Patent Application
20240101813
The present application is based on, and claims priority from JP Application Serial Number 2022-153440, filed Sep. 27, 2022, the disclosure of which is hereby incorporated by reference herein in its entirety.
The present disclosure relates to a molding material.
In the related art, molding materials containing cellulose fibers, resins, and the like have been known. For example, JP-A-2021-161337 discloses a molding composition containing pulp fibers and a biodegradable resin.
However, the molding composition described in JP-A-2021-161337 has a problem of difficulty in improving the strength of a molded article when a flame retardant is added to the composition in order to impart flame retardance. Specifically, the impact strength and the bending strength may be decreased when the flame retardance is ensured. Therefore, the molded article is deformed, cracked, and the like in some cases. That is, there has been a demand for a molding material that has flame retardance and improves the strength of a molded article.
According to an aspect of the present disclosure, there is provided a molding material including: linear alkyl-based polyester; highly polar polyester; cellulose fibers; and a flame retardant, in which a total content of the linear alkyl-based polyester and the highly polar polyester is less than or equal to a content of the cellulose fibers, the flame retardant has a phosphazene skeleton or a phosphoric acid ester skeleton in a molecular structure, and a content of the flame retardant is 1% by mass or greater and 10% by mass or less with respect to the total content of the linear alkyl-based polyester, the highly polar polyester, and the cellulose fibers.
FIGURE is a table showing compositions and evaluation results of molding materials according to examples and comparative examples.
A molding material according to the present embodiment contains linear alkyl-based polyester, highly polar polyester, cellulose fibers, and a flame retardant. A known molding method such as injection molding or press working can be applied to the molding material. A molded article produced from the molding material is suitable for various containers, office equipment such as sheets and printers, and housings of home electric appliances, as substitutes for polystyrene and the like. Hereinafter, various raw materials contained in the molding material will be described.
The linear alkyl-based polyester has thermoplasticity and melts to bind the cellulose fibers when a molded article is produced from the molding material. Further, the linear alkyl-based polyester and the cellulose fibers are responsible for the physical properties of the molded article. Particularly, the linear alkylene group increases the toughness and improves mainly the impact strength of the molded article.
The linear alkyl-based polyester contains, as raw material monomers, an alkyl dicarboxylic acid having an alkyl group with 2 or more and 8 or less carbon atoms and an alkylene diol having an alkylene group with 2 or more and 8 or less carbon atoms. The linear alkyl-based polyester is formed by copolymerizing the above-described two kinds of raw material monomers. The linear alkyl-based polyester is formed by copolymerizing the above-described two kinds of raw material monomers by a known synthesis method.
Examples of the alkyl dicarboxylic acid include linear saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Among these, one or more kinds thereof are used for the synthesis of the linear alkyl-based polyester.
Examples of the alkylene diol include dihydric alcohols such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Among these, one or more kinds thereof are used for the synthesis of the linear alkyl-based polyester. The above-described two kinds of raw material monomers are relatively easily available and can be applied for industrial use or commercial use.
It is preferable that the molding material contain one or more of polybutylene succinate, polybutylene succinate adipate, and polyethylene diadipate as the linear alkyl-based polyester. Since these linear alkyl-based polyesters have biodegradability, an environmental load of the molded article can be reduced.
The highly polar polyester improves the compatibility between the cellulose fibers and the linear alkyl-based polyester. In this manner, the wettability of the linear alkyl-based polyester with respect to the cellulose fibers is increased, and mainly the bending strength of the molded article is improved.
The highly polar polyester has a molecular structure with relatively high polarity and has one or more oxygen atoms for two carbon atoms in a repeating structure derived from the raw material monomer. Specifically, the highly polar polyester contains raw material monomers such as lactic acid, hydroxybutyric acid, oxysuccinic acid, citric acid, malonic acid, succinic acid, serine, threonine, acrylic acid, methyl acrylate, and vinyl acetic acid, as the raw material monomers.
Specifically, the highly polar polyester contains one or more of polylactic acid, polyhydroxybutyric acid, polyacrylic acid, polymethyl acrylate, and polyvinyl acetate. Among these, from the viewpoint of reducing the environmental load, it is preferable that the highly polar polyester contain one or more of polylactic acid and polyhydroxybutyric acid which have biodegradability. Further, the highly polar polyester may be a copolymer having a structure derived from lactic acid or acetic acid in a molecular structure such as polyethylene succinic acid.
The cellulose fibers function as a filler in the molded article and contributes to improvement of the physical properties such as bulkiness of the molding material and strength of the molded article.
