WO2017006986A1 - Resin composition and method for manufacturing same, and molded body - Google Patents

Abstract

To provide a resin composition obtained by a simple manufacturing method and which has excellent productivity and low production cost as well as high chemical strength and excellent flame-retardant properties, heat aging resistance, and weather resistance, and a method for manufacturing the resin composition, and to provide a molded body obtained from the resin composition. This resin composition is characterized by containing a lignocellulose-based mixture and a thermoplastic resin, the resin composition containing 0.5% by mass to 60% by mass of the lignocellulose-based mixture with respect to a combined total of 100% by mass of the lignocellulose-based mixture and the thermoplastic resin, and particles 1 mm or larger not being visible in a molded article of the resin composition.

Description

Resin composition, method for producing the same, and molded article

The present invention relates to a resin composition, a method for producing the same, and a molded body.

The fiber reinforced composite material, whose strength and rigidity are greatly improved by blending various fibrous reinforcing materials with resin, is widely used in industrial fields such as electric / electronics, machinery, automobiles, and building materials. As the fibrous reinforcing material blended in the fiber-reinforced composite material, glass fibers having excellent strength and lightness are mainly used. However, the glass fiber reinforced material achieves high rigidity, but has a limitation in weight reduction because of its high specific gravity. In addition, when disposing of this glass fiber reinforced material, the glass fiber itself is non-flammable, which causes problems such as damage to the combustion furnace during incineration and low combustion efficiency, making it suitable for thermal recyclability. There was also the disadvantage of not. As other fibrous reinforcements, fiber reinforcements made of organic materials such as polyester fibers, polyamide fibers, and aramid fibers have been studied, but fiber reinforcement materials containing these reinforcements can ensure light weight and thermal recyclability. However, there was a problem that the mechanical reinforcement effect was not sufficient.

In recent years, reinforced resins to which plant fibers such as bamboo, kenaf, sugar cane, and wood are added have been studied, while high-functional materials using plant-derived materials are attracting attention from the viewpoint of carbon neutral (for example, Patent Document 1 and 2).
In addition, a fiber composite material has been proposed in which cellulose fibers that have been fibrillated and microfibrillated as described above are mixed with a resin. It has been reported that when such microfibrillated cellulose fibers are used as a resin reinforcing material, the mechanical strength is improved (for example, Patent Documents 3 and 4).

For example, Patent Document 3 discloses a method in which cellulose fibers from pulp are modified in a solution, microfibrillated using a biaxial kneader, and uniformly dispersed in a matrix resin.
Patent Document 4 discloses a cellulose fiber coated with a lignophenol derivative and having an average fiber diameter of 2 nm or more and 200 nm or less, and a cellulose fiber composite material containing the cellulose fiber dispersed in a matrix resin. Yes.

JP-A-5-92527 JP 2002-69208 A JP 2005-42283 A JP 2011-38193 A

Since the composite materials proposed in Patent Documents 1 and 2 are insufficient in mechanical properties such as tensile elastic modulus, their applications are limited.
Moreover, in the invention described in Patent Document 3, the dispersion of cellulose fibers in the resin is still insufficient, and the resultant fiber composite material has insufficient mechanical strength. In addition, the modified cellulose contains moisture and the like, and it becomes a problem in terms of productivity, or a resin (for example, polyamide or polyester) that is affected by moisture can produce a cellulose fiber composite material. There were problems such as being unable to do so. Furthermore, a modification step is necessary, which is disadvantageous in terms of cost.
Further, in Patent Document 4, the thermal decomposition temperature is improved by surface-coating cellulose fibers with a lignophenol derivative, but a process of coating with a lignophenol derivative is required, and this production method is There was a problem in terms of cost.

The problem to be solved by the present invention is that the manufacturing method is simple, the productivity is excellent, the production cost is low, the mechanical strength is high, and the molded product is excellent in flame retardancy, heat aging resistance, and weather resistance. It is providing the resin composition which can be obtained, its manufacturing method, and the molded object obtained from the said resin composition.

As a result of intensive studies, the inventors of the present invention include a lignophenol derivative and a cellulose component, blend a lignophenol-based mixture and a thermoplastic resin in a specific ratio, and a 1 mm or more irregularity is visually observed in a molded product. By blending a lignocellulosic mixture obtained by adding and mixing an acid to a lignocellulosic material to which a phenolic compound is added, and a thermoplastic resin at a specific ratio The present inventors have found that the above problems can be solved.

That is, the present invention provides the following.
<1> A lignocellulose-based mixture and a thermoplastic resin are contained, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass, the lignocellulose-based mixture is contained in an amount of 0.5% by mass to 60% by mass. In addition, the resin composition is characterized in that in the molded product, no defects of 1 mm or more are visually observed.
<2> The resin composition according to <1>, wherein the lignocellulose-based mixture has an average major axis length of 10 to 500 nm and an average minor axis length of 5 to 50 nm.
<3> The resin composition according to <1> or <2>, in which the lignocellulose-based mixture is a composition containing needle-like or cage-like crystals.
<4> Any one of the above <1> to <3>, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins. The resin composition as described in one.
<5> The resin composition according to any one of <1> to <4>, wherein the thermoplastic resin is a polyolefin resin.
<6> The resin composition according to any one of <1> to <5>, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
<7> The resin composition according to <5> or <6>, wherein the obtained molded article has an elongation retention after exposure to light of 65% or more.
<8> The resin composition according to any one of <1> to <7>, further comprising an antioxidant.

<9> Contains a lignocellulose-based mixture and a thermoplastic resin, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100 mass%, the lignocellulose-based mixture is contained in an amount of 0.5 mass% to 60 mass%. The lignocellulosic mixture is obtained by adding an acid to a lignocellulosic material to which a phenol compound has been added, and mixing the lignocellulosic material. The lignocellulosic mixture comprises a lignophenol derivative and a cellulose component. The resin composition as described in any one.
<10> The resin composition according to <9>, wherein the acid is at least one selected from the group consisting of phosphoric acid, formic acid, and trifluoroacetic acid.
<11> The resin composition according to <9> or <10>, wherein the phenol compound added to the lignocellulosic material is a phenol compound having one or more substituents at least in the ortho position or the para position.
<12> The phenol compound to be added to the lignocellulosic material has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group, The resin composition according to any one of <9> to <11>, which is a phenol compound having an ortho position and / or a para position.
<13> The lignocellulosic mixture is selected from the group consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol. <9> to <12>, which is obtained by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which at least one phenol compound is added. Resin composition.
<14> The resin composition according to any one of <1> to <13>, which is obtained by hot melt mixing a lignocellulose-based mixture and a thermoplastic resin.
<15> A molded product obtained by molding the resin composition according to any one of <1> to <14>.

