting point of the thermoplastic resin (X2). For example, the temperature during melt kneading is preferably 80 to 250 ° C, more preferably 100 to 230 ° C, and further preferably 120 to 220 ° C.
In addition, when melt-kneading, an apparatus usually used in this field can be used.

As described above, when the fiber-reinforced resin mixture (X) contains water (C), for example, as described above, an aqueous dispersion of the blocked isocyanate compound (A) and the cellulose fiber (B) And the mixture can be mixed directly with the thermoplastic resin (X2) or melt-kneaded after drying the mixture.
Thus, by using the aqueous dispersion of the blocked isocyanate compound (A), as described above, water acts as a dispersion medium for sufficiently dispersing the cellulose fiber (B), and thereby, the thermoplastic resin (X2 ) In which the cellulose fibers are uniformly dispersed.
Further, when melt-kneading, an organic solvent compatible with water may be added. Examples of such solvents include ketone solvents such as acetone and methyl ethyl ketone (MEK); ether solvents such as tetrahydrofuran (THF), ethers obtained by etherification of ethylene glycol, propylene glycol, polyethylene glycol, and the like, and diethylated compounds. Is mentioned.

The method of mixing the resin reinforcing mixture (X1), the thermoplastic resin (X2), and other components is not particularly limited. For example, as a mixing method, a mixer, a blender, a single screw kneader, a twin screw kneader, a kneader, a lab plast mill, a homogenizer, a high-speed homogenizer, a high-pressure homogenizer, a planetary stirrer, an apparatus capable of mixing or stirring three rolls, etc. The method of mixing and stirring using can be mentioned.

The fiber reinforced resin (Y) of this embodiment can be molded into a resin molded body having a desired shape by using a known and commonly used molding method for resin molded bodies. Examples of such molding include compression molding, injection molding, extrusion molding, and foam molding. The molding conditions may be adapted by appropriately adjusting the molding conditions of the resin as necessary.
In addition, when the fiber reinforced resin mixture (X) contains water (C), it is preferable that the fiber reinforced resin mixture (X) is dried in advance prior to molding.
By being dried in this manner, the uniform dispersibility of the cellulose fiber (B) in the obtained fiber reinforced resin (Y) is improved, and the fiber reinforced resin (Y) is more excellent in physical properties such as strength. Become.

The bending strength of the cured body of the fiber reinforced resin (Y) is not particularly limited. For example, when 10% by mass of cellulose fiber is contained in the fiber reinforced resin (Y), the bending strength is preferably 60 MPa or more, and more preferably 62 MPa or more. For example, when 20% by mass of cellulose fiber is contained in the fiber reinforced resin (Y), the bending strength is preferably 67 MPa or more, and more preferably 69 MPa or more.
In addition, for example, the bending strength of the cured product of the fiber reinforced resin (Y) containing it is improved by 3% or more compared to the fiber reinforced resin not containing the blocked isocyanate compound (A). Preferably, it is more preferably improved by 5% or more.
In addition, this bending strength is a value measured by the method as described in the Example mentioned later.

The bending elastic modulus of the fiber reinforced resin (Y) is not particularly limited. For example, when 10% by mass of cellulose fiber is contained in the fiber reinforced resin (Y), it is preferably 2300 MPa or more, and more preferably 2350 MPa or more. For example, when 20% by mass of cellulose fiber is contained in the fiber reinforced resin (Y), the flexural modulus is preferably 2850 MPa or more, and more preferably 2900 MPa or more.
In addition, for example, compared to a fiber reinforced resin not containing the blocked isocyanate compound (A), the flexural modulus of the cured product of the fiber reinforced resin (Y) containing it is improved by 3% or more. It is preferable that it is improved by 5% or more.
In addition, this bending elastic modulus is a value measured by the method as described in the Example mentioned later.

Hereinafter, a second embodiment of the present invention will be described.
In addition, about the part which overlaps with 1st Embodiment mentioned above, that is described and description is not repeated.

The resin reinforcing mixture (X1) of this embodiment is
A blocked isocyanate compound (A) or a polyurethane compound (D);
Cellulose fibers (B);
An anionic surfactant (E) or a silicone-based or acetylene-based nonionic surfactant (F) is contained.

The resin reinforcing mixture (X1) contains an isocyanate compound (A) or a polyurethane compound (D), a cellulose fiber (B), and the surfactant (E) or the surfactant (F). Thus, the resin reinforcing mixture (X1) can be used as a raw material for the fiber reinforced resin (Y).

At this time, when the fiber reinforced resin (Y) is produced, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are heated at a temperature equal to or higher than the temperature at which the thermoplastic resin (X2) melts, and By mixing, the isocyanate compound (A) or polyurethane compound (D) and the surfactant (E) or surfactant (F) alleviate the interaction caused by hydrogen bonds in the cellulose fiber (B). Therefore, the cellulose fiber (B) is refined and its dispersion is promoted.
For example, when the resin reinforcing mixture (X1) contains the blocked isocyanate compound (A), when the fiber reinforced resin (Y) is prepared, the blocking group of the blocked isocyanate compound (A) is dissociated and heated. The block isocyanate compound (A) and the surfactant (E) or the surfactant (F) are mixed with the cellulose fiber (A) by heating and mixing at a temperature higher than the temperature at which the plastic resin (X2) melts. The interaction by hydrogen bonds in B) can be relaxed.
Further, when the resin reinforcing mixture (X1) contains the polyurethane compound (D), when the fiber reinforced resin (Y) is produced, the thermoplastic resin (X2) while the polyurethane compound (D) is fused. ) Is heated above the temperature at which it melts and mixed, so that the polyurethane compound (D) and the surfactant (E) or surfactant (F) become hydrogen in the cellulose fiber (B). Interactions due to binding can be relaxed.
In this way, the cellulose fibers (B) are sufficiently loosened and sufficiently dispersed.

Further, when the resin-reinforcing mixture (X1) contains the blocked isocyanate compound (A) during the heating and mixing described above, the isocyanate group of the blocked isocyanate compound (A) takes in the cellulose fiber (B). Therefore, the adhesion between the resin component and the cellulose fiber (B) is improved in the fiber reinforced resin (Y).
Further, when the resin reinforcing mixture (X1) contains the polyurethane compound (D), the polyurethane compounds (D) are fused together so as to take in the cellulose fibers (B), so that the fiber reinforced resin (Y ), The adhesion between the resin component and the cellulose fiber (B) is improved.

In addition, when the fiber reinforced resin (Y) is produced, the presence of the surfactant (E) or the surfactant (F) causes the blocked isocyanate compound (A) or the polyurethane compound (D) with respect to the cellulose fiber (B). ) Is improved, whereby the blocked isocyanate compound (A) or the polyurethane compound (D) can permeate or uniformly adhere to the cellulose fiber (B).
Further, the presence of the surfactant (E) or the surfactant (F) between the cellulose fibers (B) imparts slipperiness to the cellulose fibers (B).
As a result, in combination with the dispersing action of the cellulose fiber (B) by the blocked isocyanate compound (A) or the polyurethane compound (D), in the fiber reinforced resin (Y), the resin component and the cellulose fiber (B) It is presumed that the adhesion of the material is further improved.
In addition, the cellulose fiber (B) is damaged when kneaded due to the slipperiness imparted to the cellulose fiber (B) by the addition of the surfactant (E) or the surfactant (F). And can be uniformly dispersed in the thermoplastic resin (X2), whereby the strength of the cured body of the fiber reinforced resin (Y) is sufficiently expressed.
Thus, the cellulose fiber (B) is dispersed in the thermoplastic resin (X2) through the isocyanate compound (A) or the polyurethane compound (D) and the surfactant (E) or the surfactant (F). Therefore, the strength of the cured body of the fiber reinforced resin (Y) is sufficiently increased.
Thereby, a cellulose fiber (B) is fully loosened, and is fully disperse | distributed. Therefore, the strength of the cured body of the fiber reinforced resin (Y) is sufficiently increased.
Further, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased as described above can be obtained even if the cellulose fiber (B) is not subjected to a surface treatment step or a plurality of types of solvents are not used. Simple to form.

