JP2019143016A - Cellulose fiber dispersant, resin composition, method for producing resin composition and molding - Google Patents

Abstract

To provide a cellulose fiber dispersant that allows cellulose fibers to be sufficiently dispersed in resin, and a resin composition that makes it possible to produce a molding having high mechanical properties.SOLUTION: A cellulose fiber dispersant contains an acid-modified rosin with an acid modification rate of 0.08-4.0 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a cellulose fiber dispersant, a resin composition, a method for producing a resin composition, and a molded body.

  Cellulose fibers are attracting attention as a resin reinforcing material because they are lightweight, have high elastic modulus, and high strength. However, since it has many hydroxyl groups in the molecular chain, it has high hydrophilicity, and when heated, moisture between the fibers evaporates and it tends to cause self-aggregation. For this reason, it is difficult to uniformly disperse the resin. In particular, cellulose nanofibers that have been fibrillated to the nano level tend to aggregate during drying, and when they are combined with a resin, aggregates tend to remain in the composite material.

Various attempts have been made to solve the above problems.
Patent Document 1 discloses a thermoplastic resin composition containing a thermoplastic resin, a vegetable fiber, a rosin resin, and a vegetable oil.
Patent Document 2 discloses a natural fiber composite composition containing natural fibers, a thermoplastic polymer, and a dispersion resin as main components.
Patent Document 3 discloses a cellulose fiber / resin composite composition obtained by a specific production method.
Cellulose nanofibers have little affinity with polypropylene, which is a nonpolar resin, and there are almost no examples in which cellulose nanofibers are uniformly dispersed in polypropylene without chemical modification.

JP 2002-294080 A JP 2012-111855 A Japanese Patent Laying-Open No. 2015-183153

Since the conventional resin composition has insufficient fiber dispersibility, there is a problem that the effects of aggregation of fibers and the addition of fibers (improvement of mechanical properties, etc.) are not sufficiently exhibited. Moreover, although a fiber dispersion | distribution process etc. may be further provided in order to improve a dispersibility, it was not economical.
An object of the present invention is to provide a cellulose fiber dispersant capable of sufficiently dispersing cellulose fibers in a resin, and a resin composition capable of producing a molded article having high mechanical properties.

As a result of intensive studies by the present inventors, when a rosin compound having specific physical properties is used, cellulose fibers can be sufficiently dispersed in the resin, and molding having excellent mechanical properties by using a resin composition using the same. It was found that a body was obtained, and the present invention was completed.
According to the present invention, the following resin composition and the like are provided.
1. A cellulose fiber dispersant containing an acid-modified rosin having an acid modification rate of 0.08 to 4.0% by mass.
2. 2. The cellulose fiber dispersant according to 1, wherein the acid-modified rosin is an α, β-unsaturated dicarboxylic acid-modified rosin.
3. The 1st resin composition which contains the following (A) component and (B) component in the following ratio.
(A) Cellulose fiber dispersant according to 1 or 2 0.1 to 99.9% by mass
(B) Cellulose fiber 0.1-99.9 mass%
4). 4. The resin composition according to 3, wherein the cellulose fiber as the component (B) has an average fiber diameter of 3 nm to 50 μm.
5. The resin composition according to 3 or 4, wherein the component (B) is a plant-derived cellulose fiber.
6). The 2nd resin composition containing the following (A)-(C) component in the following ratio.
(A) Cellulose fiber dispersant described in item 1 or 2 0.01 to 89.0% by mass
(B) Cellulose fiber 0.05-80.0 mass%
(C) Thermoplastic resin 10.0-99.9 mass%
7). 7. The resin composition according to 6, wherein the cellulose fiber as the component (B) has an average fiber diameter of 3 nm to 50 μm.
8). The resin composition according to 6 or 7, wherein the component (B) is a plant-derived cellulose fiber.
9. The resin composition according to any one of 6 to 8, wherein the component (C) is a polyolefin resin.
10. The resin composition according to any one of 6 to 9, wherein the component (C) is polypropylene.
11. The resin composition according to any one of 6 to 10, wherein the melt flow rate at 230 ° C. and a load of 2.16 kg of the component (C) is 0.1 to 200 g / 10 minutes.
12 The content ratio of the component (A) is 0.01 to 50.0 mass%, the content ratio of the component (B) is 0.05 to 50.0 mass%, and the content ratio of the component (C) The resin composition in any one of 6-11 whose is 20.0-99.9 mass%.
13. A step of kneading cellulose fiber containing water and a cellulose fiber dispersant containing an acid-modified rosin having an acid modification rate of 0.08 to 4.0% by mass; and
A method for producing a resin composition, comprising melt-kneading the mixture obtained in the above step and a thermoplastic resin.
The molded object produced using the resin composition in any one of 14.6-12.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can manufacture the cellulose fiber dispersing agent which can fully disperse | distribute a cellulose fiber in resin, and a molded object with high mechanical property can be provided.

