JP6544675B2 - Method of manufacturing multilayer resin molded article - Google Patents

Description

  The present invention relates to a method for producing a multilayer resin molded article and a multilayer resin molded article produced by the method.

  Conventionally, a multilayer resin molded product molded using a plurality of resin materials is known. As a resin material of these multilayer resin molded products, thermoplastic resins are generally used for reasons such as easy molding. For example, a thermoplastic resin having a function according to the application is selected for the surface layer of the molded article, and a combination of plural types of thermoplastic resins is adopted for the base layer, such as selecting a cheaper thermoplastic resin. ing.

  A multilayer resin molded article using such a thermoplastic resin is advantageous in that the manufacturing cost is low and weight reduction of the molded article becomes possible. However, since the thermoplastic resin is inferior to the thermosetting resin in heat resistance and scratch resistance, the use of the molded article is limited.

  Then, the multilayer resin molded product comprised by the combination of a thermoplastic resin and a thermosetting resin is proposed until now. For example, Patent Document 1 uses a mixture of a thermosetting resin and wood as a surface layer mat for the front and back, and a three-layer or two-layer using a mixture of a thermoplastic resin melt and a piece of wood as a core layer mat. A wood board of structure has been proposed. In Patent Document 2, a mixture of a thermosetting resin and a wood material is used as a surface layer mat for the front and back, and a three-layer or two layer using a mixture of a thermoplastic resin melt and a wood material as a core layer mat. Layered wood-plastic composite boards have been proposed.

JP 2003-94411 A JP, 2003-1611, A

  However, in the case of a double-layered resin molded product combining a thermoplastic resin and a thermosetting resin, wood chips mixed with these, or wood materials, mixing of wood with a thermoplastic resin material or thermosetting resin material with wood chips etc. In the process of and the process of multilayer resin molding, inhomogenization tends to occur. And it was not avoided that an unevenness | corrugation arises on the surface of a molded article resulting from this heterogenization. For this reason, in spite of the various improvement attempts so far, the application of a multilayer resin molded product was still limited to the application which is permitted to have unevenness as a design property. Therefore, for example, a multilayer resin molded article excellent in durability and excellent in designability, which can be applied to uses such as a water-covered member and a fire-covered member, has been desired.

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a method for producing a novel multilayer resin molded product which is excellent in durability as well as in design.

  Another object of the present invention is to provide a multilayer resin molded article produced by the novel production method.

In order to solve the above problems, the method for producing a multilayer resin molded article of the present invention comprises the following steps:
(A) kneading the biomass material and the thermoplastic resin to obtain a biomass-containing thermoplastic resin material;
(B) molding the biomass-containing thermoplastic resin material with a mold to obtain a primary molded product, and (c) supplying a thermosetting resin material to the surface of the primary molded product housed in the mold. And forming a thermosetting resin material.

  In addition, the multilayer resin molded article of the present invention is characterized by being manufactured by the above-mentioned method for manufacturing a multilayer resin molded article.

  According to the method for producing a multilayer resin molded article of the present invention, a multilayer resin has advantages such as inexpensive manufacturing cost, weight saving of molded articles, etc., and excellent durability as well as design. An article can be provided.

It is a schematic cross section which illustrated one Embodiment of shaping | molding in the manufacturing method of the multilayer resin molded product of this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

  As described above, in the method for producing a multilayer resin molded article of the present invention, (a) kneading the biomass material and the thermoplastic resin to obtain a biomass-containing thermoplastic resin material, (b) the biomass-containing thermoplastic resin A step of molding the material with a mold to obtain a primary molded product, and (c) supplying a thermosetting resin material to the surface of the primary molded product with the primary molded product remaining in the mold to obtain a thermosetting resin The process of shape | molding the resin material is included.

<Biomass material>
Examples of biomass materials used in the above-mentioned kneading step (a) include plant materials such as wood, bamboo, hemp, herbs, agricultural products, etc., and wastes and residues thereof (skin, leaves, stems, fruits) And powders, fibers and the like obtained by processing the plant material. Examples of wood include powders and fibers obtained by processing various materials such as conifers such as cedar, cypress and pine, and hardwoods such as beech, nara and hippopotamus. Examples of hemp include powders and fibers obtained by processing jute, kenaf, flax, hemp, ramie, sisal and the like.