<16> Step of obtaining a lignocellulose-based mixture comprising a lignophenol derivative and a cellulose component by adding an acid to the lignocellulosic material to which the phenol compound has been added, and the lignocellulose-based mixture and the thermoplastic resin. A resin composition containing 0.5% by mass or more and 60% by mass or less of the lignocellulose-based mixture when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass. Manufacturing method.
<17> The method for producing a resin composition according to <16>, wherein the acid is at least one selected from the group consisting of phosphoric acid, formic acid, and trifluoroacetic acid.
<18> The resin composition according to <16> or <17>, wherein the phenol compound added to the lignocellulosic material is a phenol compound having one or more substituents at least in the ortho position or the para position. Manufacturing method.
<19> The phenol compound to be added to the lignocellulosic material has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group, The method for producing a resin composition according to any one of <16> to <18>, wherein the resin composition is a phenol compound having an ortho position and / or a para position.
<20> The lignocellulose-based mixture is selected from the group consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol. <16> to <19> obtained by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which at least one phenol compound is added. A method for producing the resin composition.
<21> Any one of the above <16> to <20>, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins. The manufacturing method of the resin composition as described in one.
<22> The method for producing a resin composition according to any one of <16> to <21>, wherein the thermoplastic resin is a polyolefin resin.
<23> The method for producing a resin composition according to any one of <16> to <22>, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
<24> The resin according to any one of <16> to <23>, wherein the step (2) is a step of heat-melting and mixing an antioxidant in addition to the lignocellulose-based mixture and the thermoplastic resin. A method for producing the composition.

According to the present invention, a resin composition capable of producing a molded product with a simple manufacturing method, excellent productivity, low production cost, high mechanical strength, excellent flame resistance, heat aging resistance, and weather resistance. Articles, methods for producing the same, and molded articles obtained from the resin composition can be provided.

Hereinafter, the present invention will be described. In this specification, the term “to” relating to the description of numerical values represents a numerical range including end points. Moreover, mass% and mass part are synonymous with weight% and weight part, respectively. In the present invention, a combination of preferred embodiments is a more preferred embodiment.

(Resin composition)
The first resin composition of the present invention contains a lignocellulose-based mixture and a thermoplastic resin, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass, the lignocellulose-based mixture is 0.5%. It is characterized by containing not less than 60% by mass and not visually confirming 1 mm or more in the molded product.
The second resin composition of the present invention contains a lignocellulosic mixture and a thermoplastic resin. When the total of the lignocellulosic mixture and the thermoplastic resin is 100% by mass, the lignocellulosic mixture is 0. The lignocellulosic mixture is contained by adding an acid to a lignocellulosic material to which a phenol compound is added, and is composed of a lignophenol derivative and a cellulose component. It is characterized by.
The inventors have found that a high-strength material can be obtained and a heat aging resistance and a weather resistance are excellent by blending a specific amount of a lignocellulose-based mixture with a thermoplastic resin. Although the detailed mechanism of the effect is unknown, the cellulose component is uniformly dispersed in the resin by covering the cellulose component with a lignophenol derivative excellent in compatibility with the resin, and the resin is reinforced. It is presumed that this is a result of excellent aging resistance and weather resistance due to the lignophenol derivative that contributes to relaxation of stress and further has an antioxidant function and an ultraviolet absorbing ability.

1. Lignocellulose-based mixture In the present invention, the lignocellulose-based mixture is obtained by adding an acid to a lignocellulosic material to which a phenol compound has been added and mixing, and is composed of a lignophenol derivative and a cellulose component.
(1) Lignocellulosic material Examples of the lignocellulosic material include wooded materials, various materials mainly made of wood, such as wood flour, chips, waste materials, and scrap materials. Moreover, as wood to be used, any kind of wood such as conifers and hardwoods can be used. Furthermore, various herbaceous plants and related samples such as agricultural wastes can be used.
A lignocellulosic substance may be used individually by 1 type, and may use 2 or more types together.

The lignocellulosic material is preferably subjected to pretreatment such as pulverization and drying in advance, and it is preferable to perform a degreasing treatment as necessary.
In the pulverization of the lignocellulosic material as the raw material, the opening at the time of sieving after pulverization is preferably 5 mm or less, more preferably 2 mm or less, still more preferably 1 mm or less, and 0.5 mm. It is particularly preferable that it is not more than 0.3 mm, and most preferably not more than 0.3 mm.
Further, the water content is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. It is preferable to perform drying so as to achieve the above moisture content. By setting the moisture content within the above range, clogging is suppressed during sieving and the yield of the raw material powder is improved, which is preferable.

Depending on the type of lignocellulosic material, it is preferable to perform a degreasing treatment. By the degreasing treatment, unnecessary oil and fat can be removed. As a degreasing method, for example, a lignocellulosic material and an organic solvent can be charged into a stirring tank, and sufficiently mixed and stirred. By degreasing with an organic solvent, an effect of removing water in the lignocellulosic material can also be obtained. For this purpose, it is preferable to use an organic solvent such as acetone or hexane.
Further, the organic solvent for performing the degreasing treatment is not particularly limited, and an ethanol-benzene mixed solvent, an acetone-methanol mixed solvent and the like are preferably exemplified.
The amount of the organic solvent used is preferably 1 to 10 times the amount of lignocellulosic material. The “double amount” defined here means the amount of the organic solvent (liters) relative to 1 kg of the raw material. For example, the “5-fold amount” means that 5 L of the organic solvent is added to 1 kg of the raw material. Means. Further, after the addition of the organic solvent, the mixture is preferably stirred for 1 to 120 hours, more preferably 1 to 60 hours.
Before adding the phenol compound, it is preferable to remove the organic solvent used for degreasing, but if the phenol compound solvent and the organic solvent used for degreasing are the same, the removal step may be omitted. Good.