  Hereinafter, embodiments of the present invention will be described. In the present specification, “x to y” represents a numerical range of “x or more and y or less”.

[Cellulose fiber dispersant]
The cellulose fiber dispersant according to one embodiment of the present invention includes an acid-modified rosin having an acid modification rate of 0.08 to 4.0% by mass.
Cellulose fiber dispersants have high affinity with cellulose fibers, thermoplastic resins and water. That is, it has a function as a hydrophobizing agent capable of hydrophobizing the cellulose fiber, and the cellulose fiber can be uniformly dispersed in the resin composition. Moreover, aggregation of a cellulose fiber can be suppressed. Thereby, as described later, when a resin composition containing the cellulose fiber dispersant is used, a molded article having high mechanical properties can be obtained.

  The acid-modified rosin is a compound obtained by modifying rosin with an acid such as α, β-unsaturated carboxylic acid. The acid-modified rosin can be obtained, for example, by a Diels-Alder reaction between rosin and an α, β-unsaturated carboxylic acid.

Rosin is a substance containing a resin acid having a reactive double bond, obtained as a solid hydrocarbon or the like secreted from a tree such as a conifer (eg, pine). The resin acid is a compound having a carboxyl group derived from a tree, and specific examples of the resin acid having a reactive double bond include abietic acid, parastolic acid, neoabietic acid, and levopimaric acid.
When rosin is reacted with α, β-unsaturated carboxylic acid, the reactive double bond in the resin acid in rosin and α, β-unsaturated carboxylic acid undergo a Diesle-Alder reaction to form an acid-modified product. can get.

The rosin may be an unmodified rosin (unmodified rosin) that has not undergone modification treatment such as disproportionation treatment, hydrogenation (hydrogenation) treatment, petroleum resin modification treatment, polymerization treatment, or the like. It may be a modified rosin subjected to one or more of them.
Examples of the unmodified rosin include tall oil rosin, gum rosin, and wood rosin, and gum rosin is preferable.
A rosin may be used individually by 1 type and may use 2 or more types together.

Examples of the α, β-unsaturated carboxylic acid include α, β-unsaturated monocarboxylic acid and α, β-unsaturated dicarboxylic acid. Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid and methacrylic acid, and the α, β-unsaturated dicarboxylic acid includes fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and anhydrous Citraconic acid and the like can be mentioned. From the viewpoint of addition reaction with rosin, α, β-unsaturated dicarboxylic acid is preferable, and fumaric acid, maleic acid and maleic anhydride are more preferable.
The α, β-unsaturated carboxylic acid may be used alone or in combination of two or more.

The blending ratio of rosin and α, β-unsaturated carboxylic acid is, for example, 1 mol or less of α, β-unsaturated carboxylic acid with respect to 1 mol of rosin.
The reaction temperature of rosin and α, β-unsaturated carboxylic acid is, for example, 150 to 300 ° C., and the reaction time is, for example, 1 to 24 hours. In this reaction, a known catalyst can be blended at an appropriate ratio as necessary.
An acid-modified rosin having a predetermined acid modification rate can be obtained by appropriately adjusting the blending ratio, reaction temperature, and reaction time.

Examples of the acid-modified rosin include an α, β-unsaturated dicarboxylic acid-modified rosin that is a modified product of α, β-unsaturated dicarboxylic acid, and preferably a fumaric acid-modified rosin that is a modified product of fumaric acid ( Fumarated rosin), maleic acid-modified rosin (maleinized rosin) which is a modified product with maleic acid or maleic anhydride, and more preferably maleic acid-modified rosin.
The acid-modified rosin may be used alone or in combination of two or more.

The acid modification rate of the acid-modified rosin is 0.08% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 2.0% by mass or more, and particularly preferably 2%. .5% by mass or more.
The acid modification rate of the acid-modified rosin is 4.0% by mass or less, preferably 3.7% by mass or less, more preferably 3.4% by mass or less, still more preferably 3.2% by mass or less, and particularly preferably 3% or less. .1% by mass or less.

  The acid modification rate is the mass ratio of the acid used for modification to the raw material rosin (modified rosin or non-modified rosin), and is calculated by (mass of acid / mass of raw material rosin) × 100.