  In addition, as plant materials other than the above, rice straw, rice straw, rice husk, palm fruits, sugarcane swarf, etc. may be used. In addition, in the manufacturing method of the multilayer resin molded product of this embodiment, you may use together 2 or more types of biomass materials as needed.

<Thermoplastic resin>
As a thermoplastic resin used by this embodiment, PE (polyethylene), PP (polypropylene), PS (polystyrene), PET (polyethylene terephthalate), acryl (PMMA), an ABS resin, an ASA resin etc. are mentioned, for example . These thermoplastic resins can be selected according to the required purpose, application, and characteristics. For example, from the viewpoint of enhancing the adhesion between the biomass-containing thermoplastic resin material layer and the thermosetting resin material layer in a multilayer resin molded product, at least a part can be dissolved or softened during the heat molding of the thermosetting resin material Is preferred. In addition, depending on the combination of the thermoplastic resin and the thermosetting resin material, peeling may easily occur between the biomass-containing thermoplastic resin material layer and the thermosetting resin material layer in the multilayer resin molded product. Therefore, it is preferable to select in consideration.

  Further, the thermoplastic resin is not limited to the new material raw material (virgin), and for example, a recycled raw material such as waste plastic or recycled plastic may be used. In addition, 2 or more types of thermoplastic resins may be used together as needed.

  It is preferable that the ratio of the thermoplastic resin in the biomass containing thermoplastic resin material obtained after the said kneading | mixing exists in the range of 30-70 wt%. When the proportion of the thermoplastic resin is within the above range, an excessive increase in the melt viscosity of the biomass-containing thermoplastic resin material is suppressed, and injection into the mold can be performed more smoothly. In addition, when the proportion of the thermoplastic resin is within the above range, a fine shape is more efficiently formed on the surface of the biomass-containing thermoplastic resin material layer in the multilayer resin molded product, and the thermosetting resin material layer The adhesion between the two can be maintained more effectively. If the proportion of the thermoplastic resin is less than 30 wt%, the melt viscosity of the biomass-containing thermoplastic resin material may be high, and it may be difficult to inject the biomass-containing thermoplastic resin material into the mold during molding. When the proportion of the thermoplastic resin exceeds 70 wt%, the adhesion between the biomass-containing thermoplastic resin material layer and the thermosetting resin material layer in the multilayer resin molded product may be lowered. From the economical point of view and the point of view of reducing the weight of molded articles, it is preferable to reduce the proportion of the thermoplastic resin.

<Thermosetting resin material>
As a thermosetting resin material used by this embodiment, thermosetting resins, such as an epoxy resin, unsaturated polyester resin, an acrylic resin, a melamine resin, a phenol resin, are mentioned, for example. These thermosetting resin materials can be selected according to the required purpose, application, and characteristics. As the thermosetting resin material, a resin that can be cured at a temperature lower than the melting point of the thermoplastic resin is used.

  In the present embodiment, the thermosetting resin material preferably contains glass fibers. The glass fiber used in the present embodiment is used for the purpose of improving the elastic modulus and improving the adhesion between the thermosetting resin material and the biomass-containing thermoplastic resin material. For example, E glass, NE glass, T glass Etc. glass fibers. Since these glass fibers have different refractive indices (physical properties affecting the appearance of the multilayer resin molded product) and heat resistance (physical properties affecting the molding conditions), they should be selected according to the required purpose and application. it can.

  Moreover, it is preferable that the length of glass fiber exists in the range of 1.5-6.0 mm. The adhesiveness of a thermosetting resin material and the biomass containing thermoplastic resin material improves more effectively that the length of glass fiber is in said range. If the glass fiber length is less than 1.5 mm, the desired adhesion may not be obtained. If the glass fiber length exceeds 6.0 mm, desired adhesion may not be obtained, or the appearance of the multilayer resin molded article may be affected.

