JP6468030B2 - Method for producing composite film and composite material - Google Patents

Description

  The present invention relates to a method for producing a composite film and a composite material. Specifically, the present invention relates to a method for producing a composite film in which a continuous reinforcing fiber is impregnated with a thermoplastic resin having a high melting point.

In recent years, fiber reinforced resin materials in which a continuous reinforcing fiber is impregnated with a thermoplastic resin have been studied. As a method for impregnating the continuous reinforcing fiber with the thermoplastic resin, a method of impregnating the continuous reinforcing fiber (for example, a carbon fiber sheet) aligned in one direction with a thermoplastic resin film heated and impregnated, or impregnating with a molten resin There is a method (melt lamination method).
Specifically, in Patent Document 1, a polyamide resin (A) obtained from a diamine component containing 30 mol% or more of metaxylylenediamine and a dicarboxylic acid component is laminated with a polyolefin resin (B) to obtain a polyamide resin (A ) / Process for producing a polyolefin resin (B) laminated film, a process for producing a polyamide resin (A) film by peeling off the polyolefin resin (B) layer from the laminated film, and producing a fiber from the obtained polyamide resin (A) film. The manufacturing method of the composite material characterized by including the process of heating-pressing the laminated body laminated | stacked with material (C) is disclosed. Although the method described in Patent Document 1 is a useful method, it requires two steps: a step of producing a polyamide resin film and a step of heating and impregnating the continuous reinforcing fibers with the polyamide resin film superimposed thereon. As a method that does not require such two steps, there is a melt laminating method.
The melt laminating method is a method of impregnating a continuous reinforcing fiber with a molten material as it is. The melt lamination method is described in Patent Document 2. That is, in Patent Document 2, a sheet-like reinforcing fiber base material and a thermoplastic resin are introduced between a pair of rolls, and the thermoplastic material melted in the reinforcing fiber base material while rotating the pair of rolls. A method of manufacturing a fiber-reinforced resin sheet by impregnating with a resin, wherein a metal main roll and a metal press roll are used as the pair of rolls, and the press roll with respect to the main roll The thermoplastic fiber is impregnated with the thermoplastic resin while deforming the peripheral surface of the pressing roll so that the peripheral surface of the pressing roll follows the shape of the peripheral surface of the main roll. A method for producing a featured fiber reinforced resin sheet is disclosed.

JP 2012-021062 A JP 2012-110935 A

Here, in order to improve the impregnation property, the melting temperature of the thermoplastic resin (for example, the temperature of the thermoplastic resin extruded from the extruder) needs to be equal to or higher than the melting point of the thermoplastic resin. However, when the melting point of the thermoplastic resin is as high as 190 ° C. or higher, for example, when extruded from the die, the temperature of the molten thermoplastic resin is lowered due to the space between the die and the roll called the air gap. Thus, it has been found that impregnation of the thermoplastic resin may not proceed well. Moreover, the thermoplastic resin may adhere to the pressure-bonding roll.
An object of the present invention is to solve such a problem, and even if a thermoplastic resin having a high melting point is used, a continuous reinforcing fiber can be impregnated with a thermoplastic resin by a simple method. An object is to provide a manufacturing method and a composite material.