The acid modification rate of the acid-modified rosin is measured as follows.
A small amount of acid-modified rosin and tetramethylammonium hydroxide are put in a pyrolysis furnace, pyrolyzed, transferred to a connected gas chromatography, and subjected to gas chromatography analysis under the following conditions. From the decomposed peak, the acid modification rate is calculated from the area ratio of the rosin part and the acid-modified part.
・ Model used: Gas chromatography “Agilent 7890A” (manufactured by Agilent Technologies)
・ Pyrolysis furnace: “PY3030S” (manufactured by Frontier Laboratories)
-Gas chromatography (GC) operating conditions Column: UA-5 (30 m / 0.25 μm)
Temperature: 150-250 ° C (20 minutes hold), 4 ° C / min Inlet / FID: 250 ° C
Split ratio: 60/1
Helium flow rate: 1 ml / min. Pyrolysis furnace operating conditions Pyrolysis furnace temperature: 500 ° C
Interface temperature: 320 ° C

  An acid-modified rosin ester obtained by esterifying an acid-modified rosin may be used as the acid-modified rosin. An acid-modified rosin ester is preferable in terms of heat resistance because the softening point is improved. The acid-modified rosin ester can be obtained by esterifying an acid-modified rosin and a polyhydric alcohol by a known esterification method.

  Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,6-hexanediol; glycerin, trimethylolpropane, Trihydric alcohols such as methylolethane and triethylolethane; tetrahydric alcohols such as pentaerythritol and diglycerine; hexavalent alcohols such as dipentaerythritol; triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, N -Amino alcohols such as normal butyl diethanolamine. The blending amount of the polyhydric alcohol is not particularly limited and may be set as appropriate.

  As the acid-modified rosin ester, an ester obtained without using an epoxy compound is preferable.

  The acid-modified rosin may be liquid or solid, but is preferably solid at 25 ° C. If it is solid, the resin composition can be prepared easily and inexpensively with a small number of steps, which is economical.

The cellulose fiber dispersant according to one embodiment of the present invention may include other additives (for example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur lightening agent, and the like).
For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, or 99.9% by mass or more of the cellulose fiber dispersant is the acid-modified rosin. Also good. The cellulose fiber dispersant may consist essentially of the acid-modified rosin described above. In this case, inevitable impurities may be included. The cellulose fiber dispersant may consist only of the acid-modified rosin.

[First resin composition]
The resin composition (1st resin composition) which concerns on 1 aspect of this invention contains the following (A) component and (B) component in the following ratio.
(A) Cellulose fiber dispersant 0.1-99.9 mass%
(B) Cellulose fiber 0.1-99.9 mass%

  The first resin composition is a resin composition obtained by previously mixing the cellulose fiber dispersant and the cellulose fiber before kneading with the thermoplastic resin. As will be described later, these components are once kneaded and then kneaded with the thermoplastic resin, whereby cellulose fibers can be more uniformly dispersed in the thermoplastic resin.

The cellulose fiber dispersant as component (A) is as described above.
There is no restriction | limiting in particular in the cellulose fiber of (B) component, Various well-known things can be used. Specifically, plant-derived cellulose fibers isolated from plants such as pulp, wood, bamboo, hemp, cotton, coconut, rice straw, seaweed, etc .; cellulose fibers produced by marine animals such as sea squirts; produced by acetic acid bacteria Bacterial cellulose fibers; cellulose fibers obtained from used paper; chemically synthesized cellulose fibers such as cellulose acetate, cellulose nitrate, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and rayon.
Among these, plant-derived cellulose fibers are preferred from the viewpoint of raw material productivity, fiber mechanical strength, and impurities, and cellulose fibers obtained from plant-derived pulp (plant pulp-derived cellulose fibers) are more preferred.

As the plant-derived pulp, general-purpose pulp such as kraft pulp, sulfite pulp, thermomechanical pulp, mechanical pulp and the like can be used. As the raw material, hardwood, conifer, bamboo and the like can be used. In particular, it is preferable to use pulp having an α-cellulose content of 60 to 99% by mass. If the purity of the α-cellulose content is 60% by mass or more, the fiber diameter and the fiber length can be easily adjusted, and the entanglement between the fibers can be suppressed, and the α-cellulose content is less than 60% by mass. Compared to the case, the coloring suppression effect is better. Moreover, if the α-cellulose content is 99% by mass or less, the fiber can be easily defibrated to the nano level.
The α-cellulose content of the pulp is measured according to JIS P 8101 (1976).

It does not specifically limit as a manufacturing method of a cellulose fiber, A well-known method can be used. For example, an underwater facing collision method in which water is dispersed and opposed to each other under high pressure, a grinder method for grinding between rotating grindstones, a homogenizer, a high-pressure collision type pulverizer, a ball mill, a roll mill, a cutter mill, an ultrasonic disperser, etc. are used. A method by mechanical processing such as a miniaturization method can be mentioned. Alternatively, the fiber may be defibrated by chemical treatment such as enzyme treatment or acid treatment.
A cellulose fiber may be used individually by 1 type, and may use 2 or more types together.