  In addition, there is no restriction | limiting in particular in content of glass fiber, However, If content of glass fiber is increased more, the adhesiveness of a thermosetting resin material and a biomass containing thermoplastic resin material will improve more effectively. On the other hand, when the content of glass fiber is large, the viscosity of the thermosetting resin material is increased. Therefore, it is preferable to adjust the content of glass fiber according to the forming method to be applied.

  In addition to the thermosetting resin, a material in which a crosslinking agent, a curing agent, and the like are mixed may be used as the thermosetting resin material. In this case, as the crosslinking agent, the curing agent and the like, various kinds can be used including those generally known. In addition, a thermosetting resin material may use together 2 or more types of thermosetting resin, a crosslinking agent, a hardening agent, etc. as needed.

  Furthermore, an inorganic filler is added to the thermosetting resin material from the viewpoint of improving the surface hardness of the multilayer resin molded product, improving the elastic modulus, and maintaining a solid feeling as the designability of the multilayer resin molded product. You may As the inorganic filler, various fillers can be used including those generally known, and examples thereof include aluminum hydroxide, magnesium hydroxide, silica and the like. From the viewpoint of the good dispersibility with the thermosetting resin and the fact that the adhesion between the biomass-containing thermoplastic resin material layer and the thermosetting resin material layer in the multilayer resin molded product is not impaired, The inorganic filler is preferably one that has been surface-treated with a surface treatment material. As the surface treating agent, any of various commonly known ones can be used, and examples thereof include organic metal compounds such as organic silicon compounds and organic titanium compounds, and phosphoric acid groups, phosphonic acid groups, sulfonic acid groups, and carboxylic acids. An acidic group containing organic compound etc. which have at least one acidic group, such as an acidic radical, etc. are mentioned.

<Biomass-containing thermoplastic resin material>
The biomass-containing thermoplastic resin material used in the present embodiment can be obtained by kneading the biomass material and the thermoplastic resin. Specifically, the biomass material and the thermoplastic resin are charged into the kneader, and shearing is applied at a temperature higher than the thermal melting temperature of the thermoplastic resin, more preferably a temperature higher than the thermal decomposition temperature of the biomass material, and kneading is performed. Do. Then, shear friction occurs between the biomass material, the thermoplastic resin, and the blades of the kneader to induce internal heat generation. In particular, when the biomass material is made to be hydrophobic by heat denaturation by kneading the biomass material and the thermoplastic resin at a temperature higher than the thermal decomposition temperature of the biomass material, the effect of improving the compatibility with the thermoplastic resin or the dispersing property Can bring. Furthermore, the biomass material can be plasticized to produce the effect of providing fluidity. As a result, integration and combination of the biomass material and the thermoplastic resin can be efficiently promoted.

  The biomass-containing thermoplastic resin material thus obtained is made hydrophobic by the heat denaturation effect of the biomass material. Also, the biomass material in the biomass-containing thermoplastic resin material is finely divided or homogeneously dispersed in the thermoplastic resin. Therefore, the biomass-containing thermoplastic resin material in the present embodiment is excellent in flowability and dimensional stability, and is easily injected into a mold for molding. Furthermore, due to the biomass material finely divided or homogeneously dispersed in the thermoplastic resin, the surface of the biomass-containing thermoplastic resin material layer in the multilayer resin molded article has fine irregularities to the extent that the designability of the molded article is not impaired. A shape arises. Due to this fine uneven shape, the adhesion area between the biomass-containing thermoplastic resin material layer and the thermosetting resin layer in the multilayer resin molded product is increased, and the adhesion is improved. Thus, the biomass material in the biomass-containing thermoplastic resin material plays a role as an anchor for improving the adhesion between the biomass-containing thermoplastic resin material layer and the thermosetting resin layer in the multilayer resin molded product.

  In a preferable embodiment, the biomass-containing thermoplastic resin material can be obtained, for example, by charging the biomass material and the thermoplastic resin into a kneader and kneading at a rotational speed of 100 to 3000 rpm at a temperature of 190 to 250 ° C. it can. In this case, when the temperature of the kneaded material is raised to about 200 to 250 ° C. by the frictional heat generation induced by the shear force applied by the kneader, the biomass material can be made hydrophobic by heat denaturation. Therefore, the effect of improving the compatibility with the thermoplastic resin or the effect of improving the dispersibility can be brought about, which is preferable.