The blocked isocyanate compound (A) is a reaction product obtained by reacting an isocyanate group of a polyisocyanate compound with a blocking agent, and regenerates the isocyanate group by heating.

When the resin reinforcing mixture (X1) contains the blocked isocyanate compound (A), the resin reinforcing mixture (X1) is mixed with the cellulose fiber (B) and the surfactant (E) or the interface. Together with the activator (F), it can be used as a raw material for the fiber reinforced resin (Y).
At this time, when the fiber reinforced resin (Y) is produced, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are dissociated from the blocking group of the blocked isocyanate compound (A) and are thermoplastic. Since the blocked isocyanate compound (A) relaxes the interaction due to hydrogen bonds in the cellulose fiber (B) by being heated and mixed at a temperature higher than the temperature at which the resin (X2) melts, the cellulose fiber (B) Is refined and its dispersion is promoted.
In this way, the cellulose fibers (B) are sufficiently loosened and sufficiently dispersed.
Further, since the blocking group of the blocked isocyanate compound (A) is dissociated, the isocyanate group is regenerated, and polymerization is performed so as to take in the cellulose fiber (B), the resin component and cellulose in the fiber reinforced resin (Y). Adhesiveness with a fiber (B) is improved.
Thus, since the cellulose fiber (B) is dispersed in the thermoplastic resin (X2) via the blocked isocyanate compound (A) and the surfactant (E) or the surfactant (F), the fiber The strength of the cured body of the reinforced resin (Y) is sufficiently increased.
Further, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased as described above can be obtained even if the cellulose fiber (B) is not subjected to a surface treatment step or a plurality of types of solvents are not used. Simple to form.

In the present embodiment, examples of the blocked isocyanate compound (A) include the same compounds as those mentioned in the first embodiment.

The polyurethane compound (D) is a reaction product produced by reacting a polyol compound and a polyisocyanate compound.

The polyol compound used for the production of the polyurethane compound (D) is not particularly limited.
As this polyol compound, the polyol compound used for the production | generation of the isocyanate group terminal urethane prepolymer in the block isocyanate compound (A) mentioned above, for example is mentioned.

The polyisocyanate compound used for production | generation of a polyurethane compound (D) is not specifically limited.
As this polyisocyanate compound, the polyisocyanate compound used for the production | generation of the block isocyanate compound (A) mentioned above is mentioned, for example.
Moreover, as this polyisocyanate compound, the reaction product produced | generated by further reacting the isocyanate group terminal urethane prepolymer mentioned above and the polyol compound mentioned above is mentioned.
Moreover, the active hydrogen compound which can react with the isocyanate group of the said prepolymer can also be used as a chain extender as needed, and an amine compound is mentioned as a chain extender. Examples of the amine compound include diamines such as ethylenediamine, trimethylenediamine, piperazine, and isophoronediamine; polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine. These can be used as one kind or a mixture of two or more kinds.

The polyurethane compound (D) may be an aqueous polyurethane compound obtained by emulsifying, in water, a polyurethane resin produced by reacting a polyol compound and a polyisocyanate compound.

In the resin reinforcing mixture (X1) of the present embodiment, the blocked isocyanate compound (A) or the polyurethane compound (D) is used from the viewpoint of strength such as bending strength and bending elastic modulus of the cured body of the fiber reinforced resin (Y). It preferably has a hydrophilic group. Although the reason why the blocked isocyanate compound (A) or the polyurethane compound (D) having a hydrophilic group is excellent in bending strength and bending elastic modulus is not clear, the interaction due to hydrogen bonding between the cellulose fibers (B) is relaxed, This is presumably due to the action of promoting the dispersion of the cellulose fiber (B) in the blocked isocyanate compound (A) or the polyurethane compound (D).

Thus, in the resin reinforcing mixture (X1) of the present embodiment,
The blocked isocyanate compound (A) or the polyurethane compound (D) may have a hydrophilic group.

Thus, when a fiber reinforced resin (Y) is produced because the blocked isocyanate compound (A) or the polyurethane compound (D) has a hydrophilic group, the blocked isocyanate compound (A) or the polyurethane compound (D). However, since the interaction by the hydrogen bond in a cellulose fiber (B) is eased more, dispersion | distribution of a cellulose fiber (B) is accelerated | stimulated more.
Thereby, a cellulose fiber (B) is fully disperse | distributed in a thermoplastic resin (X2).
Therefore, the strength of the cured body of the fiber reinforced resin (Y) is more sufficiently increased.

The hydrophilic group may be any of the anionic group, the cationic group, or the nonionic group as in the first embodiment, and is not particularly limited. Among these, the bending strength, the bending From the viewpoint of strength such as elastic modulus, an anionic group or a cationic group is preferred.

Although it does not specifically limit as a hydrophilic group compound for making a blocked isocyanate compound (A) or a polyurethane compound (D) contain a hydrophilic group and introduce | transducing, For example, it mentioned by 1st Embodiment mentioned above. The same thing is mentioned.

The content of the hydrophilic group in the blocked isocyanate compound (A) or the polyurethane compound (D) is not particularly limited. For example, the content is preferably 0.07 to 2.10 mmol / g, more preferably 0.12 to 1.80 mmol / g, and 0.17 to 1.60 mmol / g. Is more preferable.
When the fiber-reinforced resin (Y) is produced by the content of the hydrophilic group being 0.07 to 2.10 mmol / g, via the blocked isocyanate compound (A) or the polyurethane compound (D), Cellulose fibers (B) are more fully loosened and further dispersed.
Therefore, the strength such as the bending strength and the bending elastic modulus of the cured body of the fiber reinforced resin (Y) is further increased.
The content of such a hydrophilic group is a value measured by a measurement method described in Examples described later.

The blocked isocyanate compound (A) or the polyurethane compound (D) preferably has an aromatic cyclic structure from the viewpoint of strength such as bending strength and bending elastic modulus of the cured product of the fiber reinforced resin (Y). The content of the aromatic cyclic structure in the blocked isocyanate compound (A) or the polyurethane compound (D) is preferably 4% by mass to 80% by mass, and more preferably 8% by mass to 70% by mass. More preferred.
In addition, as shown in the Example mentioned later, content of the said aromatic cyclic structure is the said block isocyanate compound (A) or polyurethane compound with respect to the total mass of the said block isocyanate compound (A) or a polyurethane compound (D). The ratio of the aromatic cyclic structure contained in (D) is shown. That is, the content is the total mass of all raw materials such as polyol compound and polyisocyanate compound used in the production of the blocked isocyanate compound (A) or polyurethane compound (D), and the blocked isocyanate compound (A) or polyurethane compound. Calculated based on the content of the aromatic cyclic structure contained in the aromatic cyclic structure, such as an aromatic cyclic structure-containing polyol or aromatic cyclic structure-containing polyisocyanate, used in the production of (D). Value. Examples of the aromatic cyclic structure include a phenyl group and a naphthalene group.

It is also a preferred aspect that the blocked isocyanate compound (A) or the polyurethane compound (D) has a short-chain polyol group (a short-chain polyol group is introduced). When the blocked isocyanate compound (A) or the polyurethane compound (D) is an aqueous dispersion by having a short-chain polyol group, the blocked isocyanate compound (A) or the polyurethane compound (D) has an intramolecular structure. The urethane bond can be localized and a branched structure can be introduced. The short-chain polyol group for localizing the urethane bond and the short-chain polyol for introducing a branched structure are not particularly limited. For example, those mentioned in the first embodiment described above The same can be mentioned.

It is also a preferable aspect that a chain extender is introduced into the blocked isocyanate compound (A) or the polyurethane compound (D). By introducing the chain extender, when the blocked isocyanate compound (A) or the polyurethane compound (D) is an aqueous dispersion as described later, each molecule thereof can be increased. Although it does not specifically limit as said chain extender, For example, the same thing as what was mentioned by 1st Embodiment mentioned above is mentioned.