The average fiber diameter of the cellulose fiber is preferably 3 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, particularly preferably 20 nm or more, preferably 50 μm or less, more preferably 45 μm or less, and further preferably 40 μm or less. Especially preferably, it is 35 micrometers or less.
When the average fiber diameter is 3 nm to 50 μm, it is preferable from the viewpoint of the mechanical properties of the resin composition and the surface appearance of the molded product.
Average fiber diameter, the fibers of the fiber diameter 1nm~100μm in the region of 1 mm ² square, indiscriminately choose 100 visually using a photograph taken by an electron microscope (FEI Inc. "Tecnai Osiris"), the 100 It is obtained by calculating a simple average (arithmetic average) of the individual fiber diameters. As the fiber diameter, the major axis of the fiber is used.

The average degree of polymerization of the cellulose fiber is preferably 200 or more, more preferably 300 or more, still more preferably 500 or more, preferably 10,000 or less, more preferably 5,000 or less, and still more preferably 3,000 or less. is there.
An average polymerization degree of 200 to 10,000 is preferable from the viewpoints of mechanical properties and processability of the resin composition. When cellulose fibers having a degree of polymerization exceeding 10,000 are used, the viscosity of the resin composition becomes high and the processability may be lowered.
The average degree of polymerization is measured by the copper ethylenediamine method (cellulose fibers are delignified and have a purity of 80% or more).

The content ratio of the component (A) in the first resin composition is 0.1% by mass or more, preferably 5.0% by mass or more, more preferably 10.0% by mass or more, and further preferably 15.0%. It is at least 2% by mass, particularly preferably at least 20.0% by mass.
The content ratio of the component (A) in the first resin composition is 99.9% by mass or less, preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and further preferably 85.0%. It is 8 mass% or less especially preferably 8 mass% or less.

The content ratio of the component (B) in the first resin composition is 0.1% by mass or more, preferably 5.0% by mass or more, more preferably 10.0% by mass or more, and further preferably 15.0%. It is at least 2% by mass, particularly preferably at least 20.0% by mass.
The content ratio of the component (B) in the first resin composition is 99.9% by mass or less, preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and further preferably 85.0%. It is 8 mass% or less especially preferably 8 mass% or less.

  A 1st resin composition can be manufactured by mixing said (A) component and (B) component. There is no particular limitation on the mixing method.

  When mixing the component (A) and the component (B), it is preferable that the cellulose fiber of the component (B) is in a state of containing moisture (or dispersed in water). If it does in this way, aggregation of the cellulose fibers in the case of drying can be suppressed by substituting the water | moisture content between cellulose fibers with (A) component. Moisture is usually discharged as steam or waste water during mixing.

  The moisture content is, for example, 10.0% by mass or more, preferably 20.0% by mass or more, more preferably 30.0% by mass or more, based on the total of the cellulose fiber and moisture. Preferably it is 50.0 mass% or more, Most preferably, it is 60.0 mass% or more. If the moisture content is 10.0% by mass or more, the hydrogen bonds between cellulose fibers are moderately relaxed, so that they can be easily dispersed.

  The water content is, for example, 99.0% by mass or less, preferably 95.0% by mass or less, more preferably 90.0% by mass or less, based on the total of the cellulose fibers and the water. More preferably, it is 85.0% by mass or less, and particularly preferably 80.0% by mass or less. If the water content is 99.0% by mass or less, the component (A) can be prevented from flowing out at the same time as the water, or denatured or deteriorated. Moreover, deterioration of equipment can be suppressed. Furthermore, since the solid content rate in the mixed system becomes appropriate, the productivity is excellent.

  The first resin composition may contain other additives (for example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur lightening agent, etc.).

For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, or 99.9% by mass or more of the first resin composition comprises (A) component and ( B) component, or (A) component, (B) component, and said additive may be sufficient.
The first resin composition may consist essentially of the component (A) and the component (B), or the component (A), the component (B), and the additives described above. In this case, inevitable impurities may be included.
The first resin composition may consist of only the component (A) and the component (B), or only the component (A), the component (B), and the additives described above.

[Second resin composition]
The resin composition (2nd resin composition) which concerns on 1 aspect of this invention contains the following (A)-(C) component in the following ratio.
(A) Cellulose fiber dispersant 0.01-89.0 mass%
(B) Cellulose fiber 0.05-80.0 mass%
(C) Thermoplastic resin 10.0-99.9 mass%

  As described above, when the cellulose fiber dispersant according to one embodiment of the present invention is used, the cellulose fibers can be uniformly dispersed in the resin composition. Thereby, the molded object obtained from the 2nd resin composition containing the said component is excellent in mechanical physical properties (tensile yield strength, tensile elastic modulus, and elongation at break). Furthermore, by combining the component (A) having a polar group and the component (B), the adhesion and paintability of the surface of the molded body, and further the adhesion and affinity with the polar material can be improved. It becomes possible. In addition, the second resin composition can be easily prepared because of its high kneadability. In particular, when the solid (A) component is used, the resin composition can be prepared more easily and inexpensively. Is. Furthermore, since the component (A) and the component (B) can be prepared from a naturally-derived material, the environmental load is low and the recyclability is high. Moreover, discoloration of a cellulose fiber can be suppressed by using (A) component, and it becomes possible to improve environmental characteristics, such as heat aging resistance and a weather resistance.