  As a kneader used in the present embodiment, various types can be used including generally known types. From the viewpoint of more efficiently integrating and combining the biomass material and the thermoplastic resin, it is preferable to select a blade of the kneader which can apply a stronger shearing force. .

<Molding of primary molded product and thermosetting resin material>
In the method for producing a multilayer resin molded article of the present embodiment, as the step (b), a biomass-containing thermoplastic resin material is molded with a mold to obtain a primary molded article. As the mold, various types can be used including generally known types such as flat type and circular type. Moreover, as a molding method, generally known various molding methods such as cast molding, injection molding, blow molding, etc. can be applied.

  In the method for producing a multilayer resin molded article of the present embodiment, as the step (c), a biomass-containing thermoplastic resin material is molded with a mold to obtain a primary molded article, and then the primary molded article is used as a mold. In the stored state, a thermosetting resin material is supplied to the surface of the primary molded product to mold the thermosetting resin material. As a supply method and a molding method of the thermosetting resin material used in the present embodiment, various methods which are generally known can be applied.

  Here, one embodiment of molding in the method for manufacturing a multilayer resin molded article of the present invention will be described using the schematic cross-sectional view of FIG. 1.

  In the manufacturing method illustrated as a schematic cross-sectional view in FIG. 1, as shown in FIG. 1 (A), a mold 1 provided with an upper mold 2 and a lower mold 3 is used. The lower mold 3 of the mold 1 is provided with a thermosetting resin material injection port 4 as a clearance for injecting the thermosetting resin material. The thermosetting resin material inlet 4 can be designed according to the desired thickness of the thermosetting resin material layer in the multilayer resin molded product.

  First, as shown in FIG. 1 (B), a biomass-containing thermoplastic resin material obtained by kneading a biomass material and a thermoplastic resin in advance is introduced into the mold 1. Thereafter, the mold 1 is closed and clamped. Thereafter, by cooling the mold 1 within a temperature range from less than the melting temperature of the thermoplastic resin in the biomass-containing thermoplastic resin material to the curing temperature of the thermosetting resin material, primary of the biomass-containing thermoplastic resin material The molded article 5 is obtained. As the cooling means, various kinds of air cooling, water cooling, or a refrigerant can be used.

  Next, as shown in FIG. 1C, the upper mold 2 of the mold 1 is separated from the surface of the primary molded product 5 of the biomass-containing thermoplastic resin material, and the biomass-containing thermoplastic resin is injected from the thermosetting resin material inlet 4 The thermosetting resin material can be supplied to the surface of the primary molding 5 of the resin material.

  Then, as shown in FIG. 1D, the thermosetting resin material 6 is injected in a state where the primary molded product 5 of the biomass-containing thermoplastic resin material is accommodated in the mold 1. Thereafter, the mold pressure is maintained, and the thermosetting resin material 6 is cured. Thus, as shown in FIG. 1 (E), a multilayer resin molded article 9 composed of the biomass-containing thermoplastic resin material layer (base layer) 7 and the thermosetting resin material layer (surface layer) 8 is obtained. obtain.