式（２）

式（２）中、Ｘは、メチルペンタメチレン基またはメチルオクタメチレン基である。
＜７＞前記熱可塑性樹脂（Ａ）が、ジアミン由来の構成単位とジカルボン酸由来の構成単位を含み、ジアミン由来の構成単位の５０モル％以上がキシリレンジアミンに由来するポリアミド樹脂から選択される少なくとも１種である、＜１＞〜＜４＞のいずれかに記載の複合フィルムの製造方法。
＜８＞前記ジカルボン酸が、アジピン酸およびセバシン酸の少なくとも１種である、＜７＞に記載の複合フィルムの製造方法。
＜９＞前記連続強化繊維シート（Ｃ）が、連続強化繊維の織物または編み物である、＜１＞〜＜８＞のいずれかに記載の複合フィルムの製造方法。
＜１０＞前記ポリオレフィン樹脂（Ｂ）が、ポリエチレン樹脂およびポリプロピレン樹脂から選択される少なくとも１種を含む、＜１＞〜＜９＞のいずれかに記載の複合フィルムの製造方法。
＜１１＞前記共押出し後の、層状の熱可塑性樹脂（Ａ）と、層状のポリオレフィン樹脂（Ｂ）の厚さの比率が１０：１〜１０：５００である、＜１＞〜＜１０＞のいずれかに記載の複合フィルムの製造方法。
＜１２＞前記複合フィルムの厚さが、２０〜３００μｍである、＜１＞〜＜１１＞のいずれかに記載の複合フィルムの製造方法。
＜１３＞さらに、前記熱可塑性樹脂（Ａ）が含浸した連続強化繊維シート（Ｃ）と、層状のポリオレフィン樹脂（Ｂ）を分離することを含む、＜１＞〜＜１２＞のいずれかに記載の複合フィルムの製造方法。
＜１４＞熱可塑性樹脂（Ａ）が含浸した連続強化繊維シート（Ｃ）の表面にポリオレフィン樹脂（Ｂ）層を有する複合材料。 Under such circumstances, as a result of intensive studies by the inventor, the continuous reinforcing fiber sheet is passed through a roll in a state in which a thermoplastic resin having a melting point of 190 ° C. or more and a polyolefin resin are coextruded in layers. Thus, it was found that even a thermoplastic resin having a high melting point of 190 ° C. or higher can be easily impregnated into continuous reinforcing fibers, and the present invention has been completed. Specifically, the above problems have been solved by the following means <1> and <11>, preferably <2> to <14>.
<1> A thermoplastic resin (A) having a melting point of 190 ° C. or higher and a polyolefin resin (B) on the surface of the continuous reinforcing fiber sheet (C), and the thermoplastic resin (A) side is the continuous reinforcing fiber sheet (C And coextruding in layers so as to be in contact with the continuous reinforcing fiber sheet (C), and then rolls on the continuous reinforcing fiber sheet (C) side, impregnating the continuous reinforcing fiber sheet (C) with the thermoplastic resin (A), A method for producing a composite film.
<2> The method for producing a composite film according to <1>, wherein the temperature of the surface of the roll is equal to or higher than the melting point of the thermoplastic resin (A) + 10 ° C.
<3> The method for producing a composite film according to <1> or <2>, further comprising arranging a second roll on the polyolefin resin (B) side after co-extrusion into the layer shape.
<4> The method for producing a composite film according to <3>, wherein the surface temperature of the second roll is lower than the melting point of the polyolefin resin (B).
<5> The thermoplastic resin (A) is any one of <1> to <4>, which is at least one selected from polyamide resins, polyphenylene sulfide resins, aromatic polyether ketone resins, and polyimide resins. A method for producing a composite film.
<6> The thermoplastic resin (A) is represented by the following formula (1): polyamide 46, polyamide 6, polyamide 610, polyamide 66, polyamide 6T / 66, polyamide 6T, polyamide 6T / 6I, polyamide 9T, polyamide 10T. And a polyamide resin containing as a main component a structural unit selected from structural units represented by the following formula (2), and a structural unit derived from diamine and a structural unit derived from diamine, The method for producing a composite film according to any one of <1> to <4>, wherein 50 mol% or more of the structural units is at least one selected from polyamide resins derived from xylylenediamine;
Formula (1)

Formula (2)

In formula (2), X is a methylpentamethylene group or a methyloctamethylene group.
<7> The thermoplastic resin (A) includes a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 50 mol% or more of the structural unit derived from diamine is selected from a polyamide resin derived from xylylenediamine. The method for producing a composite film according to any one of <1> to <4>, which is at least one kind.
<8> The method for producing a composite film according to <7>, wherein the dicarboxylic acid is at least one of adipic acid and sebacic acid.
<9> The method for producing a composite film according to any one of <1> to <8>, wherein the continuous reinforcing fiber sheet (C) is a woven or knitted continuous reinforcing fiber.
<10> The method for producing a composite film according to any one of <1> to <9>, wherein the polyolefin resin (B) includes at least one selected from a polyethylene resin and a polypropylene resin.
<11> The ratio of the thickness of the layered thermoplastic resin (A) and the layered polyolefin resin (B) after the coextrusion is 10: 1 to 10: 500, <1> to <10> The manufacturing method of the composite film in any one.
<12> The method for producing a composite film according to any one of <1> to <11>, wherein the thickness of the composite film is 20 to 300 μm.
<13> Furthermore, the continuous reinforcing fiber sheet (C) impregnated with the thermoplastic resin (A) and the layered polyolefin resin (B) are separated, and any one of <1> to <12> A method for producing a composite film.
<14> A composite material having a polyolefin resin (B) layer on the surface of the continuous reinforcing fiber sheet (C) impregnated with the thermoplastic resin (A).

  According to the present invention, it is possible to provide a composite film manufacturing method and a composite material in which a continuous reinforcing fiber can be impregnated with a thermoplastic resin by a simple method even when a thermoplastic resin having a high melting point is used. became.