The cellulose fibers are derived from plants and relatively abundant natural materials. Therefore, reduction of the environmental load is promoted when cellulose fibers are used as compared with a case where synthetic fibers are used. The cellulose fibers are excellent in terms of procurement of the raw materials and the cost. Further, the cellulose fibers have theoretically high strength among various fibers and contribute to improvement of the strength of the molded article. Used paper, used cloth, or the like may be reused as the cellulose fibers in addition to using virgin pulp.
The cellulose fibers are formed mainly of cellulose, but may contain components other than cellulose. Examples of the components other than cellulose include a hemicellulose and lignin. Further, the cellulose fibers may be subjected to a treatment such as bleaching.
From the viewpoint of improving the appearance of the surface of the molded article, the fiber length of the cellulose fibers is preferably less than 500 μm and more preferably less than 50 μm. The fiber length of the cellulose fibers is acquired by the method in conformity with ISO 16065-2:2007.
The total content of the linear alkyl-based polyester and the highly polar polyester in the molding material is less than or equal to the content of the cellulose fibers. In this manner, the functions of the cellulose fibers as a filler can be remarkably exhibited in the molded article.
Here, the content of the linear alkyl-based polyester in the molding material is greater than the content of the highly polar polyester. In this manner, the impact strength and the bending strength of the molded article can be improved in a well-balanced manner.
When the content of the linear alkyl-based polyester in the molding material is set to 100 parts by mass, the content of the highly polar polyester is 10 parts by mass or greater and 70 parts by mass or less, and the content of the cellulose fibers is 110 parts by mass or greater and 570 parts by mass or less. In this manner, the strength of the molded article can be further improved.
The flame retardant has a phosphazene skeleton or a phosphoric acid ester skeleton in a molecular structure. The phosphazene skeleton denotes a cyclic or chain molecular structure in which phosphorus atoms and nitrogen atoms are alternately bonded. That is, a flame retardant having the phosphazene skeleton in a molecular structure is a phosphazene derivative. The phosphazene derivative is not particularly limited, and examples thereof include hexachlorocyclotriphosphazene, hexabromocyclotriphosphazene, cyclotrichlorotriphenoxytriphosphazene, cyclohexaphenoxytriphosphazene, cyclotrichlorotrimethoxytriphosphazene, and derivatives in which these structures are ring-opened and form linear molecular structures.
A commercially available product may be employed as the flame retardant having a phosphazene skeleton. Specific examples of the commercially available product include phosphazene-based flame retardants such as RABITLE (registered trademark) FP-110 and FP-100 (trade names, manufactured by Mitsui Fine Chemicals, Inc.).
The phosphoric acid ester skeleton denotes a structure in which one or more of hydrogen atoms of three hydroxyl groups in phosphoric acid are substituted with organic groups. A flame retardant having the phosphoric acid ester skeleton is a phosphoric acid ester derivative. The phosphoric acid ester derivative is not particularly limited, and examples thereof include triphenyl phosphate, tris(isopropylphenyl) phosphate, diphenyl monohexyl phosphate, diphenyl phosphate ammonium salt, diphenyl phosphate aluminum salt, and a compound such as a bis-body or a polymer having a structure in which the same phosphoric acid unit is repeatedly present or crosslinked with a diol compound.
A commercially available product may be employed as the flame retardant having a phosphoric acid ester skeleton. Specific examples of the commercially available product include phosphoric acid ester-based flame retardants such as Exolit (registered trademark) OP1230, OP1240, OP1312, OP1400, and OP930 (manufactured by Clariant AG), and ADK STAB (registered trademark) FP-600, FP-900L, FP-2100JC, FP-2500S, FP-2600U, and PFR (manufactured by ADEKA Corporation).
The flame retardant having a phosphazene skeleton or a phosphoric acid ester skeleton in a molecular structure exhibits flame retardance with addition of a relatively small amount of the flame retardant. Therefore, the influence of the flame retardant on the strength of the molded article can be suppressed.
The flame retardant having a phosphazene skeleton or a phosphoric acid ester skeleton in a molecular structure exhibits satisfactory dispersibility in the molding material or in the molded article as compared with other flame retardants. Therefore, the above-described flame retardant is difficult to unevenly distribute in the form of aggregates in the molded article. Therefore, degradation of the physical properties of the molded article due to uneven distribution of the flame retardant can be suppressed.
The dispersed state of the flame retardant can be observed, for example, by element mapping analysis using a scanning electron microscope. The number of flame retardant aggregates per 1 cm square in a cross section of the molding material or the molded article is preferably 1 or less in the dispersed state of the flame retardant. Further, examples of other flame retardants here include flame retardants such as an antimony compound, a metal hydroxide, a nitrogen compound, and a boron compound.
The content of the flame retardant in the molding material is set to 1% by mass or greater and 10% by mass or less with respect to the total content of the linear alkyl- based polyester, the highly polar polyester, and the cellulose fibers. In this manner, the influence of the flame retardant on the strength of the molded article can be suppressed, and thus the flame retardance can be improved.