  In addition, in the illustration of said embodiment, after obtaining the primary molded article 5 of the biomass containing thermoplastic resin material in FIG. 1 (B), it differs from FIG. 1 (C), and the upper mold of the mold 1 differs. In a state in which 2 is removed, a thermosetting resin material may be supplied to the surface of the primary molded article 5 of the biomass-containing thermoplastic resin material. In this case, when molding the thermosetting resin material, an upper mold having a shape different from the removed upper mold in accordance with the desired shape, thickness, etc. of the thermosetting resin material layer in the multilayer resin molded article. May be used. In addition, after the primary molded product 5 is cooled to a temperature less than the curing temperature of the thermosetting resin material, the thermosetting resin material 6 is injected into the mold 1, and then the mold 1 is added to the biomass-containing thermoplastic resin material. The thermosetting resin material 6 may be cured by raising the temperature to a temperature range from less than the melting temperature of the thermoplastic resin to the curing temperature of the thermosetting resin material. In addition, after obtaining the primary molded article 5 of the biomass-containing thermoplastic resin material with the mold 1, the thermosetting resin is taken out from the mold 1 and stored in a mold different from the mold 1 for molding the primary molded article 5; May be injected.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1
[Production of biomass-containing thermoplastic resin material]
65%, 35 parts, 2 parts of wood flour (100 mesh under), polypropylene (virgin PP, MFR 60), and compatibilizer “Umex 1010 (manufactured by Sanyo Chemical Industries, Ltd.)” respectively, Laboplast Mill (Made by Toyo Seiki Seisakusho). The rotational speed was kneaded at 150 rpm using a meshed co-directional rotating blade, and air cooling was started when the temperature of the kneaded product rose to 225 ° C. due to internal heat generation due to shear friction. Thereafter, the kneaded material was kneaded for 25 minutes while maintaining the temperature of the kneaded product at 220 ° C., to obtain a pellet-like biomass-containing thermoplastic resin material.
[Primary molding of biomass-containing thermoplastic resin material]
A flat plate shape (100 mm × 100 mm × 100 mm) of the above-mentioned biomass-containing thermoplastic resin material adjusted to a lower mold temperature of 100 ° C. using a table-top manual injection molding machine (made by Toyo Seiki Seisakusho Co., Ltd.) heated to 190 ° C. cylinder temperature. The primary molding of the biomass-containing thermoplastic resin material was obtained by injection molding in a 100 mm × t 3 mm) mold.
[Preparation of thermosetting resin material]
100 parts of an acrylic resin pellet "VH000 (manufactured by Mitsubishi Rayon Co., Ltd.)" was dissolved with 300 parts of methyl methacrylate "MMA (manufactured by Mitsubishi Gas Chemical Co., Ltd.)". In this solution, 4 parts of ethylene glycol dimethacrylate "NK ester 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.)" as a crosslinking agent, and alkylperester "Trigonox 121-50E (manufactured by Kayaku Akzo Co., Ltd.)" 1 as a curing agent A thermosetting resin material was obtained by mixing 6 parts and 600 parts of fused silica “F-HD05 (manufactured by Kinseimatech Co., Ltd.) (average particle diameter: 5 μm)”.
[Manufacture of multilayer resin molded articles]
The mold obtained by molding the primary molded article of the biomass-containing thermoplastic resin material described above was adjusted to a lower mold 80 ° C. upper mold 95 ° C. at t 5 mm while leaving the primary molded article. The above thermosetting resin material is insert-molded in the upper void of the mold, and the molded product is held in the mold for 20 minutes to obtain the biomass-containing thermoplastic resin material layer (base layer, 3 mm in thickness) and the heat. The multilayer resin molded product comprised with the curable resin material layer (surface layer, thickness 2 mm) was obtained.

Example 2
A multilayer resin molded article was obtained in the same manner as in Example 1 except that fused silica was not used when producing a thermosetting resin material.

Example 3
The same as Example 1, except that thermoplastic acrylic resin pellet "VH000 (Mitsubishi Rayon Co., Ltd.)" was used instead of the polypropylene used in Example 1 when preparing the biomass-containing thermoplastic resin material. Then, a multilayer resin molded product was obtained.

Example 4
Wood flour (100 mesh under), polypropylene (virgin PP, MFR 60), and compatibilizer “Yumex 1010 (manufactured by Sanyo Chemical Industries, Ltd.) used in Example 1 when producing a biomass-containing thermoplastic resin material A double-layered resin molded article was obtained in the same manner as in Example 1 except that the ratio of 50% to 50 parts was changed to 2.8 parts.

Example 5
[Production of biomass-containing thermoplastic resin material]
The proportions of wood flour (100 mesh under), polypropylene (commercially available virgin PP, MFR 60), and the compatibilizer "Umex 1010 (manufactured by Sanyo Chemical Industries, Ltd.)" used in Example 1 are 35 parts, 65 respectively. A biomass-containing thermoplastic resin material was obtained in the same manner as in Example 1 except that the ratio was 3.7 parts.