FIG. 1 is a schematic diagram of the first half of a production process of a composite film in the present invention. FIG. 2 is a schematic diagram of the latter half of the manufacturing process of the composite film in the present invention.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  In the method for producing a composite film of the present invention, a thermoplastic resin (A) having a melting point of 190 ° C. or higher and a polyolefin resin (B) are placed on the surface of the continuous reinforcing fiber sheet (C), After coextruding in layers so as to contact the continuous reinforcing fiber sheet (C), a roll is disposed on the continuous reinforcing fiber sheet (C) side, and the thermoplastic resin (A) is added to the continuous reinforcing fiber sheet (C). It is characterized by impregnating. By adopting such a configuration, even if a thermoplastic resin having a melting point of 190 ° C. or higher is used, continuous reinforcing fibers can be impregnated by the melt lamination method.

Hereinafter, the manufacturing method of the present invention will be described with reference to FIGS.
FIG. 1 is a schematic view of a production process of a composite film in the present invention, wherein 1 is a first roll, 2 is a continuous reinforcing fiber sheet (C), 3 is a thermoplastic resin (A), 4 shows a polyolefin resin (B), 5 shows a second roll, and 6 shows a laminate.
In the present invention, the thermoplastic resin (A) 3 and the polyolefin resin (B) 4 are respectively melted on the surface of the continuous reinforcing fiber sheet (C) 2 and are layered from the T die via the feed block. Are coextruded. As shown in FIG. 1, a laminate 6 of a continuous reinforcing fiber sheet (C) 2, a layered thermoplastic resin (A) 3, and a layered polyolefin resin (B) (polyolefin resin (B) layer) 4 by coextrusion. It becomes. In this state, the thermoplastic resin (A) is in a molten state, and the polyolefin resin (B) having a melting point lower than that of the thermoplastic resin (A) may be melted or may be cured. In addition, about a multilayer film manufacturing apparatus, it is not limited to these, A well-known method is applicable.
Here, the temperature of the thermoplastic resin (A) at the time of extrusion is preferably the melting point of the thermoplastic resin (A) + 5 ° C. to the melting point + 100 ° C., more preferably the melting point + 10 ° C. to the melting point + 80 ° C. On the other hand, the temperature of the polyolefin resin (B) at the time of extrusion is preferably the melting point of the polyolefin resin (B) + 5 ° C. to the melting point + 40 ° C.

Here, the ratio of the thickness of the layered thermoplastic resin (A) and the layered polyolefin resin (B) during coextrusion is preferably 10: 1 to 10: 500, and 10:10 to 10: More preferably, it is 200. The ratio of the thickness of the layered thermoplastic resin (A) and the continuous reinforcing fiber sheet (C) is preferably 10.3: 1 to 10: 1, and 0.5: 1 to 5: 1. More preferably, it is more preferably 0.6: 1 to 4.0: 1.
Furthermore, the thickness of the layered thermoplastic resin (A) at the time of coextrusion can be appropriately determined according to the thickness of the composite film and the content of the thermoplastic resin (A) in the composite film, preferably 10 to It is 200 micrometers, More preferably, it is 20-150 micrometers. When it is desired to reduce the content of the thermoplastic resin (A) in the composite film, that is, when it is desired to increase the content of the continuous reinforcing fiber sheet, the thickness of the layered thermoplastic resin (A) is reduced.
On the other hand, the thickness of the layered polyolefin resin (B) at the time of co-extrusion is not particularly defined, but can be, for example, 70 to 600 μm.
Moreover, the extrusion width of the layered thermoplastic resin (A) and the layered polyolefin resin (B) at the time of co-extrusion is not particularly defined, but can be, for example, 350 to 550 mm.

In the present invention, for example, as shown in FIG. 1, the laminate 6 is passed over the first roll 1. At this time, the first roll is arranged so that the continuous reinforcing fiber sheet (C) 2 side is in contact with the first roll 1. At this time, since the thermoplastic resin (A) is melted, if the continuous reinforcing fiber sheet (C) side of the laminate 6 is supported by the first roll 1, the continuous reinforcing fiber sheet (C) side ( (Lower side) and impregnation proceeds. As described above, the thermoplastic resin (A) and the polyolefin resin (B) are coextruded so that the thermoplastic resin (A) is on the continuous reinforcing fiber sheet side. Compared with the case of extruding, the temperature of the resin is less likely to decrease, and a high impregnation property can be achieved. Moreover, since the polyolefin resin (B) has low affinity with the continuous reinforcing fiber sheet (C), the polyolefin resin (B) itself does not impregnate the continuous reinforcing fiber sheet (C). In addition, since the polyolefin resin (B) has a melting point lower than that of the thermoplastic resin (A), it is cured before the thermoplastic resin (A). From this viewpoint, the thermoplastic resin (A) is impregnated, but the polyolefin resin (B) is not impregnated into the continuous reinforcing fiber sheet (C).
Further, as described above, in the melt laminating method, in order to obtain a composite film having a high ratio of continuous reinforcing fibers, it is conceivable to extrude a thermoplastic resin thinly from a die. However, in the conventional melt laminating method, it is difficult to increase the thickness accuracy in the width direction of the resin to be melt-extruded, and it is sometimes difficult to suppress variations in the width direction of the resulting composite film. On the other hand, in the present invention, these problems are solved by co-extrusion of the thermoplastic resin (A) 3 and the polyolefin resin (B) 4.