The anionic surfactant (E) is a surfactant having an anionic substituent.
The anionic surfactant (E) is not particularly limited.
Examples of the anionic surfactant (E) include a sulfate ester group having a sulfate ester group, a phosphate ester group having a phosphate ester group, a carboxylic acid group having a carboxylic acid group, and a sulfonic acid (sulfuric acid) group. Examples thereof include sulfonic acid-based anionic surfactants.
As the sulfate anionic surfactant (E), a commercially available product can be used. Examples of the commercially available product include trade names of Monogen, Haitenol, Aqualon (for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) And those represented by Aqualon BC, Aqualon HS, Aqualon KH), and the like.
As the phosphate anionic surfactant (E), a commercially available product can be used. Examples of the commercially available product include those represented by Daiichi Kogyo Seiyaku Co., Ltd. trade name: Flysurf, etc. Is mentioned.
As the carboxylic acid-based anionic surfactant (E), a commercially available product can be used. Examples of the commercially available product are represented by trade names of Neo Daitenol and DK Kali Soap manufactured by Daiichi Kogyo Seiyaku Co., Ltd. And the like.
As the sulfonic acid-based anionic surfactant (E), a commercially available product can be used, and examples of the commercially available product include those represented by trade names: Neogen and Neocor, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Can be mentioned.

The silicone-based or acetylene-based nonionic surfactant (F) is a surfactant having no ionic (anionic or cationic) substituent, and has an interface having a silicone group or an acetylene group as a substituent. It is an activator.
Among these, the silicone-based nonionic surfactant (F1) is not particularly limited as long as it is a nonionic surfactant having an organosiloxane group formed by bonding an organic group to silicon having a siloxane bond.
As the silicone-based nonionic surfactant (F1), for example, polyether-modified siloxane is preferable.
Commercially available products can be used as the polyether-modified siloxane. Examples of the commercially available products include BYK-349, trade name manufactured by BYK Chemie, and trade name: modified silicone oil (eg, KF- 351A, KF-615) and the like.
The acetylene-based nonionic surfactant (F2) is not particularly limited as long as it is a nonionic surfactant having an acetylene group.
As the acetylene-based nonionic surfactant (F2), for example, polyether acetylene is preferable, and ethyne oxide-modified acetylene is more preferable.
A commercially available product can be used as the ethylene oxide-modified acetylene, and examples of the commercially available product include those represented by trade name: Surfynol (for example, Surfynol 440) manufactured by Nissin Chemical Industry Co., Ltd. .

When the resin reinforcing mixture (X1) contains the surfactant (E) or the surfactant (F), the surfactant (E) or the surfactant (E) or the surfactant (E) By the presence of the surfactant (F), the wettability of the blocked isocyanate compound (A) or the polyurethane compound (D) with respect to the cellulose fiber (B) is improved, and thereby the blocked isocyanate compound with respect to the cellulose fiber (B). The compound (A) or the polyurethane compound (D) can permeate or adhere uniformly.
Further, the presence of the surfactant (E) or the surfactant (F) between the cellulose fibers (B) imparts slipperiness to the cellulose fibers (B).
As a result, when producing the fiber reinforced resin (Y), in combination with the dispersing action of the cellulose fiber (B) by the blocked isocyanate compound (A) or the polyurethane compound (D), the fiber reinforced resin (Y) Thus, it is speculated that the adhesion between the resin component and the cellulose fiber (B) is further improved.
In addition, the cellulose fiber (B) is damaged when kneaded due to the slipperiness imparted to the cellulose fiber (B) by the addition of the surfactant (E) or the surfactant (F). And can be uniformly dispersed in the thermoplastic resin (X2), whereby the strength of the cured body of the fiber reinforced resin (Y) is sufficiently expressed.

The addition amount of the said surfactant (E) or surfactant (F) is not specifically limited, It can set suitably.
For example, considering the point that sufficient slipperiness can be imparted to the cellulose fiber (B) as described above, the amount of the surfactant (E) or the surfactant (F) added is the blocked isocyanate compound ( It is preferable that it is 0.1 mass part or more with respect to 100 mass parts of solid content of A) or a polyurethane compound (D), and it is more preferable that it is 0.3 mass part or more.
On the other hand, in consideration of the fact that it is possible to suppress adverse effects on the strength such as bending strength and flexural modulus of the fiber reinforced resin (Y) to be obtained, the surfactant (E) or the surfactant (F) The addition amount is preferably 30 parts by mass or less and more preferably 20 parts by mass or less with respect to 100 parts by mass of the solid content of the blocked isocyanate compound (A) or the polyurethane compound (D).

In the resin reinforcing mixture (X1) of the present embodiment, the blocked isocyanate compound (A) or the polyurethane compound (D) is contained in the resin reinforcing mixture (X1) without being dispersed in water (C). Alternatively, it may be contained in the resin reinforcing mixture (X1) as an aqueous dispersion dispersed in water (C).
Thus, the resin reinforcing mixture (X1) comprises the blocked isocyanate compound (A) or the polyurethane compound (D), the cellulose fiber (B), the surfactant (E) or the surfactant (F). And water (C) may be contained.
Thus, by containing water (C), when the fiber reinforced resin (Y) is produced, the cellulose fibers are more easily dispersed.
Thereby, the intensity | strength of the hardening body of fiber reinforced resin (Y) is raised more fully.

The blocked isocyanate compound (A) or the polyurethane compound (D) is a cellulose fiber (as a water dispersion dispersed in water (C) containing the surfactant (E) or surfactant (F)). After being mixed with B), it may be contained in the resin reinforcing mixture (X1) by drying.
That is, the resin reinforcing mixture (X1) includes a blocked isocyanate compound (A) or a polyurethane compound (D), a cellulose fiber (B), the surfactant (E) or the surfactant (F), water, It may be dried after (C) is mixed.
Thus, since it is what was dried after mixing, when fiber reinforced resin (Y) is produced, since it is not necessary to remove water (C), fiber reinforced resin (Y) It is formed more simply.

When the blocked isocyanate compound (A) or the polyurethane compound (D) is an aqueous dispersion, the average particle size of the blocked isocyanate compound (A) or the polyurethane compound (D) is 0.3 μm or less from the viewpoint of the strength. Preferably, it is 0.15 μm or less.
This average particle diameter is a value measured by the method described in the examples described later.

The resin reinforcing mixture (X1) contains the blocked isocyanate compound (A) or the polyurethane compound (D), the cellulose fiber (B), and the surfactant (E) or the surfactant (F). If so, the form is not particularly limited.

The cellulose fiber (B) is not particularly limited, and examples thereof include the same as those mentioned in the first embodiment.

The content ratio of the blocked isocyanate compound (A) or polyurethane compound (D) and the cellulose fiber (B) in the resin reinforcing mixture (X1) is not particularly limited, but the fiber reinforced resin (Y) is cured. From the viewpoint of strength such as bending strength and flexural modulus of the body, the blocked isocyanate compound (A) or the polyurethane compound (D) is 0.01 to 4.0 parts by mass with respect to 1 part by mass of the cellulose fiber (B). It is preferably 0.03 to 3.0 parts by mass, more preferably 0.05 to 2.5 parts by mass.

The content of water (C) in the resin reinforcing mixture (X1) is preferably 1 to 99% by mass, and more preferably 2 to 95% by mass. When the content of water (C) is 1 to 99% by mass, the mixing property between the resin reinforcing mixture (X1) and the thermoplastic resin (X2) becomes good.

The fiber reinforced resin mixture (X) of the present embodiment contains a resin reinforcing mixture (X1) and a thermoplastic resin (X2).

The thermoplastic resin (X2) is not particularly limited, and examples thereof include the same ones as mentioned in the first embodiment.

The blending ratio of the cellulose fiber (B) and the thermoplastic resin (X2) in the fiber reinforced resin mixture (X) is not particularly limited. For example, considering the viewpoint of excellent mechanical properties, heat resistance, surface smoothness and appearance, the blending amount of the cellulose fiber (B) is 1 to 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin (X2). It is preferably about 1 to 200 parts by mass, more preferably about 1 to 100 parts by mass.