The molding material may contain other additives in addition to the flame retardant. Examples of the other additives include a colorant, an insect repellent, a fungicide, an antioxidant, an ultraviolet absorbing agent, an aggregation inhibitor, and a release agent. Further, the molding material may contain other resins in addition to the linear alkyl-based polyester and the highly polar polyester.
A method of producing the molding material will be described. A known method can be employed to produce the molding material. Specifically, for example, the following method can be employed.
First, the above-described raw materials are kneaded by a single-screw kneader or a twin-screw kneader to form strands. Next, a pelletizing process is performed on the raw materials to obtain a pellet-like molding material.
Further, the following method may be employed as the method of producing the molding material. First, used paper or a pulp material is coarsely crushed with a shredder to form cellulose fibers. Further, the cellulose fibers, the linear alkyl-based polyester, the highly polar polyester, and the flame retardant are weighed and kneaded. Next, the kneaded raw materials are accumulated in air to obtain sheet-like accumulations. Since the accumulations contain a large amount of air and thus have a small density, the density thereof is increased by compressing the accumulations with a calender device to remove the air. Next, the accumulations are heated with a heating furnace in a non-contact manner and heated and pressed with a heat press.
The accumulations are heated with the heating furnace and the heat press at a temperature higher than the melting temperature of the linear alkyl-based polyester and the highly polar polyester by approximately 20° C. In this manner, uneven distribution of the raw materials is suppressed, and a sheet in which the raw materials are dispersed is formed.
Next, the sheet is cut into a desired shape with a shredder so that a pellet-like molding material is obtained. The desired shape of the molding material is not particularly limited, but a substantially cubic shape with a volume of 2 cubic mm to 5 cubic mm may be employed. The molding material is produced by the method described above. Further, the method of producing the molding material is not limited to the method described above.
According to the present embodiment, the following effects are obtained. The molded article has flame retardance and the strength thereof can be improved. The flame retardant having a phosphazene skeleton or a phosphoric acid ester skeleton exhibits flame retardance with addition of a relatively small amount of the flame retardant. Further, the linear alkyl-based polyester contains a linear alkyl group and thus improves mainly the impact strength. Further, the highly polar polyester enhances the compatibility between the linear alkyl-based polyester and the cellulose fibers and thus improves mainly the bending strength. Therefore, the impact strength and the bending strength are improved in a well-balanced manner by using the linear alkyl-based polyester and the highly polar polyester in combination. Therefore, it is possible to provide a molding material that has flame retardance and improves the strength of a molded article.
Hereinafter, the effects of the present disclosure will be described in more detail based on examples and comparative examples. FIGURE shows the compositions of raw materials and the evaluation results of molded articles related to each of the molding materials in Examples 1 to 9 and Comparative Examples 1 to 9.
In the columns of the composition in FIGURE, the numerical values are in units of parts by mass, and “-” in the columns without description of numerical values denotes that the corresponding material is not contained. In the description of the raw material names, abbreviations are used for some names. Each abbreviation will be described below. In the description below, Examples 1 to 9 will also be simply and collectively referred to as examples, and Comparative Examples 1 to 9 will also be simply and collectively referred to as comparative examples. Further, the present disclosure is not limited to the following examples.
Based on the compositions of FIGURE, molding materials of the examples and the comparative examples were produced. Specifically, the linear alkyl-based polyester, the highly polar polyester, the cellulose fibers, and the flame retardant were weighed, put into a twin-screw kneader KZW15TW-45MG (manufactured by Technovel Corporation), and kneaded. The kneading was performed under conditions of a maximum heating temperature of 180° C. and an extrusion discharge amount of 1 kg/hr. Next, the materials were processed into strands, and pellet-like molding materials were obtained by a pelletizer.
The details of the abbreviations and the trade names listed in FIGURE are as follows.
Test pieces for evaluation were prepared by injection molding or press working using the molding materials of the examples and the comparative examples. Specifically, both the injection molding and the press working were carried out by setting the heating temperature of the molding materials to 200° C. Further, THX40-5V (manufactured by Nissei Plastic Industrial Co., Ltd.) was used as the injection molding device, and a hydraulic press PHKS-40ABS (manufactured by Towa Seiki Co., Ltd.) was used as the press working device.
Here, the content of PBS was set to 40 parts by mass, the content of PLA was set to 10 parts by mass, the content of the cellulose fibers was set to 50 parts by mass, and the content of the flame retardant a was set to 1 part by mass, thereby preparing a molded article of Example 1 by injection molding.
