JP7036640B2 - Laminated plate and its manufacturing method, molded product using laminated plate and its manufacturing method - Google Patents

Description

The present invention relates to a laminated board which is used as, for example, an automobile member, an electric device, a civil engineering / building member, etc. and can exhibit antistatic performance, a method for manufacturing the same, and a molded product using the laminated board and a method for manufacturing the same.

In recent years, many molded products obtained by molding a composite material such as a reinforced resin material have been used as automobile members, electric devices, and civil engineering / building members. Such a molded product is molded into a desired shape by a press molding method in which a molding material containing a reinforcing material such as glass fiber and a matrix material such as a resin binder is heated and pressed.

This kind of sheet molding material is disclosed in, for example, Patent Document 1. This sheet forming material includes a sheet-shaped forming material layer containing a reinforcing material and a matrix material, and protective film layers arranged on both sides of the forming material layer. The protective film layer is composed of a laminated film of a low-density polyethylene resin layer and a high-density polyethylene resin layer, and the high-density polyethylene resin layer side is in contact with the molding material layer. Further, the protective film layer of the sheet molding material may be subjected to antistatic treatment.

Japanese Unexamined Patent Publication No. 7-323507

In the sheet molding material having the conventional structure described in Patent Document 1 described above, the protective film layer is composed of a high-density polyethylene resin layer and a low-density polyethylene resin layer, and the high-density polyethylene resin layer side is arranged on the molding material layer side. Has been done. Therefore, the protective film layer is easily peeled off from the molding material layer, and the molded product is manufactured in a state where the protective film layer is peeled off from the molding material layer. Therefore, even if the protective film layer is subjected to antistatic treatment, the molded product cannot exhibit antistatic performance.

Further, if an antistatic agent is blended in the molding material layer so that the molded product can exhibit antistatic performance, the mechanical strength of the molded product increases as the content of the antistatic agent contained in the molding material layer increases. Shows a tendency to decrease, and the performance of the molded product deteriorates, which is not preferable.

Therefore, an object of the present invention is to use a laminated board, a manufacturing method thereof, and a laminated board capable of exhibiting effective antistatic performance with a small amount of antistatic agent and maintaining good mechanical strength. The present invention is to provide a molded product and a method for manufacturing the same.

In order to achieve the above object, the laminated board of the present invention has a main body layer having a fiber mat containing glass fibers, an antistatic layer laminated on at least one surface of the main body layer, and the inside of the main body layer. The antistatic layer comprises a thermoplastic resin existing in the voids and the antistatic layer and adhering the main body layer and the antistatic layer, and the antistatic layer is configured such that the antistatic agent is held by the thermoplastic resin. Has been done.

The antistatic function of this laminated board is exhibited by the antistatic agent held in the thermoplastic resin in the antistatic layer. Therefore, the antistatic agent may be blended in a predetermined amount with the thermoplastic resin forming the antistatic layer, and therefore it is not necessary to blend the antistatic agent with the entire laminated plate in a predetermined amount. As a result, the amount of the antistatic agent used can be reduced, and the decrease in the mechanical strength of the laminated board due to the addition of the antistatic agent can be suppressed.

According to the laminated board of the present invention, it is possible to exhibit effective antistatic performance with a small amount of antistatic agent and to maintain good mechanical strength.

It is sectional drawing which shows the laminated board in 1st Embodiment, (a) is the sectional drawing which shows the outline of the first polymer, (b) is the sectional view which shows the outline of the second polymer, (c) is the first. A cross-sectional view showing an outline of the three polymers and (d) is a sectional view showing an outline of the fourth polymer. (A) is a schematic perspective view showing a molded product having a first polymer processed from a laminated plate, and (b) is a schematic cross-sectional view showing a molded product having a first polymer processed from a laminated plate. (A) is a front view showing an apparatus for manufacturing a fiber mat of the first embodiment, and (b) is a front view showing an apparatus for manufacturing a laminated board of the first embodiment. (A) is a sectional view showing an outline of the first polymer in the second embodiment, (b) is a sectional view showing an outline of the first polymer in the third embodiment, and (c) is a sectional view showing an outline of the first polymer in the fourth embodiment. A cross-sectional view showing an outline of one polymer, (d) is a sectional view showing an outline of the first polymer in the fifth embodiment. (A) is a sectional view showing an outline of the first polymer in the sixth embodiment, (b) is a sectional view showing an outline of the first polymer in the seventh embodiment, and (c) is a sectional view showing an outline of the first polymer in the eighth embodiment. FIG. 5 is a cross-sectional view showing an outline of a polymer. (A) is a sectional view showing an outline of the first polymer in the ninth embodiment, (b) is a sectional view showing an outline of the first polymer in the tenth embodiment, and (c) is a sectional view showing an outline of the first polymer in the eleventh embodiment. A cross-sectional view showing an outline of one polymer, (d) is a sectional view showing an outline of the first polymer in the twelfth embodiment. The cross-sectional view which shows by decomposing the first polymer in Example 1. FIG. The graph which shows the relationship between the addition rate (mass%) of the antistatic agent, and the surface intrinsic resistance value (Ω) about Example 1 and Comparative Example 1. A graph showing the relationship between the addition rate of the antistatic agent (mass%) and the ratio of the addition amount of the antistatic agent to the entire material (mass%) for Example 1 and Comparative Example 1. The graph which shows the relationship between the addition rate (mass%) of an antistatic agent and the change rate (%) of a tensile strength about Example 1 and Comparative Example 1.