The blend of the blocked isocyanate compound (A) or the polyurethane compound (D) and the thermoplastic resin (X2) in the fiber reinforced resin mixture (X) is not particularly limited. For example, considering the viewpoint of excellent mechanical properties, heat resistance, surface smoothness and appearance, the amount of the blocked isocyanate compound (A) or polyurethane compound (D) is 100 parts by mass of the thermoplastic resin (X2). On the other hand, it is preferably about 1 to 300 parts by mass, more preferably about 1 to 200 parts by mass, and still more preferably about 1 to 100 parts by mass.

The fiber reinforced resin mixture (X) may further contain any additive. Optional additives are not particularly limited. For example, examples of the additive include the same ones as those mentioned in the first embodiment.

The blending ratio of such additives can be set as appropriate as long as the effect of the obtained fiber reinforced resin (Y) is not impaired. For example, it is preferable that it is about 10 mass% or less to a fiber reinforced resin mixture (X), and it is more preferable that it is about 5 mass% or less.

As described above, the fiber reinforced resin mixture (X) of the present embodiment contains the above-described resin reinforcing mixture (X1) and the thermoplastic resin (X2).

According to such a configuration, the fiber reinforced resin (Y) can be produced simply by heating the fiber reinforced resin mixture (X). That is, the resin reinforcing mixture (X1) can be used as a raw material for the fiber reinforced resin (Y).
At this time, as described above, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are heated and mixed at a temperature equal to or higher than the temperature at which the thermoplastic resin (X2) melts, thereby reinforcing the fiber The resin (Y) has a sufficiently hardened body and is easily formed.
For example, when the resin reinforcing mixture (X1) contains a blocked isocyanate compound (A), the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are blocked groups of the blocked isocyanate compound (A). The fiber-reinforced resin (Y) is sufficiently formed with the strength of the cured body being easily increased by heating and mixing at a temperature at which the thermoplastic resin (X2) melts while being dissociated. Will be.
For example, when the resin reinforcing mixture (X1) contains the polyurethane compound (D), the resin reinforcing mixture (X1) and the thermoplastic resin (X2) are fused with the polyurethane compound (D). However, the fiber reinforced resin (Y) was sufficiently formed with the strength of the cured body being easily increased by heating and mixing at a temperature higher than the temperature at which the thermoplastic resin (X2) melts. It will be a thing.

When the blocked isocyanate compound (A) or the polyurethane compound (D) is an aqueous dispersion, the fiber-reinforced resin mixture (X) contains the blocked isocyanate compound (A) or the polyurethane compound (D) and cellulose fibers ( B), the surfactant (E) or the surfactant (F), and water (C) may be contained.
As described above, by containing water (C), the cellulose fiber (B) is more sufficiently dispersed in the blocked isocyanate compound (A) or the polyurethane compound (D).
Thereby, the intensity | strength of the hardening body of fiber reinforced resin (Y) can be raised more fully.

The fiber reinforced resin mixture (X) of this embodiment is
The resin reinforcing mixture (X1) containing the water (C) and the thermoplastic resin (X2) may be mixed and dried.
For example, in the case where the blocked isocyanate compound (A) or the polyurethane compound (D) is an aqueous dispersion, the fiber reinforced resin mixture (X) includes a resin reinforcing mixture (X1), a thermoplastic resin (X2), and May be mixed and dried.
According to this, since it is not necessary to remove water when the fiber reinforced resin (Y) is produced, the fiber reinforced resin (Y) is more easily formed.

The fiber reinforced resin (Y) of this embodiment is obtained by heating and mixing the fiber reinforced resin mixture (X) at a temperature higher than the temperature at which the thermoplastic resin (X2) melts.

For example, when the fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A), the fiber reinforced resin (Y) has a blocked group of the blocked isocyanate compound (A). A mode in which the thermoplastic resin (X2) is heated at a temperature equal to or higher than the melting temperature while being dissociated and mixed may be employed.
For example, when the fiber reinforced resin mixture (X) contains the polyurethane compound (D), the fiber reinforced resin (Y) is fused with the fiber reinforced resin mixture (X) and the polyurethane compound (D). On the other hand, a mode in which the thermoplastic resin (X2) is heated at a temperature equal to or higher than the melting temperature and mixed may be employed.

According to such a configuration, as described above, the fiber reinforced resin (Y) has a sufficiently high strength and is easily formed.

The manufacturing method of the fiber reinforced resin (Y) of this embodiment described above is
Block isocyanate compound (A) or polyurethane compound (D), cellulose fiber (B), anionic surfactant (E), silicone-based or acetylene-based nonionic surfactant (F), and thermoplasticity A step (heat mixing step) of heating and mixing the fiber reinforced resin mixture (X) containing the resin (X2) to a temperature equal to or higher than the temperature at which the thermoplastic resin (X2) melts is provided.

According to such a configuration, as described above, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is easily formed.

For example, when the fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A), the block group of the blocked isocyanate compound (A) is dissociated from the fiber reinforced resin mixture (X) in the heating and mixing step. However, a mode in which the thermoplastic resin (X2) is heated and mixed at a temperature equal to or higher than the melting temperature can be employed.
According to this aspect, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is more easily formed.

For example, when the fiber reinforced resin mixture (X) contains the polyurethane compound (D), in the heating and mixing step, the fiber reinforced resin mixture (X) is fused to the polyurethane compound (D). A mode in which the thermoplastic resin (X2) is heated and mixed at a temperature equal to or higher than the melting temperature may be employed.
According to this aspect, the fiber reinforced resin (Y) in which the strength of the cured body is sufficiently increased is more easily formed.

Moreover, in the manufacturing method of the fiber reinforced resin (Y) of this embodiment, the fiber reinforced resin mixture (X) may further contain water (C).
Thus, by containing water (C), as above-mentioned, the fiber reinforced resin (Y) in which the intensity | strength of the hardening body was fully raised is formed more simply.

The production method of the blocked isocyanate compound (A) used in the present embodiment is not particularly limited, but for example, the same method as described in the first embodiment described above can be adopted.

The method for producing the polyurethane compound (D) used in the present embodiment is not particularly limited. For example, for example, the same method as described in the first embodiment can be adopted.

The method for producing the resin reinforcing mixture (X1) used in the present embodiment is not particularly limited. For example, the blocked isocyanate compound (A) or the polyurethane compound (D), the cellulose fiber (B), and the surfactant ( A method of mixing E) or the surfactant (F) by a known method may be employed.
Moreover, a block isocyanate compound (A) or a polyurethane compound (D), a cellulose fiber (B), the said surfactant (E) or surfactant (F), and water (C) are mixed by a well-known method. The method to do can be adopted.
In addition, water (C) may be added as a blocked isocyanate compound (A) aqueous dispersion or a polyurethane compound (D) aqueous dispersion as described above, or may be added separately.

In the heating and mixing step of the fiber reinforced resin (Y) of the present embodiment, for example, the resin reinforcing mixture (X1) and the thermoplastic resin (X2) can be melt-kneaded.
These blending amounts may be adjusted as described above.
In addition to the resin reinforcing mixture (X1) and the thermoplastic resin (X2), any additive may be blended as described above.

When the resin reinforcing mixture (X1) contains the blocked isocyanate compound (A), the temperature during melt kneading is such that the blocked group of the blocked isocyanate compound (A) is dissociated and the thermoplastic resin (X2). If it is more than the temperature which melt | dissolves, it will not specifically limit. For example, the temperature can be appropriately set according to the dissociation temperature of the blocking group and the melting point of the thermoplastic resin (X2). For example, the temperature at the time of melt kneading is preferably 80 to 250 ° C., more preferably 100 to 230 ° C., and further preferably 120 to 220 ° C.
In addition, when melt-kneading, an apparatus usually used in this field can be used.

When the resin reinforcing mixture (X1) contains the polyurethane compound (D), the melt kneading temperature is a temperature at which the polyurethane compound (D) is fused and the thermoplastic resin (X2) is melted. If it is above, it will not specifically limit. For example, the temperature can be appropriately set according to the fusion temperature of the polyurethane compound (D), the melting point of the thermoplastic resin (X2), and the like. For example, the temperature at the time of melt kneading is preferably 80 to 250 ° C., more preferably 100 to 230 ° C., and further preferably 120 to 220 ° C.
In addition, when melt-kneading, an apparatus usually used in this field can be used.