(2) Phenol compound Although a phenol compound will not be specifically limited if it is a compound which has at least 1 OH group on an aromatic ring, It is preferable that it is a compound which has at least 1 OH group on a benzene ring.
Specifically, a monovalent phenol compound, a divalent phenol compound, a trivalent phenol compound, or the like can be used as the phenol compound.
Specific examples of the monovalent phenol compound include phenol that may have one or more substituents, naphthol that may have one or more substituents, and one or more substituents. Good antroll and the like.
Specific examples of the divalent phenol compound include catechol which may have one or more substituents, resorcinol which may have one or more substituents, and one or more substituents. Examples include good hydroquinone.
Specific examples of the trivalent phenol compound include pyrogallol, which may have one or more substituents.
A phenol compound may be used individually by 1 type and may use 2 or more types together.

The type of substituent that the monovalent to trivalent phenol compound may have is not particularly limited, and may have any substituent, but is preferably an electron donating group, for example, Alkyl groups having 1 to 6 carbon atoms (such as methyl, ethyl, and propyl groups), alkoxy groups having 1 to 6 carbon atoms (such as methoxy, ethoxy, and propoxy groups), aryl groups (such as phenyl groups), and the like. Can be mentioned. Among these, the phenol compound preferably has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Further, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The alkoxy group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The alkyl group and alkoxy group may further have a substituent, and examples of the substituent include a hydroxyl group.
The phenol compound is preferably a phenol compound having one or more substituents at least in the ortho-position or para-position, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group More preferably, it is a phenol compound having at least one substituent selected from the group consisting of at the ortho position and / or the para position.
In the phenol compound, at least one of the ortho positions is preferably unsubstituted.

Preferred examples of the phenol compound include p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol, Loglucinol and the like, and p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol are more preferable.

By controlling the type of phenolic compound used, the overall function (chemical / physical functions such as hydrophilicity and hydrophobicity) of the lignocellulosic mixture that is the component of the present invention obtained is controlled. Can do.
The phenol compound used in the present invention is a phenol compound having a substituent at the 4-position (para-position), a phenol compound having a substituent at the 2-position (ortho-position), the 2-position (ortho-position) and the 4-position (para-position). Phenol compounds having a substituent at the position) are preferred. The phenol compound having a substituent at the 4-position (para-position) is a phenol compound having no substituent at two ortho positions. In addition, the phenol compound having a substituent at the 2-position (ortho position) and the 4-position (para-position) is a phenol compound having no substituent at the 6-position (one ortho position).

By reacting the lignophenol derivative with a crosslinkable functional group-forming compound under alkaline conditions, a crosslinkable lignophenol derivative having a crosslinkable functional group at the ortho position of the phenolic hydroxyl group in the lignophenol derivative is prepared. It is also possible to prepare and use a polymer material by crosslinking lignophenol. In this case, the frequency of introduction of the crosslinkable functional group can be adjusted by selecting the type of phenol compound to be used. That is, when a phenol compound having a substituent at the 4-position (para-position) is used, the phenol compound is bonded to the carbon atom at the benzyl position of the phenylpropane unit of lignin at the 2-position or 6-position carbon atom. become. In this case, one of the remaining carbon atoms at the 2nd or 6th position is left free to serve as a site for introducing a crosslinkable functional group.
On the other hand, when a phenol compound having a substituent at the 2-position (ortho position) and the 4-position (para-position) is used, the phenol compound is a carbon atom at the 6-position and the carbon atom at the benzyl position of the phenylpropane unit of lignin. Will be bound to. In this case, since there are no free ortho-position and para-position, the introduced phenol compound does not have a crosslinkable functional group introduction site. Therefore, the crosslinkable functional group is introduced only on the lignin matrix side.
In this way, a phenol compound having a crosslinkable functional group introduction site with different reactivity, or a number of introduction sites, or one or two or more different phenol compounds are introduced into lignin to introduce a lignophenol derivative. The number of crosslinkable functional group introduction sites in can be controlled, and as a result, the crosslink density of the crosslinkable lignin derivative can be controlled.

That is, in a lignophenol derivative separated by treating a lignocellulosic substance with an acid in the presence of a phenol compound or a polymer material containing the same, a substituent is located at the 2-position (ortho position) or the 4-position (para position). The function of the lignophenol derivative or the use of a phenol compound having a substituent at the 2-position (ortho position) and 4-position (para-position) as a blocking switching element It is also possible to control the structure.

Further, when a phenol compound having a substituent at the 2-position (ortho position) and the 6-position (ortho position) is used as the introduced phenol compound, the phenol compound is a benzyl of a phenylpropane unit of lignin at the 4-position carbon atom. To the carbon atom at the position. In this case, since there are no free ortho-position and para-position, the introduced phenol compound does not have a crosslinkable functional group introduction site. In addition, a phenol compound having a substituent at the 2-position (ortho position) and the 6-position (ortho position) does not exhibit a switching function, and thus functions as a stable control element. In the present invention, a phenol compound having a substituent at the 4-position (para-position), a phenol compound having a substituent at the 2-position (ortho-position) and the 4-position (ortho-position), or the 2-position (ortho-position) and the 6-position ( A phenol compound having a substituent at the ortho position can be appropriately selected and used depending on the purpose.

The addition amount of the phenol compound added to the lignocellulosic material is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, with respect to 100 parts by mass of the lignocellulosic material. More preferably, it is 40 mass parts.
In addition, it is preferable to add 1 to 5 moles of a phenol compound per phenylpropane unit (hereinafter also referred to as “C9 unit”) of lignin of the lignocellulosic material, and 1.5 to 4.5 moles It is more preferable to add an amount of a phenol compound, and it is even more preferable to add a 2 to 4 molar amount of a phenol compound.
Here, the phenylpropane unit of lignin is obtained as follows. Specifically, a formula for C9 units is calculated from the elemental analysis values, and this is used as the average basic skeleton (C9 units). The variation in conifers and hardwoods is not so great. Here, the molecular weight of conifer C9 units (all guaiacyl units, one OCH ₃ per C9 unit) is 200, and the broad-leaved tree C9 units (guayacyl units (one OCH ₃ )): syringyl The molecular weight of the unit (2 OCH ₃ ) = 50: 50) is calculated as 215.