(First Embodiment)
Hereinafter, the first embodiment of the present invention will be described in detail with reference to the drawings.
As shown in FIG. 1 (c) or FIG. 1 (d), the laminated plate 11 of the first embodiment is laminated on a main body layer 12 having a fiber mat containing glass fibers and at least one surface of the main body layer 12. The antistatic layer 13 is provided with a void in the main body layer 12 and a thermoplastic resin existing in the antistatic layer 13 and adhering the main body layer 12 and the antistatic layer 13. The antistatic layer 13 is configured by holding an antistatic agent in a thermoplastic resin.

As shown in FIGS. 1A or 1B, the antistatic layer 13 constituting the laminated plate 11 is a thermoplastic resin sheet 14 and a thermoplastic resin impregnating sheet 15 such as a non-woven fabric (hereinafter, impregnated). It may be formed by using (also referred to as a sheet). In that case, the antistatic layer 13 is configured by impregnating the impregnating sheet 15 with a thermoplastic resin and an antistatic agent.

The main body layer 12 made of the fiber mat has voids, and a thermoplastic resin is present in the voids. The antistatic layer 13 is made of a thermoplastic resin containing an antistatic agent as described above. Therefore, the main body layer 12 and the antistatic layer 13 are adhesively fixed by the thermoplastic resin. Further, the impregnating sheet 15 has a gap penetrating the front and back surfaces of the sheet, and a thermoplastic resin is present in the gap. Therefore, the main body layer 12 and the impregnating sheet 15 are adhesively fixed by the thermoplastic resin.

Next, the material and the thermoplastic resin forming the main body layer 12, the antistatic layer 13, and the impregnating sheet 15 will be described in order.
(Main body layer 12)
As the material of the fiber mat, glass fiber alone, glass fiber with reinforcing fiber added, or resin fiber alone is used. As the glass fiber, continuous glass fiber alone or a mixture of continuous glass fiber and chopped glass fiber is preferable. As the reinforcing fiber, one kind or a mixture of two or more kinds selected from resin fiber, basalt fiber, natural fiber, pulp fiber and the like is used. As the resin fiber, polyester fiber, nylon fiber, vinylon fiber, rayon fiber, acrylic fiber, aramid fiber, polylactic acid fiber and the like are used.

It is preferable that these fibers have a higher melting point than the thermoplastic resin described later and can retain the non-woven fabric form, the woven fabric form or the knitted form when subjected to the heat treatment and the cooling and pressurizing treatment.
As the form of the fiber mat, the non-woven fabric may be used alone, or one or two selected from the woven fabric and the knitted fabric may be laminated on the non-woven fabric in a multi-layered manner.

(Antistatic layer 13)
Antistatic agents are intended to suppress the harmful effects of static electricity, such as malfunction and damage of electrical equipment, electric shock, and adhesion of dust. They are permanent antistatic agents (polymer antistatic agents) and temporary. Any antistatic agent (surfactant or the like) can be used, but a permanent antistatic agent is preferable from the viewpoint of maintaining the antistatic performance of the laminated board for a long period of time.

Polymer-type antistatic agents as permanent antistatic agents include anionic, cationic, amphoteric and nonionic polymers (polymers), and polyethylene oxide (PEO) having ionic conductivity. A polymer using a chain as a conductive unit is preferable. Examples of such an antistatic agent include those using a polyether block copolymer, specifically, Pelectron and Perestat manufactured by Sanyo Chemical Industries, Ltd. Examples of the Pelectron include Pelectron HS, Pelectron AS and Pelectron PVL.