As described above, when the fiber-reinforced resin mixture (X) contains water (C), for example, as described above, the aqueous dispersion of the blocked isocyanate compound (A) or the polyurethane compound (D) The aqueous dispersion, the cellulose fiber (B), the surfactant (E) or the surfactant (F) are mixed, and the mixture is directly or after the mixture is dried, the thermoplastic resin ( X2) and melt kneaded.
Thus, by using an aqueous dispersion of the blocked isocyanate compound (A) or an aqueous dispersion of the polyurethane compound (D), as described above, water (as a dispersion medium for sufficiently dispersing the cellulose fibers (B)) C) acts, and thereby the cellulose fibers (B) are more uniformly dispersed in the thermoplastic resin (X2).
Further, when melt-kneading, an organic solvent compatible with water (C) may be added. Examples of the solvent include the same solvents as those mentioned in the first embodiment.

The method of mixing the resin reinforcing mixture (X1), the thermoplastic resin (X2), and other components is not particularly limited. For example, as the mixing method, the same method as mentioned in the first embodiment described above can be used.

The fiber reinforced resin (Y) of this embodiment can be molded into a resin molded body having a desired shape by using a known and commonly used molding method for resin molded bodies. Examples of such molding include the same molding as that described in the first embodiment.
In addition, when the fiber reinforced resin mixture (X) contains water (C), it is preferable that the fiber reinforced resin mixture (X) is dried in advance prior to molding.
By being dried in this manner, the uniform dispersibility of the cellulose fiber (B) in the obtained fiber reinforced resin (Y) is improved, and the fiber reinforced resin (Y) is more excellent in physical properties such as strength. Become.

The bending strength of the cured body of the fiber reinforced resin (Y) is not particularly limited. For example, when the cellulose fiber (B) is contained in 10% by mass in the fiber reinforced resin (Y), the bending strength is preferably 60 MPa or more, and more preferably 62 MPa or more. For example, when 20% by mass of the cellulose fiber (B) is contained in the fiber reinforced resin (Y), the bending strength is preferably 67 MPa or more, and more preferably 69 MPa or more.
Moreover, for example, the bending strength of the cured product of the fiber reinforced resin (Y) containing it is 3 as compared with the fiber reinforced resin not containing the blocked isocyanate compound (A) and the polyurethane compound (D). % Or more is preferable, and 5% or more is more preferable.
In addition, this bending strength is a value measured by the method as described in the Example mentioned later.

The bending elastic modulus of the fiber reinforced resin (Y) is not particularly limited. For example, when 20% by mass of the cellulose fiber (B) is contained in the fiber reinforced resin (Y), it is preferably 2850 MPa or more, and more preferably 2900 MPa or more.
In addition, for example, compared to a fiber reinforced resin not containing the blocked isocyanate compound (A), the flexural modulus of the cured product of the fiber reinforced resin (Y) containing it is improved by 3% or more. It is preferable that it is improved by 5% or more.
In addition, this bending elastic modulus is a value measured by the method as described in the Example mentioned later.

As described above, according to each of the embodiments described above, a resin reinforcing mixture and a fiber reinforced resin mixture that can easily form a fiber reinforced resin with sufficiently increased strength, and the strength can be sufficiently increased and simplified. A fiber reinforced resin formed in the above and a method for producing the same are provided.

Since the cured product of the fiber reinforced resin obtained by the resin reinforcing mixture, the fiber reinforced resin mixture, the fiber reinforced resin, and the manufacturing method thereof according to each of the above embodiments has high strength and high elasticity, for example, a molded product of cellulose fiber. In addition to the field where the microfibrillated plant fiber-containing resin molding is used, it can also be used in fields where higher mechanical strength (such as bending strength) is required. For example, interior materials, exterior materials, structural materials, etc. of transportation equipment such as automobiles, trains, ships, airplanes, etc., housings such as personal computers, televisions, telephones, etc. It can be used effectively as a housing for office equipment such as office automation equipment, sports / leisure goods, and structural materials.

The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

Example 1
(Production of blocked isocyanate compounds)
(Blocked isocyanate compound A-1)
The following raw materials were added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube, and reacted at 75 ° C. for 1 hour to obtain a methyl ethyl ketone solution of an isocyanate-terminated urethane prepolymer. After cooling the methyl ethyl ketone solution to 40 ° C. and reacting with 200 parts by mass of methyl ethyl ketone oxime as a blocking agent, 325 parts by mass of a 40% aqueous solution of sodium aminoethyl sulfonate is added to the free isocyanate group with respect to the non-volatile content as a hydrophilic group. Was introduced. Thereafter, 2700 parts by mass of water was gradually added while being stirred with a homogenizer, and emulsified and dispersed. The solvent was removed at 50 ° C. under reduced pressure to obtain an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-1).
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 130 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 540 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-2)
The following were used as raw materials. All the same as the blocked isocyanate compound (A-1) except that 300 parts by mass of o-sec-butylphenol was used as a blocking agent and the addition amount of a 40% aqueous solution of sodium aminoethylsulfonate was 275 parts by mass. Thus, an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-2) was obtained.
<Raw materials>
・ Ethylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BPE-40” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 110 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 480 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-3)
The following were used as raw materials. Except that 240 parts by mass of ε-caprolactam was used as a blocking agent and that the addition amount of a 40% aqueous solution of sodium aminoethylsulfonate was 300 parts by mass, the same method as for the blocked isocyanate compound (A-1) And an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-3) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 130 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 510 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-4)
The following were used as raw materials. All the same as the blocked isocyanate compound (A-1) except that 160 parts by mass of o-sec-butylphenol was used as a blocking agent and the addition amount of a 40% aqueous solution of sodium aminoethylsulfonate was 275 parts by mass. Thus, an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-4) was obtained.
<Raw materials>
-Polypropylene glycol molecular weight 2000 (polyether polyol)
Product name “Exenol 2020” (Asahi Glass, Mw = 2000) 410 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 320 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-5)
The following were used as raw materials. All the same as the blocked isocyanate compound (A-1) except that 180 parts by mass of o-sec-butylphenol was used as a blocking agent and the addition amount of 40% aqueous solution of sodium aminoethylsulfonate was 575 parts by mass. Thus, an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-5) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 110 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 480 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-6)
The following were used as raw materials. All the same as the blocked isocyanate compound (A-1) except that 300 parts by mass of o-sec-butylphenol was used as a blocking agent and the addition amount of 40% aqueous solution of sodium aminoethylsulfonate was 125 parts by mass. Thus, an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-6) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 180 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 470 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-7)
The following were used as raw materials. The use of 335 parts by mass of o-sec-butylphenol as a blocking agent, the addition amount of a 40% aqueous solution of sodium aminoethylsulfonate to 37.5 parts by mass, and the surfactant Neugen EA-137 was added before adding water. Except for the addition of 30 parts by mass, the same procedure as for the blocked isocyanate compound (A-1) was performed to obtain an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-7).
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 180 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 470 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-8)
The following were used as raw materials. The above-mentioned blocked isocyanate compound (A-1) except that 145 parts by mass of o-sec-butylphenol was used as a blocking agent and the addition amount of a 40% aqueous solution of sodium aminoethylsulfonate was 662.5 parts by mass. In the same manner as above, an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-8) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 110 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 480 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-9)
The following were used as raw materials. Except for using 1200 parts by mass of a 10% aqueous solution of sodium bisulfite as a blocking agent and using 300 parts by mass of ethyl acetate as a solvent, all were performed in the same manner as for the blocked isocyanate compound (A-1). An aqueous dispersion containing 30% by mass of the isocyanate compound (A-9) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Chemical Co., Ltd., Mw = about 400) 545 parts by mass. Hexamethylene diisocyanate product name “Duranate 50M” (manufactured by Asahi Kasei Chemicals, isocyanate group content 50% by mass) 335 parts by mass. 300 parts by mass of ethyl acetate