(3) Acid The lignocellulosic material, more preferably, the acid added to the lignocellulosic material sorbed with the phenolic compound has an action of swelling cellulose and a low action of hydrolyzing cellulose. Is preferred. The acid added to the lignocellulosic material, preferably the lignocellulosic material sorbed with the phenolic compound, is an acid excluding the above-mentioned phenolic compound. Specific examples include phosphoric acid, hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, formic acid and the like. Preferred is phosphoric acid, formic acid or trifluoroacetic acid, and particularly preferred is phosphoric acid. The concentration of phosphoric acid is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The concentration of hydrochloric acid is preferably 38% by mass or more.
The phosphoric acid having the above concentration is preferably prepared from 99% phosphoric acid. The hydrochloric acid having the above concentration is preferably prepared under cooling and pressure.
The amount of the acid added is preferably 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the lignocellulosic material treated with the phenol compound. More preferably, it is part by mass.

(4) Method for producing lignocellulose-based mixture In the present invention, the lignocellulose-based mixture comprises a lignophenol derivative and a cellulose component, and an acid is added to and mixed with a lignocellulosic material to which a phenolic compound has been added. Manufactured.
The “lignophenol derivative” in the present specification means a polymer containing a diphenylpropane unit in which a phenol compound is introduced by a C—C bond at the side chain α-position of the phenylpropane unit of lignin. The amount and molecular weight of the introduced phenol compound in this polymer vary depending on the lignocellulosic material used as a raw material and the reaction conditions.

In order to obtain the lignocellulose-based mixture of the present invention from the lignocellulosic material, it is necessary to treat the lignin in the lignocellulosic material with a phenol compound to obtain a lignophenol derivative. As a method for converting lignin in a lignocellulosic substance into a lignophenol derivative, the following two methods may be mentioned.
The first method is to impregnate a lignocellulosic material such as wood flour with a liquid phenolic compound (as described above, such as p-cresol), solvate the lignin with the phenolic compound, A concentrated acid (what was demonstrated above, for example, 95 mass% phosphoric acid) is added and mixed with a lignocellulosic substance, and a cellulose component is melt | dissolved. According to this method, a phenol compound obtained by solvating lignin and a concentrated acid dissolving a cellulose component form a two-phase separation system. The lignin solvated by the phenolic compound is contacted with the acid only at the interface where the phenolic compound phase is in contact with the concentrated acid phase, and the side chain α-position, which is a highly reactive site of the lignin basic structural unit generated by contact with the acid. The (benzylic) cation is attacked by the phenolic compound. As a result, the phenol compound is introduced into the α-position by a C—C bond, and the benzyl aryl ether bond is cleaved to reduce the molecular weight. As a result, the molecular weight of lignin is reduced, and at the same time, a lignophenol derivative in which a phenol compound is introduced at the benzyl position of the basic structural unit is produced in the phenol compound phase.

In the second method, a lignocellulosic material is infiltrated with a solvent (for example, ethanol, acetone, hexane, etc.) in which a solid or liquid phenol compound is dissolved, and then the solvent is distilled off (recovery of the phenol compound). Wearing process). Next, concentrated acid (as described above, for example, 95% by mass phosphoric acid) is added to the lignocellulose-based material to dissolve the cellulose component. As a result, as in the first method, the lignin solvated with the phenol compound is attacked by the phenol compound with the cation at the highly reactive site (side chain α-position) of the lignin generated upon contact with the concentrated acid. A compound is introduced. In addition, the benzyl aryl ether bond is cleaved to reduce the lignin molecular weight.

In the second method, it is preferable to add the phenol compound in a state in which the phenol compound is sufficiently dispersed or dissolved in the lignocellulosic material. For this purpose, the phenol compound is mixed and dissolved in an organic solvent. It is preferable to add to the lignocellulosic material in a state of being dispersed or dissolved. In order to efficiently perform the reaction between the phenol compound and the lignocellulosic substance, a solution in which the phenol compound is dispersed or dissolved in an organic solvent (hereinafter also referred to as a phenol compound solution) is added to 1 kg of the lignocellulosic substance. On the other hand, it is preferably added at a ratio of 3 to 50 L (herein referred to as 3 to 50 times the amount), and more preferably 5 to 15 times the amount.
The temperature of the phenol compound solution is not particularly limited, but is preferably 10 to 50 ° C., more preferably 15 to 40 ° C., and still more preferably 20 to 30 ° C.
After adding the phenolic compound solution to the lignocellulosic material, stirring is performed, and it is preferable to impregnate the phenolic compound solution with the lignocellulosic material, preferably for 1 to 60 hours. It is more preferably 2 to 48 hours, and further preferably 4 to 36 hours. In the case of small scale, a method of stirring with a glass rod or a method using a magnetic stirrer can be used for a small scale, and for a large scale, a method using a magnetic stirrer or a tank having a stirring blade. Etc. are used.
Further, after the impregnation, it is preferable to remove the organic solvent and sorb the phenol compound.

The acid is preferably added at 10 to 50 ° C., more preferably at 20 to 40 ° C. Moreover, after adding an acid, in order to advance reaction uniformly, it is preferable to fully stir uniformly and a kneader may be used.
The treatment time with the acid is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour.

(5) Lignocellulose-based mixture To prepare a lignocellulose-based mixture from the above reaction mixture, the entire reaction solution after concentrated acid treatment was poured into excess water, and the insoluble fraction was collected by centrifugation and deacidified. Then, it may be dried. In this dried product, the lignophenol derivative and the cellulose component are uniformly present, that is, the cellulose component is uniformly present in the lignophenol matrix.
That is, the lignocellulose-based mixture obtained by the above-described method is a composition that uniformly contains a lignophenol derivative and a cellulose component, and that the cellulose component is uniformly present in the matrix of the lignophenol derivative without being unevenly distributed. As described in Patent Document 4, cellulose fibers are not coated with a lignophenol derivative. In the lignocellulose-based mixture, a crystalline cellulose component monodispersed in the lignophenol derivative is uniformly distributed by hydrolyzing the amorphous portion of cellulose. In the present invention, by using such a lignocellulose-based mixture, it is possible to obtain a molded article having an excellent appearance in which no defects of 1 mm or more are visually observed.