Example 6
When preparing a biomass-containing thermoplastic resin material, multilayers were carried out in the same manner as in Example 1 except that a roller type blade was used instead of the mesh type co-rotating blade of the laboplast mill used in Example 1. A resin molded product was obtained. It is generally known that, in the meshed co-directional rotating blade and the roller type blade, the meshed co-directional rotating blade can apply a higher shearing force to the material to be kneaded.

Example 7
Example of Example except that 0.5 parts of a 3.0 mm — E glass fiber “CS3E-227 (manufactured by Nitto Boseki Co., Ltd.)” was added to the acrylic resin when producing the thermosetting resin material. A multilayer resin molded article was obtained in the same manner as in 1.

Example 8
Example of Example except that 0.5 parts of a 0.3 mm length E glass fiber “SS10-420 (manufactured by Nitto Boseki Co., Ltd.)” was added to the acrylic resin when producing the thermosetting resin material. A multilayer resin molded article was obtained in the same manner as in 1.

Example 9
Example 1 and Example 1 except that 0.5 part of a 13 mm--E glass fiber "CS13-J 917 (manufactured by Nitto Boseki Co., Ltd.)" was added to the acrylic resin when producing the thermosetting resin material. A multilayer resin molded article was obtained in the same manner.

Comparative Example 1
[Production of biomass-containing thermoplastic resin material]
In the same manner as in Example 1, a biomass-containing thermoplastic resin material was obtained.
[Primary molding of biomass-containing thermoplastic resin material]
In the same manner as Example 1, a primary molded article of a biomass-containing thermoplastic resin material was obtained.
[Manufacture of multilayer resin molded articles]
Instead of the thermosetting resin material used in Example 1, a thermoplastic acrylic resin pellet "VH000 (manufactured by Mitsubishi Rayon Co., Ltd.)" was used. The mold obtained by molding the primary molded article of the biomass-containing thermoplastic resin material described above was adjusted to a lower mold 80 ° C. upper mold 95 ° C. at t 5 mm while leaving the primary molded article. The above-mentioned thermoplastic acrylic resin pellet is insert-molded into this mold using a table-top manual injection molding machine (made by Toyo Seiki Seisakusho Co., Ltd.) heated to a cylinder temperature of 230 ° C., and the molding is molded for 20 minutes in the mold By holding, a multilayer resin molded product composed of the biomass-containing thermoplastic resin material layer (base layer, thickness 3 mm) and the thermoplastic acrylic resin layer (surface layer, thickness 2 mm) was obtained.

Comparative Example 2
The thermosetting resin material was molded alone. Specifically, the mold molded in Example 1 was adjusted to t 5 mm, lower mold 80 ° C. upper mold 95 ° C. A thermosetting resin material similar to that of Example 1 was injected into the voids of the mold and held for 20 minutes to obtain a resin molded article of a thermosetting resin material (thickness 5 mm) alone.

  The following measurement and evaluation were carried out on the multilayer resin molded articles of Examples 1 to 9 and Comparative Examples 1 and 2 obtained in this manner (however, Comparative Example 2 is a single-layer resin molded article). .

[Evaluation of moldability of biomass-containing thermoplastic resin material]
The injection suitability to the mold was evaluated when producing a primary molded article of a biomass-containing thermoplastic resin material. Those that were easily injection molded by an injection molding machine were evaluated as having good moldability. In Table 1 below, those that could be easily injection molded were marked with ○, and those that took some time to inject were marked △.

[Evaluation of heat resistance]
After leaving an empty pot heated to 200 ° C. for 5 minutes on each multilayer resin molded product, the empty pot was removed and the appearance was visually observed. Those with no change in appearance before and after the test were evaluated as having good heat resistance. In Table 1 below, those with no change in appearance were marked with ○.

[Evaluation of scratch resistance]
The surface pencil hardness of each molded article was measured by the standard method of JIS K 5400.

[Evaluation of destructive adhesion]
Each molded product was subjected to impact using a hammer and then visually observed for appearance. The thing in which peeling of the biomass containing thermoplastic resin material layer and the thermosetting resin material layer in a multilayer resin molded product is not recognized was evaluated as favorable fracture adhesion. This evaluation was carried out twice, and in Table 1 below, those with no peeling were rated as ○, and those with partial peeling noted as Δ.