  The thermoplastic resin of component (C) is not particularly limited, but for example, polyolefin resins such as polypropylene, ethylene-propylene copolymer, high density polyethylene, low density polyethylene, and linear low density polyethylene; polyamide 6, Polyamide resins such as polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, polyamide 12, polyamide 11, aromatic polyamide; polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polybutylene succinate, polybutylene succinate adipate , Polybutylene adipate terephthalate, polyethylene terephthalate succinate, poly (3-hydroxyalkanoic acid), poly (3-hydroxybutyric acid), poly (3-hydroxybutyrate) -Co-3-hydroxyhexanoate), polyester resins such as polyglycolic acid; polystyrene, acrylonitrile-styrene resins such as styrene resin and ABS resin; polycarbonate; polyacrylate; polymethyl methacrylate; polyacetal; polycaprolactone; Alcohol; ethylene-vinyl acetate alcohol and the like.

Among the above, polyolefin resins are preferable, and polypropylene and polyethylene are more preferable.
Although there is no restriction | limiting in particular as a polypropylene and polyethylene, From the viewpoint of obtaining the resin composition which is lightweight and excellent in a moldability, 230 degreeC and the melt flow rate in 2.16 kg of loads are 0.1-200 g / 10min. preferable. Furthermore, it is more preferable that the melt flow rate at 230 ° C. and a load of 2.16 kg is from 0.1 to 30 g / 10 min from the viewpoint of obtaining a molded article having excellent rigidity and impact resistance.
The melt flow rate is measured by a method based on ASTM standard D-1238.

The content ratio of the component (A) in the second resin composition is 0.01% by mass or more, preferably 0.02% by mass or more, for example, 0.1% by mass or more, 0.5% by mass. As mentioned above, it is good also as 1.0 mass% or more or 3.0 mass% or more.
The content ratio of the component (A) in the second resin composition is 89.0% by mass or less, preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and further preferably 50.0%. It is at most 40.0% by mass, particularly preferably at most 40.0% by mass.

The content ratio of the component (B) in the second resin composition is 0.05% by mass or more, preferably 0.08% by mass or more, for example, 0.1% by mass or more, 0.5% by mass. As mentioned above, it is good also as 1.0 mass% or more or 3.0 mass% or more.
The content ratio of the component (B) in the second resin composition is 80.0% by mass or less, preferably 70.0% by mass or less, more preferably 60.0% by mass or less, and further preferably 50.0%. It is at most 40.0% by mass, particularly preferably at most 40.0% by mass.

The content ratio of the component (C) in the second resin composition is 10.0% by mass or more, preferably 15.0% by mass or more, more preferably 20.0% by mass or more, and further preferably 25.0%. It is at least 3% by mass, particularly preferably at least 30.0% by mass.
The content ratio of the component (C) in the second resin composition is 99.9% by mass or less, preferably 99.89% by mass or less, for example, 98.0% by mass or less, 95.0% by mass. Hereinafter, it is good also as 93.0 mass% or less or 92.0 mass% or less.

The second resin composition can contain any additive depending on various purposes (for example, improvement of processability, functionality and / or mechanical properties).
Additives include UV absorbers, antioxidants, light stabilizers, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial agents, foaming agents, modified resins, pigments, dyes, reinforcing agents , Mold release agents, plasticizers, fluidity improvers and the like.
Moreover, in order to assist a flame retardance, a flame retardant and a flame retardant adjuvant can be mix | blended. The flame retardant is not particularly limited, and is a phosphorus flame retardant, silicone flame retardant, halogen compound, organic alkali metal salt, organic alkaline earth metal salt, nitrogen compound, metal hydroxide, borate, silicon compound, Known materials such as metal oxides and expanded graphite can be used according to the purpose. The flame retardant aid is not particularly limited, and antimony compounds such as antimony trioxide, zinc borate, metal oxide, melamine, pentaerythritol and the like can be used. Of these, antimony compounds are preferred.
The said additive may be used individually by 1 type, and may use 2 or more types together.

An arbitrary filler can be added to the second resin composition.
The filler is not particularly limited, and various known ones can be used. Specifically, talc, calcium carbonate, silica, clay, potassium titanate, mica, glass fiber, glass balloon, wollastonite Metal fibers, alumina, precipitated barium sulfate, calcium oxide, titanium oxide, zeolite, carbon fiber, carbon black, graphite, basic magnesium sulfate and the like.
The said filler may be used individually by 1 type, and may use 2 or more types together.