The lignocellulose-based mixture is preferably a composition containing needle-like or cage-like crystals (crystalline cellulose). The crystallinity of cellulose is a method in which only crystals are produced in production, but the crystallinity can be confirmed by X-ray analysis. Further, from the viewpoint of obtaining a molded article having excellent mechanical strength and ease of blending into a thermoplastic resin, the average length in the major axis direction (average major axis length) of the lignocellulosic mixture is preferably 10 to The average length (average minor axis length) in the direction perpendicular to the major axis is preferably 5 to 50 nm, more preferably 5 to 30 nm, still more preferably 500 nm, more preferably 20 nm or more, still more preferably 30 nm or more. 10 to 20 nm. Further, the major axis length / minor axis length is preferably 5 or more. The average major axis length is determined by observing an electron microscope image of the lignocellulose-based mixture. Specifically, the major axis length and the minor axis length of each of 50 randomly selected lignocellulose-based mixtures are measured using an electron microscope, and the average major axis length and the average minor axis length are obtained from the average. be able to. In addition, as for the uniaxial length when the cross section in the direction orthogonal to the major axis (uniaxial direction) is not circular, the length of the longest portion measured in the axial direction is defined as the uniaxial length.

Lignocellulosic mixtures are usually fluid. However, when the lignophenol derivative fraction in the mixture is extracted, the fluidity is lost. Therefore, in the lignocellulose-based mixture, it is considered that the lignophenol derivative fraction expresses an important plastic effect.
Moreover, the fluidity | liquidity of this mixture can be improved by acylating (for example, acetylation etc.) the lignophenol derivative in the lignocellulose-type mixture which is a component of this invention. That is, in the present invention, in the lignocellulose mixture, the lignophenol derivatives tend to bind to each other or to the cellulose section through hydrogen bonding, and the materials tend to associate with each other. In this case, the fluidity of the composition is not so high. However, the acylation of the lignophenol derivative (for example, acetylation, etc.) can eliminate the association between the materials, thereby improving the fluidity of the entire lignocellulosic mixture, and processing into a molded product or the like. The processing energy at the time can be reduced. Furthermore, the lignophenol derivative in the lignocellulose-based mixture may be used after being methylolated. When a methylolated material is used, a molded product having a relatively low density, a high water absorption rate, and excellent stability can be produced.

2. Thermoplastic resin Examples of the thermoplastic resin include the following.
(1) Polyolefin resin Examples of the polyolefin resin mainly include the following.
(1-1) Polypropylene Resin The polypropylene resin can be composed of one or more selected from a homopolymer of propylene, a copolymer containing propylene as a main component, and the like.
The propylene homopolymer is not particularly limited, but a propylene homopolymer having a melt mass flow rate at 230 ° C. of 0.1 to 200 g / 10 min is preferred from the viewpoint of obtaining light weight and excellent moldability. Further, from the viewpoint of the rigidity and impact resistance of the resin composition, the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 minutes.

The copolymer containing propylene as a main component is not particularly limited. For example, a copolymer of propylene and ethylene, or a random copolymer of one or more α-olefins other than propylene and propylene is used. And a block copolymer of propylene and one or more α-olefins other than propylene. Among the copolymers mainly composed of propylene, a propylene copolymer having a melt mass flow rate at 230 ° C. of 0.1 to 200 g / 10 min from the viewpoint of obtaining a light weight and excellent resin composition. Is preferred. Further, from the viewpoint of the rigidity and impact resistance of the resin composition, the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 minutes.
Examples of α-olefins other than propylene include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene and the like.

(1-2) Polyethylene resin The polyethylene resin can be composed of one or more selected from a homopolymer of ethylene and a copolymer containing ethylene as a main component.
Examples of the ethylene homopolymer include low-density polyethylene, linear low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. From the viewpoint of obtaining light weight and excellent moldability, the density is 0. a .910 ~ 0.965g / cm ^3, ethylene homopolymer preferably has a melt mass flow rate at 190 ° C. is 0.01 ~ 200 g / 10 min. If the melt mass flow rate at 190 ° C. is within the above range, there is no possibility of causing problems in the fluidity of the resin composition and the surface appearance of the molded body. The melt mass flow rate at 190 ° C. is more preferably 0.01 to 60 g / 10 min.

Examples of the copolymer mainly composed of ethylene include a random copolymer of ethylene and an α-olefin other than ethylene, and a block copolymer of ethylene and an α-olefin other than ethylene. Among copolymers having ethylene as a main component, an ethylene copolymer having a melt mass flow rate at 190 ° C. of 0.01 to 200 g / 10 min from the viewpoint of obtaining a light weight and excellent resin composition. Is preferred. Moreover, if the melt mass flow rate at 190 ° C. is within the above range, there is no possibility of causing problems in the fluidity of the resin composition and the surface appearance of the molded body. The melt mass flow rate at 190 ° C. is more preferably 0.01 to 60 g / 10 min.
Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene and the like.

Examples of commercially available polyolefin resins include the series of polypropylene resins “Prime Polypro”, “Polyfine” and “Prime TPO” manufactured by Prime Polymer Co., Ltd., for example, product number: J-700GP, Idemitsu Kosan Co., Ltd. Polypropylene resin (product number: J-966HP) manufactured by Prime Polymer Co., Ltd. and various polyethylene resins “Hi-Zex”, “Neo-Zex”, “Ult-Zex”, “Moretech”, “Evolue” series (for example, high Density polyethylene resin, product number: 2200J), and low density polyethylene (for example, product number: Petrocene 190) manufactured by Tosoh Corporation.

(2) Polystyrene resins Polystyrene resins are, for example, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (M-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units. These polystyrene resins may be used alone or in combination of two or more.
Examples of commercially available polystyrene resins include PS Japan Co., Ltd., PSJ-polystyrene series (for example, product number: H8672), Toyo Styrene Co., Ltd., and Toyostyrene series.