Using the above-mentioned Pelectron, it is possible to reduce the surface intrinsic resistance value of the laminated board 11 to ¹⁰⁶ Ω with a blending amount of 10% by mass or less with respect to the thermoplastic resin constituting the antistatic layer 13, and it is semi-permanent. Can be imparted with antistatic properties. Further, by using the perestat, it is possible to reduce the surface intrinsic resistance value of the laminated plate 11 to ¹⁰⁷ to 109 Ω with a blending amount of about ¹⁰ % by mass with respect to the thermoplastic resin constituting the antistatic layer 13. Therefore, antistatic properties can be imparted semi-permanently.

(Thermoplastic resin impregnated sheet 15)
As the material of the impregnating sheet 15, resin fiber, glass fiber, natural fiber (including plant fiber, animal fiber, mineral fiber), pulp fiber and the like are used.

When resin fiber is used as the material of the impregnating sheet, it is preferable to include polyester fiber, nylon fiber, vinylon fiber, rayon fiber, acrylic fiber, aramid fiber, polylactic acid fiber and the like.

The form of the impregnating sheet 15 is preferably a single layer of a non-woven fabric, but is not limited to the non-woven fabric, and is selected from one single layer selected from a woven fabric and a knitted fabric, or from the above-mentioned non-woven fabric, a woven fabric and a knitted fabric. Two or more types may be configured in a multi-layered manner. These impregnating sheets 15 are passed through a softened thermoplastic resin described later. That is, the impregnating sheet 15 has a large number of voids that pass through the front and back surfaces, and the voids allow the softened thermoplastic resin to pass through.

(Thermoplastic resin)
Examples of the thermoplastic resin include polypropylene, polyester, polyethylene, polystyrene, nylon, polyvinyl chloride, polycarbonate, ABS resin, polylactic acid and the like. Here, polypropylene, polyester, polyethylene, polystyrene, nylon and polylactic acid are crystalline resins, and polyvinyl chloride, polycarbonate and ABS resins are amorphous resins.

When the fiber mat and the impregnating sheet 15 are made of a thermoplastic resin, the thermoplastic resin for adhesively fixing between the fiber mat and the impregnating sheet 15 is used in the fiber mat and the impregnating sheet 15. Use a thermoplastic resin whose softening temperature is lower than that of the thermoplastic resin.

Further, any additive such as an ultraviolet absorber, an antioxidant, a light stabilizer, a dispersant, a surfactant, a colorant, a plasticizer, and a flame retardant may be added to the thermoplastic resin.
Next, a method of manufacturing the laminated board 11 configured as described above will be described.

As shown in FIG. 3A, chopped glass fibers are drawn out from the chopped glass fiber container 16 via the feeding device 17, and continuous glass fibers are drawn out from the continuous glass fiber container 18 via the feeding device 19. Is done. After the glass fibers are supplied to the net conveyor 20, they are needle punched by the needle punching device 21, and are carried out as a non-woven fabric fiber mat 22.

As shown in FIG. 3 (b), a pair of non-woven fabric impregnating sheets 15 on which the thermoplastic resin sheets 14 are laminated and the fiber mat 22 are conveyed, respectively, and the first shown in FIG. 1 (a). It becomes the polymer 23. Here, the thermoplastic resin sheet 14 is a mixture of a predetermined amount of a permanent antistatic agent. That is, in the first polymer 23, one impregnating sheet 15 is superposed on the front side of the main body 12a having one fiber mat 22 so as to sandwich the main body 12a between the two impregnating sheets 15. There is. Further, one thermoplastic resin sheet 14 is laminated on the front side of both of these impregnating sheets 15 so as to sandwich the impregnating sheet 15 with the fiber mat 22.

(Heat and pressure treatment)
As shown in FIG. 3B, when the first polymer 23 passes through the heat-pressurized zone 24, it is heat-treated and pressure-treated. The heating temperature in this heat treatment is preferably equal to or higher than the softening temperature of the thermoplastic resin constituting the thermoplastic resin sheet 14. When the fiber mat 22 and the impregnating sheet 15 contain fibers made of a thermoplastic resin different from the thermoplastic resin sheet 14, the heating temperature is lower than the softening temperature of the thermoplastic resin. Set to temperature. On the other hand, the pressure in the pressure treatment is a pressure sufficient to integrate the fiber mat 22, the impregnating sheet 15, and the thermoplastic resin sheet 14, and is appropriately set according to a conventional method.