(Blocked isocyanate compound A-10)
The following were used as raw materials. 290 parts by weight of o-sec-butylphenol was used as a blocking agent, 60 parts by weight of dimethylaminoethanol was added instead of 40% aqueous solution of sodium aminoethylsulfonate, and then 80 parts by weight of dimethyl sulfate was added. Except that the quaternization step was carried out at 40 ° C. for about 30 minutes, it was carried out in the same manner as the above-mentioned blocked isocyanate compound (A-1), and water containing 30% by mass of the blocked isocyanate compound (A-10) A dispersion was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 110 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 460 parts by mass, dimethylaminoethanol 60 parts by mass, dimethyl sulfate 80 parts by mass, methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-11)
The following were used as raw materials. Except for using 210 parts by mass of 3,5-dimethylpyrazole as a blocking agent, the same procedure as for the blocked isocyanate compound (A-1) was carried out. Water containing 30% by mass of the blocked isocyanate compound (A-11) A dispersion was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Chemical Co., Ltd., Mw = about 400) 130 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 530 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-12)
The following were used as raw materials. The above-mentioned blocked isocyanate compound (except that 300 parts by mass of o-sec-butylphenol was used as a blocking agent and 200 parts by mass of 40% aqueous solution of sodium aminoacetate instead of 40% aqueous solution of sodium aminoethylsulfonate) In the same manner as in A-1), an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-12) was obtained.
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 130 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 490 parts by mass / 300 parts by mass of methyl ethyl ketone

(Blocked isocyanate compound A-13)
The following raw materials were added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, and reacted at 75 ° C. for 2 hours to obtain a methyl ethyl ketone solution of an isocyanate-terminated urethane prepolymer. After the methyl ethyl ketone solution was cooled to 40 ° C. and reacted with 180 parts by mass of methyl ethyl ketone oxime as a blocking agent, 200 parts by mass of a 10% aqueous sodium hydroxide solution was added to neutralize dimethylolpropionic acid in the prepolymer. Thereafter, 2700 parts by mass of water was gradually added while being stirred with a homogenizer, and emulsified and dispersed. The solvent was removed at 50 ° C. under reduced pressure to obtain an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-13).
<Raw materials>
・ Propylene oxide adduct of bisphenol A (polyether polyol)
Product name “New Pole BP-3P” (manufactured by Sanyo Kasei Co., Ltd., Mw = about 400) 200 parts by mass / polymeric MDI
Product name "PAPI-27" (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 550 parts by mass, dimethylolpropionic acid 70 parts by mass, methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-14)
The following were used as raw materials. Except for using 300 parts by mass of o-sec-butylphenol as a blocking agent, the same procedure as for the blocked isocyanate compound (A-1) was carried out. Water containing 30% by mass of the blocked isocyanate compound (A-14) A dispersion was obtained.
<Raw materials>
-Polyethylene glycol molecular weight 600
Product name “PEG600S” (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 600) 250 parts by mass / Methoxy-polyethylene glycol molecular weight 2500
Product name “m-PEGcp 2500” (Daiichi Kogyo Seiyaku Co., Ltd., Mw = 2500) 70 parts by mass / polymeric MDI
Product name “PAPI-27” (manufactured by Dow Chemical Japan Co., Ltd., isocyanate group content 32% by mass) 380 parts by mass / methyl ethyl ketone 300 parts by mass

(Blocked isocyanate compound A-15)
The following raw materials are added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube, reacted at 75 ° C. for 1 hour, the ethyl acetate solution is cooled, and the following surfactant is added. Then, 1600 parts by mass of water was gradually added and emulsified and dispersed while stirring with a homogenizer. The solvent was removed at 50 ° C. under reduced pressure to obtain an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-15).
<Raw materials>
・ TDI adduct product name “Coronate L” (containing ethyl acetate, 75% active ingredient, isocyanate group content 13% by mass) (manufactured by Tosoh Corp.) 967 parts by mass • methyl ethyl ketone oxime 275 parts by mass Brand name “Epan 485” (Daiichi Kogyo Seiyaku) 70 parts by mass Brand name “Epan 785” (Daiichi Kogyo Seiyaku) 70 parts by mass

(Blocked isocyanate compound A-16)
All of the isocyanate TDI adducts except for using 685 parts by mass of urelate HMDI (trade name “Duranate TPA-100” instead of 21% isocyanate group content) and 315 parts by mass of methyl ethyl ketone oxime (block isocyanate compound ( In the same manner as in A-15), an aqueous dispersion containing 30% by mass of the blocked isocyanate compound (A-16) was obtained.
<Raw materials>
-Ethyl acetate 400 parts by mass-Surfactant trade name "Epan 485" (Daiichi Kogyo Seiyaku) 70 parts by mass Trade name "Epan 785" (Daiichi Kogyo Seiyaku) 70 parts by mass

(Manufacture of polyurethane compounds)
(Polyurethane compound D-1)
The following raw materials were added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, and reacted at 75 ° C. for 1 hour to obtain a polyurethane methylethylketone solution. The methyl ethyl ketone solution was cooled to 40 ° C., and 100 parts by mass of a 10% aqueous solution of sodium hydroxide was added to neutralize dimethylolpropionic acid in the polyurethane. Thereafter, 2700 parts by mass of water was gradually added while stirring with a homogenizer, and emulsified and dispersed. The solvent was removed at 50 ° C. under reduced pressure to obtain an aqueous dispersion containing 30% by mass of the polyurethane compound (D-1).
<Raw materials>
-Polyester polyol formed by 3-methyl-1,5-pentanediol, adipic acid, and isophthalic acid, trade name "Kurapol P-2012" (Kuraray Co., Ltd., Mw = about 2000) 820 parts by mass
Product name “Millionate MT, isocyanate group content 32% by mass” (manufactured by Tosoh Corporation) 140 parts by mass, dimethylolpropionic acid 40 parts by mass, methyl ethyl ketone 1000 parts by mass

(Experimental example 1: Production of fiber reinforced resin mixture and fiber reinforced resin (molded body))
According to the composition shown in Table 1 (raw materials and blending parts), the blocked isocyanate compound (A) and water (C) are added to the cellulose fiber (B) (conifer kraft pulp), and the thermoplastic resin (X2-1) is further added. (PP powder) and thermoplastic resin (X2-2) (maleic acid-modified PP (MAPP)) were added and mixed using an automatic revolution mixer (trade name: manufactured by Shinky Co., Ltd., trade name: Foaming Netaro). The obtained mixture was dried at 80 ° C. for 6 hours to obtain a fiber reinforced resin mixture (X).
Thermoplastic resin (X2-3) (PP pellet, melting point 167 ° C.) was further mixed with the obtained fiber reinforced resin mixture (X), and the mixture was mixed with a twin-screw extruder (trade name: KZW15-60MG, manufactured by Technobel). The mixture was melt-kneaded to obtain a pellet-shaped molded body. The cylinder temperature of the twin screw extruder was set to 140 ° C., 150 ° C., 160 ° C., 170 ° C., 170 ° C., 170 ° C., 170 ° C. and 170 ° C. from the upstream side.
The obtained molded body is put into an injection molding machine (Nissei Plastic Industry, NPX7) and injected into a flat plate mold having a thickness of 4 mm, a width of 10 mm, and a length of 80 mm to obtain a resin molded body (test piece). (Molding temperature 180 ° C. to 185 ° C., mold temperature 30 ° C.). The type of the block isocyanate compound (A) was changed, and molded articles (test pieces) of the fiber reinforced resins (Y) of Examples 1 to 16 were obtained.
Also, instead of using the blocked isocyanate compound (A), the polyurethane compound (D) is similarly produced, and the blocked isocyanate compound (A) is produced in the same manner without using the polyurethane compound (D). The molding (test piece) of the fiber reinforced resin of Comparative Examples 1 and 2 was obtained.
The results are shown in Tables 3 and 4.