(3) Polyester resin Examples of the polyester resin include polyol-polycarboxylic acid type polyester resin and hydroxycarboxylic acid type polyester resin. Examples of the polyol-polycarboxylic acid type polyester resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and a copolymer of terephthalic acid and 1,3-propanediol or 1,4-butanediol.
Examples of the hydroxycarboxylic acid type polyester resin include polylactic acid and / or a copolymer resin containing polylactic acid. A polylactic acid resin and / or a copolymer resin containing polylactic acid is obtained by subjecting lactic acid or lactic acid and other hydroxycarboxylic acid to heat dehydration polymerization to obtain low molecular weight polylactic acid or a copolymer thereof. Lactide, which is a cyclic dimer of lactic acid or a copolymer thereof, is obtained by thermal decomposition under reduced pressure, and then lactide is polymerized in the presence of a catalyst such as a metal salt to produce polylactic acid resin and / or polylactic acid. A copolymer resin containing is obtained.
These polyester resins may be used alone or in combination of two or more.

Examples of commercially available polyol-polycarboxylic acid type polyester resins include Mitsui Chemicals, Mitsui PET ^™ series (for example, product number: Mitsui J125), Toyobo Co., Ltd., Byron series, and the like.
Examples of commercially available polylactic acid resins and / or copolymer resins containing polylactic acid include crystalline polylactic acid resins manufactured by Zhejiang Haisheng Biological Materials Co., Ltd. (Product No .: Levoda series, L-form / D-form ratio = 100 / 0 to 85/5) and Laissia series, which is a polylactic acid resin (manufactured by lactic acid fermentation of plant starch) manufactured by Mitsui Chemicals, Inc.

(4) Polyamide resin Examples of the polyamide resin include a ring-opening polymer of lactam, a polycondensate of diamine and dibasic acid, and a polycondensate of ω-amino acid. These polyamide resins may be used alone or in combination of two or more.
Examples of commercially available polyamide resins include nylon 6 and nylon 66 made by Toray Industries, Inc., Leona series made by Asahi Kasei Co., Ltd., and Teijin's n-nylon and n, m. -Nylon series and the like.

(5) Polycarbonate resin The polycarbonate resin may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin. From the viewpoint of affinity with the lignocellulosic mixture and from the viewpoint of impact resistance and heat resistance, the polycarbonate resin It is more preferable to use a group polycarbonate resin.
As the aromatic polycarbonate resin, an aromatic polycarbonate resin usually produced by a reaction of a dihydric phenol and a carbonate precursor can be used. The aromatic polycarbonate resin can be a main component of the resin composition because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.
In addition, when an aromatic polycarbonate-polyorganosiloxane copolymer or a resin containing an aromatic polycarbonate-polyorganosiloxane copolymer is used as the aromatic polycarbonate resin, the flame retardancy and impact resistance at low temperatures are further improved. be able to. The polyorganosiloxane constituting the copolymer is more preferably polydimethylsiloxane from the viewpoint of flame retardancy.
As commercially available aromatic polycarbonate resin, Idemitsu Kosan Co., Ltd. Toughlon series, Teijin Ltd. Panlite series, etc. are mentioned.

As the thermoplastic resin, compatible ones may be appropriately mixed and used. For example, if an appropriate amount of a polyester resin is mixed with an aromatic polycarbonate resin generally considered to have poor fluidity, the fluidity is improved.
In addition to the thermoplastic resins described in the above (1) to (5), other thermoplastic resins compatible with them, for example, AS resin (acrylonitrile-styrene resin), (meth) acrylic ester ( A suitable amount of (co) polymer may be mixed.
The thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins, and more preferably polyolefin resins.

3. Proportion The resin composition of the present invention contains a lignocellulose-based mixture in an amount of 0.5% by mass to 60% by mass when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass.
If the content of the lignocellulose-based mixture is less than 0.5% by mass, the strength and flame retardancy are insufficient, and if it exceeds 60% by mass, the fluidity is greatly reduced and the appearance of the molded product is greatly reduced. The content of the lignocellulose-based mixture is preferably 2% by mass or more and 40% by mass or less, and more preferably 4% by mass or more and 30% by mass or less.
As will be described later, the resin composition of the present invention may contain components other than the lignocellulose-based mixture and the thermoplastic resin, for example, various additives, but the lignocellulose-based mixture in the resin composition. And the total content of the thermoplastic resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and more preferably 95% by mass or more. Particularly preferred.

4). Other additives (various additives)
The resin composition of the present invention may contain various additives as necessary. Examples of such additives include ultraviolet absorbers, antioxidants, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial / antifungal agents, pigments and the like. Among these, it is preferable that the resin composition of the present invention contains at least an antioxidant.
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, benzoate compounds, polyamide polyether block copolymers (providing permanent antistatic performance), and the like.
Although it does not specifically limit as antioxidant, A phenolic antioxidant, phosphorus antioxidant, thioether type antioxidant, etc. are mentioned. Examples of commercially available antioxidants include Irganox 1010, Irganox 1076 (manufactured by BASF, phenolic antioxidant), Adekastab 2112 and Adekastab PEP36 (manufactured by ADEKA, phosphorous antioxidant). These may be used alone or in combination of two or more.
The lubricant is not particularly limited, and examples thereof include fatty acid amide lubricants, fatty acid ester lubricants, fatty acid lubricants, and fatty acid metal salt lubricants. These may be used alone or in combination of two or more.
The crystal nucleating agent is not particularly limited, and examples thereof include sorbitols, phosphorus nucleating agents, rosins, and petroleum resins.
The softening agent is not particularly limited, and examples thereof include liquid paraffin, mineral oil softener (process oil), and non-aromatic rubber mineral oil softener (process oil). These may be used individually by 1 type and may be used in combination of 2 or more type.

The antistatic agent is not particularly limited, and examples thereof include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, and fatty acid partial esters such as glycerin fatty acid monoesters.
Although it does not specifically limit as a metal deactivator, A hydrazine type metal deactivator, a nitrogen compound type metal deactivator, a phosphite ester type metal deactivator, etc. are mentioned. These may be used alone or in combination of two or more.
The antibacterial / antifungal agent is not particularly limited, and examples thereof include an organic compound antibacterial / antifungal agent, a natural organic antibacterial / antifungal agent, and an inorganic antibacterial / antifungal agent.
Although it does not specifically limit as a pigment, An inorganic pigment, an organic pigment, etc. are mentioned. Examples of inorganic pigments include titanium oxide, calcium carbonate, and carbon black. Examples of organic pigments include azo pigments, acidic dye lakes, basic dye lakes, and condensed polycyclic pigments. These pigments may be used alone or in combination of two or more.
The amount of the additive component is not particularly limited as long as the properties of the resin composition of the present invention are not impaired.