When the thermoplastic resin is an amorphous resin, the softening temperature is the temperature at the glass dislocation point. When the thermoplastic resin is a crystalline resin, the crystalline resin does not crystallize 100% and has an amorphous portion. From this, the crystalline resin has a glass dislocation point and a melting point higher than the glass dislocation point. Therefore, the softening temperature of the crystalline resin means the glass dislocation point or the melting point.

As shown in FIG. 1 (b), when heated at the heating temperature, the thermoplastic resin sheet 14 softens and the voids in the fiber mat 22 and the voids in the impregnation sheet 15 are each impregnated with the thermoplastic resin. The second polymer 25 is obtained. When the softened thermoplastic resin is impregnated into the impregnating sheet 15 by the pressurization, the antistatic agent mixed in the thermoplastic resin sheet 14 is removed from the impregnating sheet 15 together with a part of the softened thermoplastic resin. It is considered that the resin mat 22 is transferred to the inside.

(Cooling and pressurizing treatment)
As shown in FIG. 3 (b), when the second polymer 25 is cooled and pressurized while passing through the cooling and pressurizing zone 26, the inside of the fiber mat 22 is as shown in FIG. 1 (c). The thermoplastic resin is solidified in the voids and the voids in the impregnation sheet 15, respectively, to form a laminated plate 11 which is a tertiary polymer 27 in which both impregnation sheets 15 are adhered to the front side of the fiber mat 22. Here, in the laminated plate 11, the thickness of the impregnating sheet 15 is smaller than the thickness of the fiber mat 22 of the first polymer 23 shown in FIG. 1 (a).

When the impregnating sheet 15 is made of resin fibers, the softening temperature of the resin fibers is higher than the softening temperature of the thermoplastic resin sheet 14, so that the thermoplastic resin sheet 14 softens and is contained in the fiber mat 22. Even when the voids and the voids in the impregnation sheet 15 are impregnated with the thermoplastic resin, the form of the impregnation sheet 15 can be maintained.

(Spring back processing)
Subsequently, the laminated plate 11 which is the third polymer 27 is heated to a temperature equal to or higher than the softening temperature of the thermoplastic resin of the thermoplastic resin sheet 14 to be subjected to a springback treatment. Then, as shown in FIG. 1 (d), the thermoplastic resin solidified in the voids in the fiber mat 22 and the voids in the impregnating sheet 15 softens, and the fiber mat 22 springs back based on the properties of the glass fiber mat. Inflates with. Due to this springback, the porosity in the fiber mat 22 becomes larger than the porosity in the impregnating sheet 15.

After that, the thermoplastic resin is solidified by natural cooling in the voids in the fiber mat 22 and the voids in the impregnation sheet 15, respectively, and the fourth polymer having a thickness larger than that of the third polymer 27, for example, twice or more the thickness is obtained. It becomes the laminated board 11 which is 28. In this laminated board 11, the thickness of the impregnating sheet 15 is larger than the thickness of the fiber mat 22 shown in FIG. 1 (c).

Next, a molded product using the laminated plate 11 obtained by the above-mentioned manufacturing method will be described.
As shown in FIG. 2A, when the laminated plate 11 which is the third polymer 27 or the fourth polymer 28 is set in a mold and molded, the molded product 30 which is the fifth polymer 29 is obtained.

As shown in FIG. 2B, a molding frame is set on the laminated plate 11 which is the third polymer 27 (or the fourth polymer 28), and a part or the whole of the laminated plate 11, for example, the laminated plate 11 When the whole is heated to a temperature equal to or higher than the softening temperature of the thermoplastic resin and heat-treated, the laminated plate 11 expands. Next, when the laminated plate 11 is put into a mold and subjected to a pressure treatment, the tertiary polymer 27 is formed on the entire outer peripheral edge of the laminated plate 11 as a base plate portion which is a mold forming portion. It is a molded product 30a which is the sixth polymer 31 molded as the edge plate portion. Then, the laminated plate 11 becomes a mold molded product 30a that follows the mold shape of the mold, and the portion subjected to the pressure treatment has an arbitrary thickness depending on the shape of the mold used.

Further, the mold forming portions include the main body layer 12, the impregnating sheet 15, and the thermoplastic resin existing in the voids in the main body layer 12 and the voids in the impregnating sheet 15 in the thickness direction thereof as in the laminated plate 11. To prepare for.