  The first roll may be a roll whose surface is not thermally controlled (non-heating / non-cooling), but the surface temperature is a heating roll having a melting point of the thermoplastic resin (A) + 10 ° C. or higher. Is preferred. By employing a heating roll, the impregnation can proceed more effectively. The surface temperature of the first roll is more preferably a melting point + 10 ° C. or more, and particularly preferably a melting point + 15 ° C. or more. The upper limit value of the surface temperature of the first roll is not particularly defined, but can be a melting point + 100 ° C. or lower, and can be a melting point + 80 ° C. or lower.

In the present invention, it is preferable to dispose the second roll 5 also on the polyolefin resin (B) layer 4 side. More preferably, the polyolefin resin (B) layer 4 is in contact with the second roll 5. By providing the second roll 5, pressure is applied and the impregnation of the thermoplastic resin (A) proceeds more effectively. The second roll may be one whose surface is not thermally controlled (non-heating / non-cooling), or may be a cooling roll whose surface is cooled.
In the present invention, the surface temperature of the second roll is preferably less than the melting point of the polyolefin resin (B), more preferably (melting point of the polyolefin resin (B) −10 ° C.) to 10 ° C., 50 More preferably, the temperature is 10 ° C to 10 ° C. By making it less than melting | fusing point of polyolefin resin (B), cooling of polyolefin resin (B) advances more effectively and is preferable.
In the conventional method, when a continuous reinforcing fiber is impregnated with a thermoplastic resin having a high melting point by a melt laminating method, if a rubber roll is used, the thermoplastic resin adheres to the roll. However, in the present invention, even when a rubber roll is used as the second roll, the thermoplastic resin (A) does not adhere to the second roll, and therefore a rubber roll can be used. In addition, since the first roll that is not thermally controlled can be used, a rubber roll can be used. Of course, it goes without saying that the first and second rolls may be metal rolls. In particular, as the thermoplastic resin (A), for example, when a xylylenediamine-based polyamide resin (hereinafter sometimes referred to as “XD-based polyamide resin”) is used, the XD-based polyamide resin tends to adhere to a metal. In this method, a metal roll is difficult to use, but in the present invention, a metal roll can be used as the second roll by using the polyolefin resin (B).
In addition, the roll in this invention is the meaning containing the thing of the other form which plays the same role as a roll.

A preferred embodiment of the present invention is a heating in which the first roll and the second roll are a pair of rolls as shown in FIG. 1, and the surface temperature of the first roll is thermally controlled at the above-described temperature. It is a form that is a roll. By setting it as such a form, a thermoplastic resin (A) can be more easily impregnated to a continuous reinforcement fiber sheet (C). In such an embodiment, even if the temperature of the thermoplastic resin (A) at the time of extrusion is relatively low, such as the melting point of the thermoplastic resin (A) + 5 ° C. to the melting point + 50 ° C., the impregnation is effectively performed. Is possible.
In the manufacturing method of the composite film of this invention, you may have a conveyance roll other than the above-mentioned.

  Then, the latter half part of the manufacturing method of the composite film of this invention is demonstrated with reference to FIG. When the continuous reinforcement fiber sheet (C) is impregnated with the thermoplastic resin (A), the laminate 6 is, as shown in FIG. 2, the continuous reinforcement fiber sheet (C) impregnated with the thermoplastic resin (A). A composite material 8 having a polyolefin resin (B) layer 4 on 7 is formed. In the composite material 8 of the present invention, some or no unimpregnated thermoplastic resin (A) 9 may remain between the continuous reinforcing fiber sheet (C) 7 and the polyolefin resin (B) layer 4. It is preferable. The unimpregnated thermoplastic resin (A) 9 may be formed into a thin layer as shown in FIG. 2, or a clear layer may not be formed.