In the second resin composition, the component (A) is preferably 0.01% by mass or more, the component (B) is 0.05% by mass or more, and the component (C) is 20.0% by mass or more (more preferably 30.0% by mass or more), preferably (A) component is 50.0% by mass or less (more preferably 40.0% by mass or less), and (B) component is 50.0% by mass or less (more preferably). 40.0 mass% or less) and the component (C) is 99.9 mass% or less.
When the content of each component is within the above range, the cellulose fibers are more uniformly dispersed in the resin composition, so that a molded article having excellent mechanical properties can be obtained.

For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, or 99.9% by mass or more of the second resin composition is component (A) to ( Component C) or component (A) to component (C) and the above-described additives and / or fillers may be used.
The second resin composition may consist essentially of the components (A) to (C), or the components (A) to (C) and the additives and / or fillers described above. In this case, inevitable impurities may be included.
The 2nd resin composition may consist only of (A) ingredient-(C) ingredient, or (A) ingredient-(C) ingredient, and the above-mentioned additive and / or filler.

[Method for producing second resin composition]
The second resin composition can be produced by melt-kneading each of the components described above, but preferably, a step of kneading the component (B) containing water and the component (A), and the resulting product are obtained. The mixture and the component (C) are produced by a production method including a step of melt-kneading.

  First, by mixing the component (B) containing water and the component (A) at 50 ° C. to 230 ° C., the moisture between the cellulose fibers can be replaced with the component (A). Aggregation of cellulose fibers during drying can be suppressed. (B) The ratio of a component and water is as having mentioned above.

  Next, a resin composition is obtained by melt-kneading the mixture obtained above and the component (C). By kneading the component (B) and the component (A) once and then kneading with the component (C), the cellulose fibers can be more uniformly dispersed in the thermoplastic resin.

  Various processing machines can be used for melt-kneading. As the processing machine, a continuous extruder such as a twin-screw extruder or a 1.5-axis extruder; a batch kneader such as a kneader or a Banbury mixer; a roll or the like can be used, and a continuous extruder is preferable.

[Molded body]
Since the second resin composition has excellent processability, a molded body (resin molded product) can be obtained by a known method such as extrusion molding, blow molding, injection molding, vacuum molding, calendar molding, or the like.

  The field of use of the obtained molded body is not particularly limited. For example, automobile parts include exterior parts such as bumpers, cowl tops, weather strips, interior parts such as instrument panels, meter clusters, door trims, luggage boards, and HVAC units. , Engine parts such as air cleaner elements, etc., home appliance parts such as refrigerators, rice cookers, microwave ovens, washing machines, personal computers, air conditioners, outdoor units for air conditioners, hot water washing toilet seats, TV receivers, etc. Cases, various parts, etc. Other than that, OA equipment parts such as printer multi-function machine cases, various parts such as bearings, acoustic parts such as speaker cases, speaker frames and diaphragms, and electrical components such as clamp covers , Architecture of bathroom counters, kitchen panels, etc. Wood, can be used in various applications for medical materials utilizing biocompatible.

Example 1
[Production of cellulose fiber dispersant]
99 g of disproportionated rosin (“G-100F” manufactured by Harima Chemical Co., Ltd.) and 1 g of Chinese gum rosin are heated and dissolved at 200 ° C. under a nitrogen stream (5 ml / min), and 0.1 g of maleic anhydride is added and stirred. It was confirmed that the Diels-Alder addition reaction was completed and the anhydrous ring was opened due to the absence of turbidity in the solution. Thereafter, 10 g of glycerin was added, and the liquid temperature was raised to 270 ° C. over 8 to 10 hours. Thereafter, an esterification reaction was performed at 270 ° C. for 16 to 20 hours to obtain a maleic acid-modified disproportionated rosin glycerin ester A1 (cellulose fiber dispersant, acid modification rate 0.1% by mass).

Example 2
[Production of cellulose fiber dispersant]
100g of Chinese gum rosin was dissolved by heating at 200 ° C under a nitrogen stream (5ml / min), 2.8g of fumaric acid was added and stirred, and it was confirmed that Diels-Alder addition reaction was completed by eliminating the turbidity of the solution. As a result, fumaric acid-modified rosin A2 (cellulose fiber dispersant, acid modification rate 2.8% by mass) was obtained.