Next, the operation of the laminated board 11 of the first embodiment will be described.
The laminated plate 11 of the first embodiment exists in the main body layer 12 made of the fiber mat 22, the antistatic layer 13 laminated on the surface thereof, the voids in the main body layer 12, and the antistatic layer 13, and the main body is present. It is composed of a thermoplastic resin that adheres the layer 12 and the antistatic layer 13. The antistatic layer 13 is configured by holding the antistatic agent in the thermoplastic resin.

The antistatic function of the laminated plate 11 is exhibited by the antistatic agent held in the thermoplastic resin in the antistatic layer 13 located on the surface side. In this case, the polymer having a polyethylene oxide chain having ionic conductivity as an antistatic agent has good compatibility with the thermoplastic resin, is uniformly dispersed in the thermoplastic resin, and has a uniform and good antistatic function. Is expressed in. Therefore, the antistatic agent may be blended in a predetermined amount with the thermoplastic resin forming the antistatic layer 13, in other words, it is not necessary to blend the antistatic agent with the entire laminated plate 11 in a predetermined amount.

Then, some of the thermoplastic resin moves into the fiber mat 22 together with the antistatic agent, but the antistatic agent in the thermoplastic resin remains in the antistatic layer 13 at the desired content, so that the layers are laminated. It is presumed that a good antistatic effect is exhibited on the surface of the plate 11. As a result, the amount of the antistatic agent used in the laminated plate 11 can be reduced.

When the impregnating sheet 15 transfers only the thermoplastic resin and exhibits a filter function that hinders the transfer of the antistatic agent, the content of the antistatic agent remaining in the antistatic layer 13 becomes high and charging is performed. It is presumed that the preventive effect is enhanced.

On the other hand, as the amount of the antistatic agent added increases, the mechanical strength of the laminated plate 11 decreases, but since the amount of the antistatic agent added is suppressed in the laminated plate 11 of the first embodiment, the antistatic agent It is possible to suppress a decrease in the mechanical strength of the laminated plate 11 due to the addition of the above.

The effects obtained by the first embodiment described in detail above are summarized below.
(1) The laminated plate 11 in the first embodiment has a main body layer 12 having a fiber mat 22, an antistatic layer 13 laminated on at least one surface of the main body layer 12, and voids and charges in the main body layer 12. It has a thermoplastic resin that exists in the prevention layer 13 and adheres the main body layer 12 and the antistatic layer 13. The antistatic layer 13 is configured by holding an antistatic agent in the thermoplastic resin.

Therefore, the antistatic agent may be blended in a predetermined amount with the thermoplastic resin forming the antistatic layer 13, and therefore it is not necessary to blend the antistatic agent with the entire laminated plate 11 in a predetermined amount. As a result, it is possible to reduce the amount of the antistatic agent used, and it is possible to suppress the decrease in the mechanical strength of the laminated plate 11 due to the addition of the antistatic agent, and the mechanical strength of automobile parts and the like is required. It can also be applied to the members.

Therefore, the laminated plate 11 in the first embodiment can exhibit effective antistatic performance with a small amount of antistatic agent and can maintain good mechanical strength.
(2) The antistatic agent contains a polymer having a polyethylene oxide chain. Therefore, the antistatic agent has ionic conductivity, can exhibit a semi-permanent antistatic function, and the laminated plate 11 can maintain excellent antistatic performance for a long period of time.

(3) The antistatic layer 13 is configured by impregnating the impregnating sheet 15 with a thermoplastic resin and an antistatic agent, so that the impregnating sheet 15 holds the thermoplastic resin and prevents antistatic having a predetermined thickness. The layer 13 can be formed, and the antistatic agent held in the thermoplastic resin present in the antistatic layer 13 can exhibit excellent antistatic performance.

(4) In the mold molded products 30 and 30a having the mold molding portion, the mold molding portion is thermoplastic in the main body layer 12, the antistatic layer 13, the voids in the main body layer 12, and the antistatic layer 13. The antistatic layer 13 includes a resin, and the antistatic agent is held by a thermoplastic resin. Therefore, the molded products 30 and 30a can exhibit antistatic performance in the antistatic layer 13 on the surface thereof.

(5) The method for producing the laminated board 11 includes a step of forming the first polymer 23, a step of forming the second polymer 25, and a step of forming the third polymer 27. Therefore, the laminated plate 11 can be easily manufactured by sequentially performing the laminating treatment, the heating / pressurizing treatment, and the cooling / pressurizing treatment.