  Although the composite material 8 of the present invention may be used as it is, it is usually separated into the continuous reinforcing fiber sheet (C) 7 impregnated with the thermoplastic resin (A) and the polyolefin resin (B) layer 4. Thus, a composite film 10 which is a continuous reinforcing fiber sheet (C) impregnated with the thermoplastic resin (A) is obtained (right side in FIG. 2). In the state of the composite material 8, since the thermoplastic resin (A) and the polyolefin resin (B) are usually cured and are different from each other, the polyolefin resin (B) layer 4 is used as the composite material 8. Can be easily peeled off. At this time, if some unimpregnated thermoplastic resin (A) 9 remains, it usually remains on the composite film 10 side. The unimpregnated thermoplastic resin (A) remaining on the composite film 10 side may be peeled off or used as it is.

Thereafter, the composite film 10 is preferably wound on a winding roll.
Alternatively, the composite material 8 having the polyolefin resin (B) layer 4 may be wound and stored on a roll or the like. When the thermoplastic resin (A) is a highly hygroscopic resin, the polyolefin resin (B) layer 4 plays a role as a hygroscopic prevention film. When wound on a roll or the like in the state of the composite material 8, it is preferable to peel off the polyolefin resin (B) layer 4 when the composite film 10 is used.
Moreover, the composite film 10 in this invention can be cut and used for desired length after that.

As for the thickness of the composite film in this invention, it is more preferable that they are 20 micrometers-300 micrometers, and it is further more preferable that they are 40 micrometers-150 micrometers.
In the present invention, the surface roughness (Ry) on the side in contact with the polyolefin (B) layer of the composite film can be reduced, for example, less than 50 μm. The method for measuring the surface roughness (Ry) is a value measured by the method described in Examples described later.

The composite film in the present invention has a void ratio of preferably 15% or less, more preferably 10% or less, further preferably 9% or less, and particularly preferably 8% or less.
The void ratio in the present invention refers to a value specified by a method defined in Examples described later. When it is difficult to obtain the measuring instrument described in the examples due to the out of print version, it can be measured with another measuring instrument having equivalent performance. The same applies to other measurement methods described below.
The ratio of continuous reinforcing fibers in the composite film is preferably 10 V / V% or more, more preferably 20 V / V% or more, further preferably 30 V / V% or more, and further 40 V / V% or more. In particular, it may be 45 V / V% or more. Further, it is preferably 80 V / V% or less, more preferably 70 V / V% or less, further 60 V / V% or less, and particularly 55 V / V% or less. The ratio of the continuous reinforcing fibers in the composite film can be adjusted by the extrusion thickness of the thermoplastic resin (A) as described above.
Here, V / V% refers to the ratio of the volume of continuous reinforcing fibers to the total volume of the composite film. The ratio of the continuous reinforcing fiber in the present invention refers to a value measured by the method described in Examples described later.

The melting point of the thermoplastic resin (A) used in the present invention is not particularly defined as long as it is 190 ° C or higher, but the lower limit is preferably 200 ° C or higher, more preferably 210 ° C or higher. , 220 ° C. or higher, and further 230 ° C. or higher. The upper limit is preferably 350 ° C. or less, more preferably 330 ° C. or less, can be 320 ° C. or less, can be 310 ° C. or less, and particularly 300 ° C. or less. You can also
The melting point in the present invention is the temperature at the peak top of the endothermic peak at the time of temperature rise observed by the DSC (Differential Scanning Calorimetry) method, and specifically refers to the value measured by the following method. .
<Measurement method>
Using DSC-60 manufactured by SHIMADZU CORPORATION, the sample amount is about 1 mg, nitrogen gas is flowed at 30 ml / min as the atmospheric gas, and the temperature rising rate is from room temperature (25 ° C.) at 10 ° C./min. An endothermic peak observed when the molten thermoplastic resin is heated and melted to a temperature above the expected melting point, and then the molten thermoplastic resin is quenched with dry ice and heated again to a temperature above the melting point at a rate of 10 ° C./min. The peak top temperature of is taken as the melting point.
When the thermoplastic resin has two or more melting points, the lower melting point is set as the melting point of the thermoplastic resin (A) in the present invention. In addition, as described later, the thermoplastic resin (A) in the present invention may be two or more types. In this case, the thermoplastic resin (A) in the present invention has the melting point of the thermoplastic resin having the lowest melting point. Of melting point.