Example 3
[Production of cellulose fiber dispersant]
500 g of Chinese gum rosin was charged into a 1 L four-necked flask, 380 g of mineral spirit was added, and dissolved under heating in a nitrogen stream (5 ml / min). When it was completely melted and allowed to stir, it was cooled to 130 ° C., 5 g of zinc chloride catalyst was added and reacted at the same temperature for 4 hours. The mixture was washed with neutralized water three times or more with 0.5% sodium bicarbonate water to obtain a crude polymerization rosin. The obtained crude polymerized rosin was distilled to obtain a polymerized rosin by removing the decomposition product and the containing solvent. Next, 100 g of polymerized rosin was heated and dissolved at 200 ° C. under a nitrogen stream (5 ml / min), and 3.0 g of maleic anhydride was added and stirred. The Diels-Alder addition reaction was completed by eliminating the turbidity of the solution. It was confirmed that the anhydrous ring was opened. 10 g of pentaerythritol was added, and the liquid temperature was raised to 270 ° C. over 8 to 10 hours. Thereafter, an esterification reaction was carried out at 270 ° C. for 16 to 20 hours to obtain maleic acid-modified polymerized rosin pentaerythritol ester A3 (cellulose fiber dispersant, acid modification rate: 3.0% by mass).

Comparative Example 1
[Production of rosin compounds]
500 g of Chinese gum rosin was charged into a 1 L four-necked flask, 380 g of mineral spirit was added, and dissolved under heating in a nitrogen stream (5 ml / min). When it was completely melted and allowed to stir, it was cooled to 130 ° C., 5 g of zinc chloride catalyst was added and reacted at the same temperature for 4 hours. The mixture was washed with neutralized water three times or more with 0.5% sodium bicarbonate water to obtain a crude polymerization rosin. The obtained crude polymerized rosin was distilled to obtain a polymerized rosin by removing the decomposition product and the containing solvent. Next, 100 g of polymerized rosin was heated and dissolved at 200 ° C. in a nitrogen stream (5 ml / min), 10 g of pentaerythritol was added, and the liquid temperature was raised to 270 ° C. over 8 to 10 hours. Esterification reaction was performed at 270 ° C. for 16 to 20 hours to obtain polymerized rosin pentaerythritol ester A′1 (acid modification rate: 0% by mass).

Comparative Example 2
[Production of rosin compounds]
100 g of Chinese gum rosin was dissolved by heating at 200 ° C. under a nitrogen stream (5 ml / min), 5.8 g of maleic anhydride was added and stirred, and the Diels-Alder addition reaction was completed by eliminating the cloudiness of the solution. It was confirmed that the ring was opened. Thereafter, petroleum resin (“Quinton 1345” manufactured by Nippon Zeon Co., Ltd.) was charged, and the liquid temperature was raised to 270 ° C. over 8 to 10 hours. A polymerization reaction was carried out at 270 ° C. for 16 to 20 hours to obtain petroleum resin-modified maleic acid-modified rosin A′2 (acid modification rate 5.8% by mass).

Comparative Example 3
[Production of rosin compounds]
100g Chinese gum rosin was dissolved by heating at 200 ° C under a nitrogen stream (5ml / min), 4.3g of fumaric acid was added and stirred, and the Diels-Alder addition reaction was confirmed by the solution becoming cloudy. did. 15 g of glycerin was added, and the liquid temperature was raised to 270 ° C. over 8 hours. Esterification reaction was performed at 270 ° C. for 15 to 20 hours to obtain fumaric acid-modified rosin glycerin ester A′3 (acid modification rate 4.3 mass%).

Examples 4 to 10, Comparative Examples 4 to 8 and Experimental Example 1
[Production of resin composition and molded article]
Among the components shown in Table 1, the component (A) or the component (A ′) and the component (B) (containing water, the amount of water is 78% by mass with respect to the sum of the component (B) and water. Are blended at a ratio shown in Table 1 and kneaded at 120 to 180 ° C. to obtain a resin composition (first resin composition). The water contained in the component (B) was discharged out of the system during the kneading. Thereafter, a resin composition (second resin composition) was prepared by blending with the component (C). The numerical value in “resin composition” in Table 1 indicates the blending ratio (mass%) of each component in the second resin composition. Also, 0.2 parts by mass of Irganox 1010 (manufactured by BASF) and 0.2 parts by mass of ADK STAB 2112 (manufactured by ADEKA) were blended as an antioxidant with respect to 100 parts by mass of the obtained resin composition. .
The obtained resin composition was supplied to an extruder (“PCM-30” manufactured by Ikegai Co., Ltd.), melt-kneaded at 180 to 240 ° C., and pelletized. The obtained pellets were dried at 80 ° C., and then molded at 190 to 240 ° C. by an injection molding machine (“NEX110III-18E” manufactured by Nissei Plastic Industry Co., Ltd.), and test pieces (molded bodies, dimensions were ASTM of each evaluation described later). According to the standard).