(6) The antistatic layer 13 is configured by impregnating the impregnating sheet 15 with a thermoplastic resin and an antistatic agent, and the fiber mat 22 containing glass fibers has a springback property. Then, the tertiary polymer 27 is heat-treated to soften the thermoplastic resin to inflate the fiber mat 22 of the main body 12a, and the thermoplastic resin is solidified to be thicker than the tertiary polymer 27. It comprises the step of forming a large quaternary polymer 28. Therefore, the laminated plate 11 can be formed into a thick one, and the antistatic layer 13 on the surface thereof can exhibit antistatic performance.

(7) In the method for manufacturing the molded products 30 and 30a, a part or the whole of the laminated plate 11 is heat-treated, and the heat-treated laminated plate 11 is put into a mold and pressure-treated. This includes a step of molding the molded products 30 and 30a that follow the mold shape of the mold. Therefore, the molded products 30 and 30a can be easily manufactured by the heat treatment of the laminated plate 11 and the pressure treatment in the mold.

(2nd to 12th embodiments)
Next, the second embodiment to the twelfth embodiment will be described focusing on the differences from the first embodiment.

As shown in FIG. 4A, in the first polymer 23 of the second embodiment, the impregnation sheet 15 of both impregnation sheets 15 in the first polymer 23 of the first embodiment is omitted. Has been done.

As shown in FIG. 4B, in the first polymer 23 of the third embodiment, the double impregnation sheet 15 in the first polymer 23 of the first embodiment is omitted.
As shown in FIG. 4 (c), in the first polymer 23 of the fourth embodiment, the thermoplastic resin sheets 14 are laminated on both sides of one fiber mat 22, and further, the thermoplastic resin sheets thereof. The impregnation sheet 15 is superposed on both sides of the 14. That is, the fiber mat 22 is sandwiched between two thermoplastic resin sheets 14, and the thermoplastic resin sheets 14 are sandwiched between the fiber mat 22 and the impregnation sheet 15.

As shown in FIG. 4D, in the first polymer 23 of the fifth embodiment, the impregnation sheet 15 of both impregnation sheets 15 in the first polymer 23 of the fourth embodiment is omitted. Has been done.

As shown in FIG. 5A, in the first polymer 23 of the sixth embodiment, the main body layer 12 of the first polymer 23 of the first embodiment is between the two fiber mats 22 and them. It is composed of a single thermoplastic resin sheet 14 sandwiched between the two.

As shown in FIG. 5B, in the first polymer 23 of the seventh embodiment, the impregnation sheet 15 of both impregnation sheets 15 in the first polymer 23 of the sixth embodiment is omitted. Has been done.

As shown in FIG. 5 (c), in the first polymer 23 of the eighth embodiment, the double impregnation sheet 15 in the first polymer 23 of the sixth embodiment is omitted.
As shown in FIG. 6A, in the first polymer 23 of the ninth embodiment, the thermoplastic resin sheet 14 and the impregnation sheet 15 of the first polymer 23 of the sixth embodiment are replaced, and the impregnation sheet 15 is replaced. The main body layer 12 is composed of a mat group consisting of three fiber mats 22 on which they are superposed on each other. The material of both fiber mats 22 and the material of the fiber mat 22 between the fiber mats 22 are different from each other. For example, the fiber mat 22 is a non-woven fabric made of chopped glass fibers as in the first embodiment, and the fiber mat 22 is composed of a mixture of glass fibers of the non-woven fabric, for example, a woven fabric or the like other than the glass fibers.

As shown in FIG. 6B, in the first polymer 23 of the tenth embodiment, the double impregnation sheet 15 in the first polymer 23 of the ninth embodiment is omitted.
As shown in FIG. 6 (c), in the first polymer 23 of the eleventh embodiment, the main body layers 12 of the first polymer 23 of the ninth embodiment are two fiber mats on which they are superposed on each other. It is composed of a pair of mats having 22 as a set and a single thermoplastic resin sheet 14 sandwiched between the two mat groups. Of the set of fiber mats 22, the material of one fiber mat 22 stacked on the thermoplastic resin sheet 14 and the material of the other fiber mat 22 are different from each other.

As shown in FIG. 6D, in the first polymer 23 of the twelfth embodiment, the double impregnation sheet 15 in the first polymer 23 of the eleventh embodiment is omitted.