The type of the thermoplastic resin (A) used in the present invention is not particularly defined, and a wide range of thermoplastic resins having a melting point of 190 ° C. or higher can be used. A crystalline thermoplastic resin having a melting point of 190 ° C. or higher is preferable. A polyamide resin having a melting point of 190 ° C. or higher is more preferable.
The thermoplastic resin (A) used in the present invention is preferably selected from polyamide resins, polyphenylene sulfide resins, aromatic polyetherketone resins and polyimide resins having a melting point of 190 ° C. or higher, and polyamides having a melting point of 190 ° C. or higher. A resin is preferred. Only one type of thermoplastic resin (A) may be used, or two or more types of blends may be used.

式（２）

（式（２）中、Ｘは、メチルペンタメチレン基またはメチルオクタメチレン基である。） Polyamide resins having a melting point of 190 ° C. or higher used in the present invention include polyamide 46, polyamide 6, polyamide 610, polyamide 66, polyamide 6T / 66, polyamide 6T, polyamide 6T / 6I, polyamide 9T, polyamide 10T, and the following formula (1 ) And a polyamide resin mainly composed of a structural unit selected from the structural unit represented by the following formula (2), and an XD-based polyamide resin are preferable, and an XD-based polyamide resin is more preferable.
Formula (1)

Formula (2)

(In Formula (2), X is a methylpentamethylene group or a methyloctamethylene group.)

Here, the polyamide 46 is a polymer obtained by polycondensation of butylene diamine and adipic acid, but may contain a constituent unit derived from diamine or dicarboxylic acid other than these as long as the melting point is not less than 190 ° C. Moreover, the structural unit derived from lactams and aliphatic aminocarboxylic acids may be included. The same applies to polyamide 6, polyamide 610, polyamide 66, polyamide 6T / 66, polyamide 6T, polyamide 6T / 6I, polyamide 9T, polyamide 10T and the like.
Further, “having a structural unit selected from the structural unit represented by the following formula (1) and the structural unit represented by the following formula (2) as a main component” means that the structure represented by the formula (1) The total amount of the unit and the structural unit represented by the formula (2) is 50 mol% or more of the total structural unit, more preferably 70 mol%, and still more preferably 90 mol% or more. X is preferably a 2-methylpentamethylene group or a 2-methyloctamethylene group.
On the other hand, the XD polyamide resin in the present invention refers to a polyamide resin containing a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, and 50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine.

The XD-based polyamide resin is preferably composed of 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more of the structural unit derived from diamine derived from xylylenediamine and derived from dicarboxylic acid. The α, ω-straight chain is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, preferably 4 to 20 carbon atoms. It is preferably derived from an aliphatic dicarboxylic acid.
The xylylenediamine may be paraxylylenediamine, metaxylylenediamine, or a mixture of both.

Examples of diamines other than metaxylylenediamine and paraxylylenediamine that can be used as a raw material diamine component of the XD polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, Aliphatic diamines such as octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis ( Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bi Alicyclic diamines such as (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene, etc. The diamine etc. which have the following aromatic ring can be illustrated, and can be used 1 type or in mixture of 2 or more types.
When a diamine other than xylylenediamine is used as the diamine component, it is less than 50 mol% of the structural unit derived from diamine, preferably 30 mol% or less, more preferably 1 to 25 mol%, particularly preferably. Used in a proportion of 5 to 20 mol%.

Preferred examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms to be used as a raw material dicarboxylic acid component of the XD-based polyamide resin include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid can be exemplified, and adipic acid and sebacic acid are preferable, and one or a mixture of two or more can be used.
As an example of the embodiment of the dicarboxylic acid component in the present invention, there may be mentioned an embodiment in which 70 mol% or more, preferably 90 mol% or more of the structural unit derived from dicarboxylic acid is adipic acid. Another example of the embodiment of the dicarboxylic acid component in the present invention is an embodiment in which 70 mol% or more, preferably 90 mol% or more of the structural unit derived from dicarboxylic acid is sebacic acid.

  Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- Examples thereof include naphthalenedicarboxylic acid such as isomers such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and one kind or a mixture of two or more kinds can be used.

  When a dicarboxylic acid other than an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component, terephthalic acid or isophthalic acid may be used from the viewpoint of molding processability and barrier properties. preferable. The proportion of terephthalic acid and isophthalic acid is preferably 30 mol% or less, more preferably 1 to 30 mol%, and particularly preferably 5 to 20 mol% of the dicarboxylic acid structural unit.

  Furthermore, in addition to the diamine component and the dicarboxylic acid component, as components constituting the XD-based polyamide resin, lactams such as ε-caprolactam and laurolactam, aminocaproic acid, aminoundecanoic acid, etc., as long as the effects of the present invention are not impaired. Aliphatic aminocarboxylic acids can also be used as copolymerization components. These components are preferably 3% by mass or less of the XD polyamide resin.