(Experimental example 2: Production of fiber reinforced resin mixture and fiber reinforced resin (molded body))
According to the composition shown in Table 1 (used raw materials and blending part), all except that the cylinder temperature was 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C, 190 ° C, 190 ° C, 190 ° C from the upstream side, In the same manner as in Production Example 1, fiber reinforced resin molded articles (test pieces) of Examples 17 to 20 and Comparative Examples 3 and 4 were obtained.
The results are shown in Table 5.

(Experimental example 3: Production of fiber reinforced resin mixture and fiber reinforced resin (molded article))
Except for changing to the composition shown in Table 2 (used raw materials and blending parts), the same as in Production Example 1, fiber-reinforced resin moldings (test pieces) of Examples 21 to 24 and Comparative Examples 5 and 6 were obtained. It was.
The results are shown in Table 6.

About content of the hydrophilic group in a block isocyanate compound, content of a block group, and content of an aromatic cyclic structure, it measured as follows.
The hydrophilic group content, block group content, and aromatic cyclic structure content in the polyurethane compound were also measured as follows.

(Measurement method of hydrophilic group content)
The content (mmol / g) of the hydrophilic group was calculated as the ratio of the molar amount (charge amount) of the hydrophilic group compound to the total mass of the blocked isocyanate compound using the following formula.
Hydrophilic group content (mmol / g) = {(charge amount of hydrophilic group compound (g) / molecular weight of hydrophilic group compound) / total mass of blocked isocyanate compound (g)} × 1000
The content (mmol / g) of the hydrophilic group was calculated as a ratio of the molar amount of the hydrophilic group compound (amount charged) to the total mass of the polyurethane compound using the following formula.
Hydrophilic group content (mmol / g) = {(charge amount of hydrophilic group compound (g) / molecular weight of hydrophilic group compound) / total mass of polyurethane compound (g)} × 1000
In this example, dimethylolpropionic acid, sodium aminoethylsulfonate, sodium aminoacetate, dimethylaminoethanol and sodium bisulfite correspond to the hydrophilic group compound.

(Measurement method of block group content)
The content (mmol / g) of the blocking group was calculated using the following calculation formula as the ratio of the mole of the blocking agent (the amount charged) to the total mass of the blocked isocyanate compound.
Block group content (mmol / g) = {(charging amount of blocking agent (g) / molecular weight of blocking agent) / total mass of blocked isocyanate compound (g)} × 1000
In this example, methyl ethyl ketone oxime, o-sec-butylphenol, caprolactam, 3,5-dimethylpyrazole and sodium bisulfite correspond to the blocking agent.
In Example 9, sodium bisulfite corresponds to both the hydrophilic group compound and the blocking agent.

(Measurement method of content of aromatic cyclic structure)
The content (mass%) of the aromatic cyclic structure is the total of the aromatic cyclic structure (benzene ring: molecular weight 78) in the raw material used for the production of the blocked isocyanate compound with respect to the total mass (g) of the blocked isocyanate compound. It was calculated as a mass (g) ratio.
In this example, specifically, the content (mass%) of the aromatic cyclic structure is the mass of the aromatic cyclic structure (phenyl group) in the isocyanate compound relative to the total mass of the blocked isocyanate compound, and the polyol. It calculated using the following formula as a ratio of the sum total of the mass of the aromatic cyclic structure in the inside, and the mass of the aromatic cyclic structure in the blocking agent.
Aromatic content (mass%) = {(mass of aromatic cyclic structure in isocyanate compound (g) + mass of aromatic cyclic structure in polyol (g) + of aromatic cyclic structure in blocking agent Mass (g)) / total mass of blocked isocyanate compound (g)} × 100
Specifically, for example, in blocked isocyanate compound A-1, since the blocking agent does not have an aromatic cyclic structure, the mass (g) of the aromatic cyclic structure in the isocyanate compound and the aromatic ring in the polyol compound The mass (g) of the formula structure was calculated as follows.
Regarding the mass (g) of the aromatic cyclic structure in the isocyanate compound, PAPI-27 has 32 mass% of isocyanate groups. In PAPI-27, the number of moles of isocyanate groups and the moles of benzene rings are Since the number is approximately equal, it was calculated using the following formula. The molecular weight of benzene (78) was used as the molecular weight of the phenyl group. Further, the molecular weight of naphthalene (128) can be adopted as the molecular weight of the naphthyl group.
Mass (g) of aromatic cyclic structure in isocyanate compound = (number of moles of isocyanate group) × (molecular weight 78 of benzene as phenyl group) = [{charge amount of isocyanate compound 540 (g) × (32 (mass %) / 100)} / 42] × 78 = 320.9 (g)
The mass (g) of the aromatic cyclic structure in the polyol compound was calculated using the following formula, for example, since Newpol BP-3P has 38% by mass of the aromatic cyclic structure.
Mass of aromatic cyclic structure in polyol compound = (charge amount of polyol compound (g)) × (38 (mass%) / 100) = 130 × 0.38 = 49.4 (g)
Therefore, from the above, the content (mass%) of the aromatic cyclic structure in the blocked isocyanate compound A-1 is calculated as {(320.9 g + 49.4 g) / 1000} × 100 = 37.0%.
In addition, when a blocking agent has an aromatic cyclic structure, after calculating the mass (g) of an aromatic cyclic structure using a following formula, the result should just be substituted into said formula.
Mass of aromatic cyclic structure in blocking agent (g) = Amount of blocking agent charged (g) × (Ratio of aromatic cyclic structure in blocking agent (mass%) / 100)
Further, the content of the aromatic cyclic structure in the polyurethane compound was measured in the same manner as described above except that the total mass of the polyurethane compound was used instead of the total mass of the blocked isocyanate compound.

(Evaluation methods)
Evaluation was performed by the following method using the obtained test piece.

(Bending strength, flexural modulus)
Using an autograph universal testing machine (manufactured by Shimadzu Corp., load cell 100 kg), the test speed was 10 mm / min and the distance between the fulcrums was 64 mm, according to JIS K 7017 (Fiber-Reinforced Plastic-Determination of Bending Properties).

(Average particle size measurement method)
The average particle sizes of the blocked isocyanate compound and the polyurethane compound in the obtained aqueous dispersion were measured using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.).

<Evaluation results>
From Examples 1 to 24 and Comparative Examples 1 to 6, it was found that the resin molded bodies of the examples had higher bending strength and bending elastic modulus than the comparative examples.

Example 2
(Production of blocked isocyanate compounds)
In the same manner as described above, aqueous dispersions each containing the blocked isocyanate compounds (A-1), (A-2), and (A-9) were produced.

(Manufacture of polyurethane compounds)
In the same manner as described above, an aqueous dispersion containing the polyurethane compound (D-1) was produced as the polyurethane compound (D).

(Experimental example 4: Production of fiber reinforced resin mixture and fiber reinforced resin (molded body))
According to the composition shown in Table 7 (raw materials and blending parts), the blocked isocyanate compound (A) and water (C) are added to the cellulose fiber (B) (conifer kraft pulp), and a thermoplastic resin (X2- 1) The fiber-reinforced resin mixture (X) of Production Example 1 was added in the same manner as in Experimental Example 1 except that (PP powder) and thermoplastic resin (X2-2) (maleic acid-modified PP (MAPP)) were added. )
A pellet-shaped molded body was obtained in the same manner as in Experimental Example 1 except that the obtained fiber-reinforced resin mixture (X) was further mixed with a thermoplastic resin (X2-3) (PP pellet, melting point 167 ° C.). Obtained.
The obtained molded body was processed in the same manner as in Experimental Example 1 to obtain a molded resin body (test piece) of Production Example 1.
Further, according to the composition shown in Table 7, the type of the blocked isocyanate compound (A) was changed, and the same procedure as in Production Example 1 was conducted except that the polyurethane compound (D) was used instead of the blocked isocyanate compound (A). Molded bodies (test pieces) of the fiber reinforced resin mixture (X) and the fiber reinforced resin (Y) of Production Examples 2 to 4 were obtained.
The results are shown in Table 7.