The components used are shown below.
((A) component: cellulose fiber dispersant)
A1 to A3 obtained in Examples 1 to 3.
A1: maleic acid-modified disproportionated rosin glycerin ester (acid modification rate 0.1% by mass)
A2: fumaric acid-modified rosin (acid modification rate 2.8% by mass)
A3: Maleic acid-modified polymerized rosin pentaerythritol ester (acid modification rate: 3.0% by mass)
All of A1 to A3 are solid at 25 ° C.

((A ′) component: rosin compound)
A′1 to A′3 obtained in Comparative Examples 1 to 3.
A′1: Polymerized rosin pentaerythritol ester (acid modification rate 0 mass%)
A′2: petroleum resin-modified maleic acid-modified rosin (acid modification rate 5.8% by mass)
A′3: fumaric acid-modified rosin glycerin ester (acid modification rate 4.3 mass%)
All of A′1 to A′3 are solid at 25 ° C.

((B) component: cellulose fiber)
B1: Plant pulp-derived cellulose fiber, average fiber diameter: 30 nm, average degree of polymerization: 600, α-cellulose content of plant pulp: 85% by mass
B2: Plant pulp-derived cellulose fiber, average fiber diameter: 30 μm, average degree of polymerization: 2000, α-cellulose content of plant pulp: 85% by mass

((C) component: thermoplastic resin)
C1: Homopolypropylene, MFR: 0.5 g / 10 min MFR is a value measured under conditions of 230 ° C. and 2.16 kg / 10 min in accordance with ASTM D-1238 (2013).

[Evaluation of molded body]
The following evaluation was performed about the obtained molded object. The results are shown in Table 1.
(1) Density Density was measured by a method based on ASTM D792 (2013) (unit: g / cm ³ ).
(2) Tensile yield strength Measured according to ASTM D638 (1986) (unit: MPa).
(3) Tensile modulus Measured according to ASTM D638 (1986) (unit: MPa).
(4) Elongation at break (between chucks)
Measured according to ASTM D638 (1986) (unit:%).
(5) Dispersion state (dispersibility)
The dispersion state of the material in the test piece was evaluated. Specifically, the test piece was immersed in liquid nitrogen for 1 minute, frozen, then bent and broken, and the cross section was observed at 2000 times using a scanning electron microscope (SEM), and aggregates were not seen. A case where an agglomerate was observed was evaluated as “X”. Since Comparative Example 8 and 9 which did not mix | blend cellulose did not evaluate a dispersion state, it was set as "-".

  From Table 1, it can be seen that the resin composition according to one embodiment of the present invention has high dispersibility of cellulose fibers, and the obtained molded body is excellent in various mechanical properties with a good balance.

Claims (14)

  A cellulose fiber dispersant containing an acid-modified rosin having an acid modification rate of 0.08 to 4.0% by mass.   The cellulose fiber dispersant according to claim 1, wherein the acid-modified rosin is an α, β-unsaturated dicarboxylic acid-modified rosin. The 1st resin composition which contains the following (A) component and (B) component in the following ratio.
(A) Cellulose fiber dispersant according to claim 1 or 2 0.1-99.9% by mass
(B) Cellulose fiber 0.1-99.9 mass%   The resin composition according to claim 3, wherein an average fiber diameter of the cellulose fiber as the component (B) is 3 nm to 50 µm.   The resin composition according to claim 3 or 4, wherein the component (B) is a plant-derived cellulose fiber. The 2nd resin composition containing the following (A)-(C) component in the following ratio.
(A) The cellulose fiber dispersing agent of Claim 1 or 2 0.01-89.0 mass%
(B) Cellulose fiber 0.05-80.0 mass%
(C) Thermoplastic resin 10.0-99.9 mass%   The resin composition according to claim 6, wherein an average fiber diameter of the cellulose fiber as the component (B) is 3 nm to 50 μm.   The resin composition according to claim 6 or 7, wherein the component (B) is a plant-derived cellulose fiber.   The resin composition according to any one of claims 6 to 8, wherein the component (C) is a polyolefin resin.   The resin composition according to any one of claims 6 to 9, wherein the component (C) is polypropylene.   The resin composition according to any one of claims 6 to 10, wherein a melt flow rate of the component (C) at 230 ° C and a load of 2.16 kg is 0.1 to 200 g / 10 minutes.   The content ratio of the component (A) is 0.01 to 50.0 mass%, the content ratio of the component (B) is 0.05 to 50.0 mass%, and the content ratio of the component (C) The resin composition according to any one of claims 6 to 11, wherein is 20.0 to 99.9 mass%. A step of kneading cellulose fiber containing water and a cellulose fiber dispersant containing an acid-modified rosin having an acid modification rate of 0.08 to 4.0% by mass; and
A method for producing a resin composition, comprising melt-kneading the mixture obtained in the above step and a thermoplastic resin.   The molded object produced using the resin composition in any one of Claims 6-12.