5). Production Method The production method of the resin composition of the present invention is not particularly limited, but it is preferably obtained by hot melt mixing a lignocellulose-based mixture and a thermoplastic resin.
(Kneading / Molding)
The resin composition of the present invention can be obtained by blending a lignocellulose-based mixture and a thermoplastic resin in the above proportions, and further adding various additives added as necessary, followed by hot melt mixing. The compounding and kneading at this time are premixed with a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. This method can be performed by a method using a machine and a conider.

The heating temperature at the time of kneading is suitably selected in the range of usually 160 to 350 ° C. depending on the kind of the thermoplastic resin, but when the polyolefin resin is used as the thermoplastic resin, the temperature is in the range of 160 to 250 ° C. In the case of using polyester, it is preferable to select in the range of 170 to 280 ° C., and in the case of using a polyester resin, it is preferably selected in the range of 230 to 280 ° C.
In the case of using a polyamide resin, it is preferably selected in the range of 240 to 290 ° C., in the case of using a polycarbonate resin, in the range of 270 to 350 ° C., and in the case of using a polylactic acid resin, it is preferably selected in the range of 190 to 250 ° C.

The resin composition of the present invention is made from the pellets obtained by the above-mentioned melt-kneading and pelletizing as raw materials, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, and Various molded articles can be produced by a foam molding method or the like. In particular, a pellet-shaped forming raw material is manufactured by the melt kneading method, and then this pellet is used suitably for manufacturing an injection molded body by injection molding or injection compression molding, and for manufacturing an extrusion molded body by extrusion molding. be able to. Moreover, after forming into an extrusion sheet by extrusion molding, it is good also as a molded object by pressurizing and thermoforming.

As for the molded article obtained from the resin composition of this invention, it is preferable that 1 mm or more of a lump (granular material) is not recognized visually. When the lignocellulose-based mixture is mixed with a thermoplastic resin, preferably when hot-melt mixed, the lignocellulose-based mixture is excellent in dispersibility in the thermoplastic resin, so that the occurrence of blisters (particulate matter) can be suppressed. This is because the lignocellulosic mixture is uniformly present in the matrix of lignophenolphenol derivative without the cellulose component being unevenly distributed.
Moreover, it is preferable that the molded article obtained from the resin composition of this invention is excellent in tensile yield strength and a tensile elasticity modulus compared with the case where a lignocellulose type mixture is not added.
Furthermore, it is preferable that the molded article obtained from the resin composition of the present invention has an improved elongation retention after exposure to light compared to the case where no lignocellulose-based mixture is added. When a polyolefin resin (preferably at least one selected from the group consisting of polyethylene and polypropylene, more preferably polypropylene) is used as the thermoplastic resin, the elongation retention after exposure to light is preferably 65% or more, more preferably It is 70% or more, more preferably 80% or more, and still more preferably 85% or more. The elongation retention after exposure to light is measured by the method described in the examples.

It is preferable that the molded article obtained from the resin composition of the present invention has an improved elongation retention after exposure to the oven as compared with the case where no lignocellulose-based mixture is added. When a polyolefin resin (preferably at least one selected from the group consisting of polyethylene and polypropylene, more preferably polypropylene) is used as the thermoplastic resin, the elongation retention after oven exposure is preferably 70% or more, more preferably 75% or more, more preferably 80% or more, and still more preferably 90 or more. The elongation retention after exposure to the oven is measured by the method described in the examples and exposed to a temperature suitable for the thermoplastic resin.
Moreover, it is preferable that the molded article obtained from the resin composition of this invention is excellent in a flame retardance (LOI) compared with the case where a lignocellulose-type mixture is not added.

6). Applications The resin composition of the present invention and the molded product obtained from the resin composition can be suitably used for OA materials, electrical / electronic materials, automotive materials, industrial materials, wire coating materials, films, fibers, and the like. .

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Production Example 1: Preparation and evaluation of lignocellulose-based mixture)
(1) Preparation of defatted sample Wood powder of cypress (Chamaecyparis obtusa) was pulverized with a vibration mill (HEIKO Mfg., TI-50) and passed through a sieve of 80 mesh (aperture 0.18 mm) (Iida Seisakusho) An 80 mesh pass wood flour was obtained. After extraction at 25 ° C. for 48 hours with ethanol: benzene = 1: 2 at room temperature (added until the color disappears under reflux. The amount is about 10 to 50 times the amount of wood flour). Solvent was removed together with the solvent, and the solvent of the extraction residue was completely distilled off in a fume hood to prepare a test sample.

(2) Phosphate phase separation treatment (2-1) Production of phenol compound sorption wood flour 23 g of the defatted wood flour was weighed into a 500 ml beaker, and p-cresol acetone solution (3 mol times per 9 units of lignin C9). (Including a phenol compound) was added, stirred with a glass rod, the beaker was covered with aluminum foil and parafilm, and allowed to stand for 24 hours. Thereafter, the wood flour was vigorously stirred in a draft for 60 minutes, and then acetone was distilled off.

(2-2) Phosphoric acid treatment (phase separation treatment)
To the phenol compound sorption wood flour obtained above, 200 ml of phosphoric acid having a concentration of 95% by mass (50 ° C.) was added in three portions, and kneaded with a glass rod and a Teflon (registered trademark) spatula for 1 hour at 50 ° C. Stir vigorously. Thereafter, the reaction mixture was poured into about 3,500 ml of deionized water to bring the phosphoric acid concentration to 10% or less, the reaction was stopped, and the mixture was further stirred vigorously for 1 hour to disperse the reaction mixture. Next, the insoluble fraction was separated and collected by centrifugation (8,800 rpm, 8 minutes, 4 ° C.), deoxidized, freeze-dried and dried under reduced pressure to obtain phase-separated wood flour.
The sample thus obtained contains the lignophenol derivative and the cellulose component uniformly because the cellulose component is once dissolved and recrystallized, that is, the cellulose component is uniformly distributed in the matrix of the lignophenol derivative. It is a composition composed of acicular or cage crystals (also referred to herein as a lignocellulosic mixture). When the size of the composition obtained with an electron microscope was observed, the average major axis length was 10 to 500 nm, and the average minor axis length was 5 to 50 nm.