[Evaluation of elastic modulus]
The modulus of elasticity was measured in accordance with ASTM D790.

[Evaluation of weight]
The weight of each multilayer resin molded article was evaluated based on the weight of the resin molded article of Comparative Example 2.

  Table 1 shows the material composition and the evaluation results of the above multilayer resin molded product.

  The double-layered resin molded articles of Examples 1 to 9 are lighter in weight as compared with the molded article of Comparative Example 2 which is a molded article of the thermosetting resin alone, and exhibit excellent characteristics with respect to any evaluation items. That was confirmed. Moreover, when Example 1 and Example 2 are compared, in the double-layered resin molded product of Example 1 which added fused silica as an inorganic filler to the thermosetting resin material, the implementation which did not add an inorganic filler. The scratch resistance and the elastic modulus were more excellent than the multilayer resin molded article of Example 2. When Example 1 and Example 3 are compared, no significant difference is seen in the characteristics of the multilayer resin molded article depending on the difference of the thermoplastic resin used as the raw material of the biomass-containing thermoplastic resin material, and any molded article Also showed excellent characteristics.

  Further, when Example 1 and Examples 7 to 9 are compared, the multilayer resin molded article of Examples 7 to 9 in which the glass fiber is added to the thermosetting resin material is the multilayer resin molding of Example 1 It was confirmed that the elastic modulus is higher than that of the product, and the resin molded product is hardly bent. Moreover, Example 7 whose glass fiber length is in the range of 1.5-6.0 mm was more excellent in destructive adhesion than Examples 8 and 9. This means that, as described above, by using the glass fiber, the adhesion between the thermosetting resin material and the biomass-containing thermoplastic resin material and the elastic modulus are improved, and the impact resistance and the deformation resistance (strain resistance) are improved. It shows that a superior multilayer resin molded article can be obtained.

  On the other hand, in the multilayer resin molded article of Comparative Example 1 in which only the thermoplastic resin was used instead of the thermosetting resin material of the surface layer of the multilayer resin molded article, the phenomenon of gloss loss was observed in the heat resistance evaluation test. It was seen. Moreover, the elastic modulus of the multilayer resin molded product of the comparative example 1 was a numerical value significantly lower than the value of the multilayer resin molded product of Examples 1-9.

  Moreover, in the multilayer resin molded product of Example 6 which was knead | mixed using a roller type | mold blade, when producing a biomass containing thermoplastic resin material, it is another for injection | pouring of the resin material at the time of primary shaping | molding of a biomass containing thermoplastic resin material. It took some time compared with the example and the comparative example. In addition, peeling was observed in part in the evaluation test for fracture adhesion.

1 mold 2 upper mold 3 lower mold 4 thermosetting resin material inlet 5 primary molded article of biomass-containing thermoplastic resin material 6 thermosetting resin material 7 biomass-containing thermoplastic resin material layer (base layer)
8 Thermosetting resin material layer (surface layer)
9 Multi-layer resin molded products

Claims (5)

Next step;
(A) a step of obtaining a biomass-containing thermoplastic resin material by kneading a biomass material and a thermoplastic resin at a temperature higher than the thermal decomposition temperature of the biomass material and applying a shearing force ;
(B) molding the biomass-containing thermoplastic resin material with a mold to obtain a primary molded product, and (c) supplying a thermosetting resin material to the surface of the primary molded product housed in the mold. And a step of molding the thermosetting resin material.   The method for producing a multilayer resin molded article according to claim 1, wherein the proportion of the thermoplastic resin in the biomass-containing thermoplastic resin material obtained in the step (a) is in the range of 30 to 70 wt%. In the said process (c), it shape | molds within the temperature range from less than the melting temperature of a thermoplastic resin to the curing temperature of the said thermosetting resin material, The multilayer resin molded article of Claim 1 or 2 characterized by the above-mentioned. Manufacturing method. The said thermosetting resin material contains glass fiber, The manufacturing method of the multilayer resin molded article as described in any one of Claim 1 to 3 characterized by the above-mentioned. The length of the said glass fiber is in the range of 1.5-6.0 mm, The manufacturing method of the multilayer resin molded product of Claim 4 characterized by the above-mentioned.

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