  The XD polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000 to 30,000, more preferably 8,000 to 28,000, still more preferably 9,000 to 9000. It is 26,000, More preferably, it is 10,000-24,000, Most preferably, it is 11,000-22,000. Within such a range, the heat resistance, elastic modulus, dimensional stability, and moldability become better.

The number average molecular weight (Mn) referred to here is the following formula based on the terminal amino group concentration [NH ₂ ] (μ equivalent / g) and the terminal carboxyl group concentration [COOH] (μ equivalent / g) of the polyamide resin. Calculated.
Number average molecular weight (Mn) = 2,000,000 / ([COOH] + [NH ₂ ])

The XD polyamide resin used in the present invention preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of 1.8 to 3.1. The molecular weight distribution is more preferably 1.9 to 3.0, still more preferably 2.0 to 2.9. By setting the molecular weight distribution in such a range, a composite material having excellent mechanical properties tends to be easily obtained.
The molecular weight distribution of the XD polyamide resin can be adjusted, for example, by appropriately selecting the polymerization reaction conditions such as the type and amount of the initiator and catalyst used during the polymerization, and the reaction temperature, pressure, and time. It can also be adjusted by mixing a plurality of types of XD polyamide resins having different average molecular weights obtained under different polymerization conditions or by separately precipitating the polymerized XD polyamide resins.

  The molecular weight distribution can be determined by GPC measurement. Specifically, using “HLC-8320GPC” manufactured by Tosoh as an apparatus and two “TSK gel Super HM-H” manufactured by Tosoh as columns, eluent trifluoro Measured under conditions of hexafluoroisopropanol (HFIP) having a sodium acetate concentration of 10 mmol / l, a resin concentration of 0.02% by weight, a column temperature of 40 ° C., a flow rate of 0.3 ml / min, and a refractive index detector (RI). It can be determined as a value in terms of methacrylate. A calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.

The XD-based polyamide resin preferably has a terminal amino group concentration ([NH ₂ ]) of less than 100 μequivalent / g, more preferably 5 to 75 μequivalent / g, and still more preferably 10 to 60 μequivalent / g. The carboxyl group concentration ([COOH]) is preferably less than 150 μeq / g, more preferably 10 to 120 μeq / g, and still more preferably 10 to 100 μeq / g. By using the XD-based polyamide resin having such a terminal group concentration, the viscosity is easily stabilized when the XD-based polyamide resin is processed into a film or fiber, and the reactivity with a carbodiimide compound described later is good. Tend to be.

The ratio of the terminal amino group concentration to the terminal carboxyl group concentration ([NH ₂ ] / [COOH]) is preferably 0.7 or less, more preferably 0.6 or less, particularly preferably 0. .5 or less. When this ratio is larger than 0.7, it may be difficult to control the molecular weight when polymerizing the XD polyamide resin.

The terminal amino group concentration can be measured by dissolving 0.5 g of XD polyamide resin in 30 ml of a phenol / methanol (4: 1) mixed solution with stirring at 20-30 ° C. and titrating with 0.01 N hydrochloric acid. . As for the terminal carboxyl group concentration, 0.1 g of XD polyamide resin is dissolved in 30 ml of benzyl alcohol at 200 ° C., and 0.1 ml of phenol red solution is added in the range of 160 ° C. to 165 ° C. The solution was titrated with a titration solution (KOH concentration 0.01 mol / l) in which 0.132 g of KOH was dissolved in 200 ml of benzyl alcohol, and when the color change changed from yellow to red, the end point was reached. Can be calculated.
Regarding the method for producing the XD-based polyamide resin, the description in paragraphs 0052 to 0053 of JP-A-2014-173196 can be referred to, and the contents thereof are incorporated in the present specification.

  The thermoplastic resin (A) used in the present invention includes a stabilizer such as an antioxidant and a heat stabilizer, a hydrolysis resistance improver, a weather resistance stabilizer, a gloss as long as the object and effect of the present invention are not impaired. Additives such as quenching agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, mold release agents and the like can be added. For details of these, reference can be made to the description of paragraph numbers 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein.