(Examples 1 to 9 and Comparative Examples 1 to 8)
Each component was blended in the proportions shown in Tables 1 and 2, supplied to an extruder (model name: PCM-30, manufactured by Ikegai Co., Ltd.), melt-kneaded at 160 to 220 ° C., and pelletized. In all of the examples and comparative examples, 0.2 parts by mass of Irganox 1010 (manufactured by BASF) and 0.1 part by mass of ADK STAB 2112 (manufactured by ADEKA) are used as an antioxidant with respect to 100 parts by mass of the resin composition. Respectively. The obtained pellets were dried at 80 ° C. for 12 hours, and then injection molded under the conditions of an injection molding machine (Toshiba Machine Co., Ltd., model: IS100N) cylinder temperature 210-260 ° C. and mold temperature 40 ° C. A standard-compliant test piece was obtained. The performance was evaluated by various tests using the obtained test pieces, and the results are shown in Tables 1 and 2.
In addition, the description of “-” in the table means that the component is not contained.

Each component used in Tables 1 and 2 is as follows.
・ Polypropylene (J-966HP): Polypropylene, manufactured by Idemitsu Kosan Co., Ltd., trade name “IDEMITSU PP: J-966HP”
・ High-density polyethylene (2200J): High-density polyethylene, manufactured by Prime Polymer Co., Ltd., trade name “HI-ZEX 2200J”
PC (A1900): Polycarbonate resin, manufactured by Idemitsu Kosan Co., Ltd., trade name “Taflon A1900”
ABS (Techno ABS130): Acrylonitrile-butadiene-styrene copolymer, manufactured by Technopolymer Co., Ltd., trade name “Techno ABS130”
PHBH (X131A): poly (R-3-hydroxybutyrate-co-R-3-hydroxyhexanate), manufactured by Kaneka Corporation, trade name “Aonilex X131A”
Lignocellulose mixture: Lignocellulose mixture prepared in Production Example 1 Cellulose: Cellulose fiber, Celite, SW-10

In addition, evaluation of the obtained resin composition and a molded object was performed about the following items.
(Tensile test)
Tensile yield strength (MPa) and tensile modulus (MPa) were measured according to ASTM D638.

(Elongation at break)
The elongation at break (%) was measured according to ASTM D638.

(Elongation retention after exposure to light)
Exposed to a xenon lamp at 83 ° C. for 300 hours, the elongation at break was measured in the same manner as described above, and the elongation retention was evaluated based on the untreated values.
(Elongation retention after exposure to oven)
The oven was exposed to an oven at 120 ° C. for 500 hours, the elongation at break was measured in the same manner as described above, and the elongation retention was evaluated based on the untreated values.

(Flame retardance (LOI))
According to JIS K7201-2, the LOI value, which is an index of flame retardancy, was measured.

(Cellulose dispersion state)
The cellulose dispersion was evaluated by visual observation of the molded product.
The evaluation criteria are as follows.
A: No spots B: Less than 1 mm is observed C: 1 mm or more is observed

Further, as a result of observing the color tone of the obtained test piece, no remarkable coloring was observed in Examples 1 to 4 in which polypropylene or high-density polyethylene was used as the resin, but examples using the polycarbonate resin were used. In No. 6, there was strong coloring (YI = 45), and coloring was also observed in Example 5 in which polycarbonate resin and ABS were used in combination (YI = 27).

The resulting lignophenol derivative-cellulose component mixture (lignocellulose-based mixture) is easy to manufacture without the steps of fibrillating cellulose or coating lignophenol, and the resulting mixture is powdery and thermoplastic. Even if it is melt-mixed with the resin, the dispersion is good and the molded appearance is not adversely affected. It was clarified that when the content ratio is within the range of the claims, the composition has high strength and is excellent in heat resistance, weather resistance, and flame retardancy.

Claims (14)

1. Containing a lignocellulosic mixture, and a thermoplastic resin,
   When the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass, the lignocellulose-based mixture is contained in an amount of 0.5% by mass to 60% by mass,
   A resin composition characterized in that no 1 mm or more irregularities are visually recognized in a molded product.
2. The resin composition according to claim 1, wherein the lignocellulose-based mixture has an average major axis length of 10 to 500 nm and an average minor axis length of 5 to 50 nm.
3. The resin composition according to claim 1 or 2, wherein the lignocellulose-based mixture is a composition containing needle-like or cage-like crystals.
4. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins. object.
5. The resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin is a polyolefin resin.
6. The resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
7. The resin composition according to claim 5 or 6, wherein the obtained molded article has an elongation retention after exposure to light of 65% or more.
8. The resin composition according to any one of claims 1 to 7, further comprising an antioxidant.
9. A molded product obtained by molding the resin composition according to any one of claims 1 to 8.
10. A step of obtaining a lignocellulosic mixture comprising a lignophenol derivative and a cellulose component by adding an acid to a lignocellulosic material to which a phenolic compound has been added, and thermally melting the lignocellulosic mixture and a thermoplastic resin Mixing, and
    The manufacturing method of the resin composition which contains a lignocellulose type mixture 0.5 mass% or more and 60 mass% or less when the sum total of the said lignocellulose type mixture and the said thermoplastic resin is 100 mass%.
11. The method for producing a resin composition according to claim 10, wherein the acid is at least one selected from the group consisting of phosphoric acid, formic acid, and trifluoroacetic acid.
12. The method for producing a resin composition according to claim 10 or 11, wherein the phenol compound added to the lignocellulosic material is a phenol compound having one or more substituents at least in the ortho position or the para position.
13. The phenol compound added to the lignocellulosic material contains at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group, The method for producing a resin composition according to any one of claims 10 to 12, which is a phenol compound having a para-position.
14. The lignocellulosic mixture is at least one selected from the group consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol. The production of a resin composition according to any one of claims 10 to 13, which is obtained by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which two phenolic compounds are added. Method.