(Experimental Example 5: Production of fiber reinforced resin mixture and fiber reinforced resin (molded article))
According to the composition shown in Tables 7 and 8 (used raw materials and blending parts), the cellulose fiber (B) (conifer kraft pulp), the blocked isocyanate compound (A) or the polyurethane compound (D), water (C), and The fiber-reinforced resin mixture of Production Examples 5 to 14 was prepared in the same manner as Production Examples 1 to 4 except that an anionic surfactant (E) or a silicone-based or acetylene-based nonionic surfactant (F) was added. A molded body (test piece) of (X) and fiber reinforced resin (Y) was produced.
The results are shown in Tables 7 and 8.

(Experimental example 6: Production of fiber-reinforced resin mixture and fiber-reinforced resin (molded body))
According to the composition shown in Table 8 (raw materials and blending parts), neither an anionic surfactant (E) nor a silicone-based or acetylenic nonionic surfactant (F) was used. The fiber-reinforced resin mixture and the fiber-reinforced resin molding (test piece) of Production Examples 15 and 16 were obtained in the same manner as Production Examples 5 to 14 except that the surfactant (G) was used.
The results are shown in Table 8.

(Experimental Example 7: Production of fiber reinforced resin mixture and fiber reinforced resin (molded article))
According to the composition shown in Table 8 (raw materials and blending parts), neither the blocked isocyanate compound (A) nor the polyurethane compound (D) is used, and the surfactants (E), (F), (G) are not used. Except for this, the fiber-reinforced resin mixture and fiber-reinforced resin molding (test piece) of Production Example 17 were obtained in the same manner as Production Examples 1 to 4.
Further, according to the composition shown in Table 8 (used raw materials and blended parts), neither the blocked isocyanate compound (A) nor the polyurethane compound (D) was used, while the surfactant (F) was used, except for using the surfactant (F). In the same manner as in Example 14, a molded product (test piece) of the fiber reinforced resin of Production Example 18 was obtained.
The results are shown in Table 8.

The content of the hydrophilic group, the content of the blocking group, and the content of the aromatic cyclic structure in the blocked isocyanate compound were measured in the same manner as described above.
Further, the content of the hydrophilic group in the polyurethane compound and the content of the aromatic cyclic structure were measured in the same manner as described above.

(Evaluation methods)
Evaluation was performed by measuring bending strength and a bending elastic modulus like the above using the obtained test piece.
Moreover, it carried out similarly to the above, and measured the average particle diameter of the block isocyanate compound and polyurethane compound in the obtained water dispersion.

<Evaluation results>
From Tables 7 and 8, the blocked isocyanate compound (A) or polyurethane compound (D), cellulose fiber (B), anionic surfactant (E), or silicone-based or acetylene-based nonionic surfactant ( It was found that Production Examples 5 to 14 containing E) had higher bending strength and flexural modulus than Production Examples 1 to 4 containing no surfactants (E), (F) and (G). .
In addition, it was found that Production Examples 5 to 14 have higher bending strength and flexural modulus than Production Examples 15 and 16 containing the higher alcohol nonionic surfactant (G).
Further, Production Examples 5 to 14 are Production Example 17 containing neither the blocked isocyanate compound (A), the polyurethane compound (D) nor the surfactants (E), (F), (G) (ie, cellulose fibers). It was found that the bending strength and the bending elastic modulus were higher than those of the sample containing only (B).
In addition, Production Examples 5 to 14 contain the surfactant (E) or the surfactant (F), but are less than the Production Example 18 containing neither the blocked isocyanate compound (A) nor the polyurethane compound (D). It was found that the bending strength and the flexural modulus were high.

As a result, Production Examples 5 to 14 contain the blocked isocyanate compound (A) or the polyurethane compound (D), the cellulose fiber (B), and the surfactant (E) or the surfactant (F). As a result, it was found that high bending strength and flexural modulus were exhibited, and that this effect was synergistic.

Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the features of the embodiments and examples. Moreover, it should be thought that embodiment and the Example which were disclosed this time are illustrations in all points, and are not restrictive. The scope of the present invention is shown not by the embodiments and examples described above but by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims.

Claims (20)

Resin reinforcing mixture (X1) containing the blocked isocyanate compound (A) and cellulose fiber (B). The resin reinforcing mixture (X1) according to claim 1, wherein the blocked isocyanate compound (A) has a hydrophilic group. The resin reinforcing mixture (X1) according to claim 2, wherein the content of the hydrophilic group in the blocked isocyanate compound (A) is 0.07 to 2.10 mmol / g. The blocked isocyanate compound (A) is an oxime block agent, a phenol block agent, a lactam block agent, an alcohol block agent, an active methylene block agent, an amine block agent, a pyrazole block agent, a bisulfite block. The resin reinforcing mixture (X1) according to any one of claims 1 to 3, wherein the isocyanate group of the polyisocyanate compound is blocked by at least one selected from the group consisting of an agent and an imidazole blocking agent. The resin reinforcing mixture (X1) according to any one of claims 1 to 4, further comprising water (C). A fiber-reinforced resin mixture (X) comprising the resin reinforcing mixture (X1) according to any one of claims 1 to 5 and a thermoplastic resin (X2). A fiber-reinforced resin mixture (X), wherein the resin reinforcing mixture (X1) according to claim 5 and the thermoplastic resin (X2) are mixed and dried. In a state where the fiber-reinforced resin mixture (X) according to claim 6 or 7 is heated above a temperature at which the blocking group of the blocked isocyanate compound (A) is dissociated and the thermoplastic resin (X2) is melted, A fiber reinforced resin (Y) mixed. The fiber-reinforced resin mixture (X) containing the blocked isocyanate compound (A), the cellulose fiber (B), and the thermoplastic resin (X2) is separated from the blocked group of the blocked isocyanate compound (A) and the heat The manufacturing method of fiber reinforced resin (Y) provided with the process mixed in the state heated more than the temperature which a plastic resin (X2) fuse | melts. The method for producing a fiber reinforced resin (Y) according to claim 9, wherein the fiber reinforced resin mixture (X) further contains water (C). A blocked isocyanate compound (A) or a polyurethane compound (D);
Cellulose fibers (B);
A resin reinforcing mixture (X1) containing an anionic surfactant (E) or a silicone-based or acetylene-based nonionic surfactant (F). The resin reinforcing mixture (X1) according to claim 11, wherein the blocked isocyanate compound (A) or the polyurethane compound (D) has a hydrophilic group. The resin reinforcing mixture (X1) according to claim 11 or 12, further comprising water (C). A fiber-reinforced resin mixture (X) comprising the resin reinforcing mixture (X1) according to any one of claims 11 to 13 and a thermoplastic resin (X2). A fiber-reinforced resin mixture (X) obtained by mixing and drying the resin reinforcing mixture (X1) according to claim 13 and a thermoplastic resin (X2). A fiber reinforced resin (Y) obtained by mixing the fiber reinforced resin mixture (X) according to claim 14 or 15 while being heated at a temperature higher than a temperature at which the thermoplastic resin (X2) melts. Block isocyanate compound (A) or polyurethane compound (D), cellulose fiber (B), anionic surfactant (E), silicone-based or acetylene-based nonionic surfactant (F), and thermoplasticity A method for producing a fiber reinforced resin (Y), comprising a step of mixing a fiber reinforced resin mixture (X) containing a resin (X2) in a state of being heated to a temperature at which the thermoplastic resin (X2) melts or higher. . The fiber reinforced resin mixture (X) contains the blocked isocyanate compound (A),
The fiber reinforced resin mixture (X) is provided with a step of mixing in a state where the block group of the blocked isocyanate compound (A) is dissociated and heated to a temperature at which the thermoplastic resin (X2) melts. Item 18. A method for producing a fiber reinforced resin (Y) according to Item 17. The fiber reinforced resin mixture (X) contains the polyurethane compound (D),
The step of mixing the fiber reinforced resin mixture (X) in a state where the polyurethane compound (D) is fused and heated at a temperature higher than a temperature at which the thermoplastic resin (X2) is melted. The manufacturing method of fiber reinforced resin (Y) of description. The method for producing a fiber reinforced resin (Y) according to any one of claims 17 to 19, wherein the fiber reinforced resin mixture (X) further contains water (C).