Hereinafter, the embodiment will be described in more detail with reference to Examples and Comparative Examples.
(Example 1)
Perectron HS manufactured by Sanyo Chemical Industries, Ltd. was blended with polypropylene pellets as a permanent antistatic agent at the addition rate shown below (addition rate to polypropylene pellets, mass%) and mixed. This mixture was charged into the hopper of an extruder, extruded according to a conventional method, and discharged from a die. The obtained extruded product was stretched with a roller to prepare a thermoplastic resin sheet 14 having a thickness of 0.3 to 0.5 mm.

The fiber mat 22 made of glass fiber is formed by subjecting long glass fibers to needle punching according to a conventional method, and has a basis weight of 640 g / cm ² . The nonwoven fabric was formed of polyester fibers, and a nonwoven fabric 1 having a basis weight of 135 g / cm ² and a nonwoven fabric 2 having a basis weight of 80 g / cm ² were prepared.

Then, as shown in FIG. 7, an impregnating sheet 15 made of a non-woven fabric 1 is laminated on the front surface side of the fiber mat 22, and a thermoplastic resin sheet 14 containing an antistatic agent is laminated on the surface thereof, and the non-woven fabric is laminated on the back surface side of the fiber mat 22. An impregnating sheet 15 made of 2 and a thermoplastic resin sheet 14 containing no antistatic agent were arranged on the back surface thereof, and these were laminated to obtain a first polymer 23. The first polymer 23 was heat-pressurized for 105 seconds at a temperature of 230 ° C. and a pressure of 1.6 MPa. Then, a cooling and pressurizing treatment was performed for 105 seconds under the condition of a temperature of 40 ° C. and a pressure of 1.6 MPa to prepare a laminated board 11 which is a tertiary polymer 27.

The surface specific resistance value (Ω) of this laminated plate 11 was measured with a surface resistance tester ST-4 manufactured by Simco Japan Co., Ltd. That is, surface resistance meters were placed at three locations on the surface of the laminated plate 11 to measure the surface specific resistance values, and the average value of these measured values is shown in Table 1.

(Comparative Example 1)
For the thermoplastic resin sheet 14 produced in Example 1, the surface intrinsic resistance values were measured in the same manner as in Example 1, and the average values thereof are shown in Table 1. The addition rate of the antistatic agent is the addition rate (mass%) with respect to the thermoplastic resin.

Further, with respect to Example 1 and Comparative Example 1, the relationship between the addition rate (mass%) of the antistatic agent and the surface intrinsic resistance value (Ω) is shown in FIG.

表１及び図８に示したように、実施例１の積層板１１では比較例１の熱可塑性樹脂シート１４に比べて表面固有抵抗値が２桁（１０^２）程度低下する結果が得られた。

As shown in Table 1 and FIG. 8, the result was obtained that the surface specific resistance value of the laminated plate 11 of Example 1 was reduced by about ^two orders of magnitude (102) as compared with the thermoplastic resin sheet 14 of Comparative Example 1. ..

Here, for Example 1 and Comparative Example 1, the relationship between the addition rate of the antistatic agent (mass%) and the ratio of the addition amount of the antistatic agent to the entire material (mass%) is shown in FIG. 9 in a bar graph.
As shown in FIG. 9, in the laminated board 11 of Example 1, the amount of the antistatic agent added to the entire material could be significantly reduced as compared with the thermoplastic resin sheet 14 of Comparative Example 1.

Next, among the laminated plates 11 of the first embodiment, five each of the antistatic agents having an addition rate of 0% by mass, 5% by mass, 10% by mass, and 15% by mass are based on ASTM-D638. A tensile test was carried out by the test method described above, and the tensile strength (MPa) was measured. The average value of the obtained tensile strength was obtained and shown in Table 2.

(Comparative Example 2)
Pelectron HS manufactured by Sanyo Chemical Industries, Ltd. as a permanent antistatic agent is mixed with polypropylene pellets at the addition rates shown in Table 2, and injection molded by an injection molding machine according to a conventional method to prepare test pieces. Made. Tensile strength (MPa) was measured by conducting a tensile test on each of these test pieces by a test method based on JIS-K7113. The average value of the obtained tensile strength was obtained and shown in Table 2. Further, when the tensile strength when the antistatic agent was not added was 100, the relative change in the tensile strength due to the addition rate of the antistatic agent was calculated and shown in Table 3.

Further, with respect to Example 1 and Comparative Example 2, the relationship between the addition rate (mass%) of the antistatic agent and the change rate (%) of the tensile strength when the case where the antistatic agent is not added is 100% is shown in FIG. It was shown to.