A molded article of Example 2 was prepared in the same manner as in Example 1 except that the content of PBS was decreased to 30 parts by mass and the content of PLA was increased to 20 parts by mass.
A molded article of Example 3 was prepared in the same manner as in Example 1 except that PBSA was used in place of PBS and the flame retardant b was used in place of the flame retardant a.
A molded article of Example 4 was prepared in the same manner as in Example 3 except that the flame retardant b was used in place of the flame retardant a and the content of the flame retardant b was increased to 5 parts by mass.
A molded article of Example 5 was prepared in the same manner as in Example 4 except that the flame retardant b was used in place of the flame retardant a.
A molded article of Example 6 was prepared in the same manner as in Example 2 except that PBSA was used in place of PBS.
A molded article of Example 7 was prepared in the same manner as in Example 3 except that the content of PLA was decreased to 10 parts by mass and the content of the cellulose fibers was increased to 60 parts by mass.
A molded article of Example 8 was prepared in the same manner as in Example 4 except that the content of PBSA was decreased to 16 parts by mass, the content of PLA was decreased to 4 parts by mass, the content of the cellulose fibers was increased to 80 parts by mass, and the molded article was prepared by press working.
A molded article of Example 9 was prepared in the same manner as in Example 5 except that the content of PBSA was decreased to 10 parts by mass, the content of the cellulose fibers was increased to 80 parts by mass, and the molded article was prepared by press working.
The content of PBS was set to 10 parts by mass, the content of PLA was set to 40 parts by mass, the content of the cellulose fibers was set to 50 parts by mass, and the content of the flame retardant c was set to 1 part by mass, thereby preparing a molded article of Comparative Example 1 by injection molding.
A molded article of Comparative Example 2 was prepared in the same manner as in Comparative Example 1 except that the content of the flame retardant c was increased to 5 parts by mass.
A molded article of Comparative Example 3 was prepared in the same manner as in Comparative Example 1 except that the content of the flame retardant c was increased to 20 parts by mass.
A molded article of Comparative Example 4 was prepared in the same manner as in Comparative Example 1 except that PBSA was used in place of PBS.
A molded article of Comparative Example 5 was prepared in the same manner as in Comparative Example 4 except that the content of the flame retardant c was increased to 5 parts by mass.
A molded article of Comparative Example 6 was prepared in the same manner as in Comparative Example 4 except that the content of the flame retardant c was increased to 20 parts by mass.
The content of PBS was set to 40 parts by mass, the content of PLA was set to 10 parts by mass, the content of the cellulose fibers was set to 50 parts by mass, and the content of the flame retardant c was set to 20 part by mass, thereby preparing a molded article of Comparative Example 7 by injection molding.
A molded article of Comparative Example 8 was prepared in the same manner as in Comparative Example 7 except that the content of PBS was decreased to 30 parts by mass and the content of PLA was increased to 20 parts by mass.
A molded article of Comparative Example 9 was prepared in the same manner as in Comparative Example 7 except that PBSA was used in place of PBS.
The test was performed by employing the Charpy impact strength as an index of the impact strength using a test method in conformity with ISO 179 (JIS K 7111). As the shape of the test piece, a rectangular plate with a long side of 80 mm±2 mm, a short side of 4.0 mm±0.2 mm, and a thickness of 10.0 mm±0.2 mm was used. An impact tester IT (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used as the test device. In the Charpy impact test, the hammer weight was set to 4 J (WR 2.14 N/m), the lifting angle was set to 150°, the remaining notch width was set to 8.0 mm±0.2 mm, and the notch angle was set to 45°.
The test was performed by employing the bending properties as an index of the bending strength using a test method in conformity with ISO 178 (JIS K 7171). As the shape of the test piece, a rectangular plate with a long side of 80 mm±2 mm, a short side of 10.0 mm±0.2 mm, and a thickness of 4.0 mm±0.2 mm was used. Further, the test was performed by using 68TM-30 (manufactured by Instron) as the test device and setting the distance between fulcrums to 64 mm.
The UL94 standard was employed as an index of the flame retardance, and the test piece was prepared in conformity with the standard test and used for the test. In the UL 94 standard, the flame retardance is in a descending order of 5 VA, 5VB, V-0, V-1, V-2, and HB.
The strength of each molded article was determined based on the obtained test results according to the following determination standards.
As shown in FIGURE, the molded articles in all the examples were evaluated at a level of B or higher, and particularly the molded articles in Examples 3 to 7 were evaluated as A. As shown in the results, it was found that the molded articles had relatively satisfactory flame retardance and the strength of the molded articles was improved in the examples. On the contrary, it was found that the molded articles were evaluated at a level of C or lower and the strength of the molded articles was difficult to improve in all the comparative examples.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-153440 | Sep 2022 | JP | national |