表２、表３及び図１０に示したように、実施例１の積層板１１では帯電防止剤の添加率が増大しても引張強度の変化率が１００％前後で推移しているのに対し、比較例２のポリプロピレンの試験片では帯電防止剤の添加率が増大するに従って引張強度の変化率が次第に低下する傾向を示した。

As shown in Table 2, Table 3 and FIG. 10, in the laminated plate 11 of Example 1, the rate of change in tensile strength remains around 100% even if the addition rate of the antistatic agent increases. In the polypropylene test piece of Comparative Example 2, the rate of change in tensile strength tended to gradually decrease as the rate of addition of the antistatic agent increased.

It is also possible to modify and embody the embodiment as follows.
The thermoplastic resin sheet 14 may be composed of two sheets. For example, of the two thermoplastic resin sheets 14, the amount of the antistatic agent blended in the inner thermoplastic resin sheet 14 may be reduced or may not be blended.

The amount of the antistatic agent added to the thermoplastic resin constituting the antistatic layer 13 includes the required antistatic performance, the mechanical strength of the laminated board 11, and the amount of the thermoplastic resin impregnated into the fiber mat 22. It may be set in consideration of.

-A thermoplastic elastomer such as a polyolefin-based thermoplastic elastomer or a polyester-based thermoplastic elastomer may be blended with the thermoplastic resin.

11 ... Laminated plate, 12 ... Main body layer, 12a ... Main body, 13 ... Antistatic layer, 14 ... Thermoplastic resin sheet, 15 ... Thermoplastic resin impregnating sheet, 22 ... Fiber mat, 23 ... First polymer, 25 ... Second polymer, 27 ... Third polymer, 28 ... Fourth polymer, 30, 30a ... Molded product.

Claims (6)

A body layer with a fiber mat containing glass fiber,
An antistatic layer laminated on at least one surface of the main body layer,
It is provided with a thermoplastic resin that exists in the voids and the antistatic layer in the main body layer and adheres the main body layer and the antistatic layer.
In the antistatic layer, the thermoplastic resin and the antistatic agent are impregnated in a non-woven fabric having voids through which the softened thermoplastic resin passes.
The antistatic layer is a laminated plate in which the antistatic agent containing a polymer type antistatic agent is held by a thermoplastic resin. The laminated board according to claim 1, wherein the polymer-type antistatic agent contains a polymer having a polyethylene oxide chain. A mold-molded product having a mold-molding part,
A main body layer having a fiber mat containing glass fibers and an antistatic layer laminated on at least one surface of the main body layer in the mold forming portion in the thickness direction thereof.
It is provided with a thermoplastic resin that exists in the voids and the antistatic layer in the main body layer and adheres the main body layer and the antistatic layer.
In the antistatic layer, the thermoplastic resin and the antistatic agent are impregnated in a non-woven fabric having voids through which the softened thermoplastic resin passes.
A molded product in which the antistatic agent containing a polymer-type antistatic agent is held in the thermoplastic resin in the antistatic layer . A step of superimposing a main body having a fiber mat containing glass fiber and a thermoplastic resin sheet mixed with an antistatic agent to form a first polymer.
By subjecting the first polymer to heat treatment and pressure treatment, the thermoplastic resin is softened and the voids in the main body are impregnated with a part of the thermoplastic resin, and the thermoplastic resin sheet is antistatic. The process of forming the second polymer in which the agent was indwelled, and
The second polymer is further subjected to a cooling treatment and a pressure treatment to solidify the thermoplastic resin, and by this solidification, a thermoplastic resin sheet is adhered to the surface of the main body and the indwelling antistatic is applied. The method for producing a laminated board according to claim 1, further comprising a step of fixing an agent to form a third polymer having an antistatic layer. The fiber mat containing the glass fiber has a springback property and has a springback property.
A step of softening the thermoplastic resin solidified in the voids in the main body and the antistatic layer by heat-treating the tertiary polymer to inflate the fiber mat of the main body.
The method for producing a laminated board according to claim 4 , further comprising a step of solidifying the thermoplastic resin in the voids in the main body and the antistatic layer to form a fourth polymer having a thickness larger than that of the third polymer. .. A part or the whole of the laminated plate formed by the manufacturing method according to claim 4 is heat-treated, the heat-treated laminated plate is put into a mold, and a pressure treatment is applied to the mold. A method for manufacturing a mold-molded product, which comprises a step of molding a mold-molded product that follows the mold shape of.

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