The polyolefin resin (B) used in the present invention is not particularly defined as to its type, but preferably contains at least one selected from polyethylene resins and polypropylene resins.
Specific examples of the polyethylene resin include low density polyethylene (LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), high pressure method low density polyethylene (HPLDPE), linear low density polyethylene (LLDPE), ultra-low Density polyethylene (VLDPE), low crystalline ethylene-1-butene random copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Etc.
A polyolefin resin (B) may be used individually by 1 type, or may use 2 or more types together.
The melting point of the polyolefin resin (B) is preferably less than 200 ° C, and more preferably 80 to 180 ° C. Further, the difference between the melting point of the thermoplastic resin (A) and the melting point of the polyolefin resin (B) is preferably 20 ° C. or higher, and more preferably 30 ° C. or higher. The upper limit of the difference between the melting points is not particularly defined, but can be set to 100 ° C. or less, for example.

The continuous reinforcing fiber sheet (C) used in the present invention is usually a sheet in which continuous reinforcing fibers are dispersed and arranged in one direction or two or more directions to form a sheet. Thus, it may be dispersed randomly like a non-woven fabric, or may be regularly arranged like a woven or knitted fabric, and is preferably arranged regularly. Also, woven or knitted of continuous reinforcing fibers, preferably has a basis weight is 10 to 1000 g / m ^2, more preferably from 50 to 500 g / m ^2, still to be 50 to 300 g / m ² preferable.
The thickness of the continuous reinforcing fiber sheet (C) depends on the thickness of the composite film, but is preferably 15 to 500 μm, for example.
Examples of continuous reinforcing fibers include plant fibers, carbon fibers, glass fibers, alumina fibers, boron fibers, ceramic fibers, aramid fibers, and the like, and are preferably at least one of carbon fibers and glass fibers, and are carbon fibers. It is more preferable. As the carbon fiber, polyacrylonitrile-based carbon fiber and pitch-based carbon fiber can be preferably used. Moreover, carbon fibers of plant-derived materials such as lignin and cellulose can also be used. Moreover, the continuous reinforcing fiber used in the present invention may be treated with a surface treatment agent or a sizing agent.

  The field of use of the composite film in the present invention is not particularly defined, such as automobile transport parts, general machine parts, precision machine parts, electronic / electric equipment parts, OA equipment parts, building materials / householding related parts, medical devices, Widely used in daily goods such as leisure sports goods, play equipment, medical products, food packaging films, defense and aerospace products.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Raw materials>
Thermoplastic resin (A1): MX nylon S6001, manufactured by Mitsubishi Gas Chemical Co., Ltd., melting point: 237 ° C. (polycondensate of metaxylylenediamine and adipic acid)
Polyolefin resin (B): Novatec PP FY6, manufactured by Nippon Polypro, melting point: 168 ° C
Continuous reinforcing fiber sheet (C): carbon fiber Sakai Obex, fabric, part number BHH-100G16WH, basis weight: 100 g / m ² , thickness: 100 μm

<Synthesis of thermoplastic resin (A2)>
6450 g (44.14 mol) of adipic acid precisely weighed in a reaction vessel having an internal volume of 50 liters equipped with a stirrer, a condenser, a cooler, a thermometer, a dropping device and a nitrogen introduction tube and a strand die, hypophosphorous acid Sodium monohydrate calcium 12.98 g (0.122 mol) and sodium acetate 6.73 g (0.082 mol) were weighed and charged. After sufficiently replacing the inside of the reaction vessel with nitrogen, the pressure was increased to 0.4 MPa with nitrogen, the temperature was raised from 20 ° C. to 190 ° C. with stirring, and adipic acid was uniformly melted in 55 minutes. Subsequently, a mixed diamine of 4172 g (30.63 mol) of metaxylylenediamine and 1788 g (13.13 mol) of paraxylylenediamine was added dropwise with stirring. During this time, the internal temperature of the reaction vessel was continuously increased to 293 ° C. In the dropping step, the pressure was controlled to 0.42 MPa, and the generated water was removed from the system through a partial condenser and a cooler. The temperature of the partial condenser was controlled in the range of 145 to 147 ° C. After completion of the dropwise addition of the mixed diamine, the polycondensation reaction was continued for 20 minutes at a reaction vessel internal pressure of 0.42 MPa. During this time, the temperature inside the reaction vessel was raised to 296 ° C. Thereafter, the internal pressure of the reaction vessel was reduced from 0.42 MPa to 0.12 MPa over 30 minutes. During this time, the internal temperature rose to 298 ° C. Thereafter, the pressure was reduced at a rate of 0.002 MPa / minute, the pressure was reduced to 0.08 MPa over 20 minutes, and the amount of the component having a molecular weight of 1,000 or less was adjusted. The temperature in the reaction vessel at the time of completion of decompression was 301 ° C. Thereafter, the inside of the system was pressurized with nitrogen, and the polymer was taken out from the strand die in a strand shape at a reaction vessel temperature of 301 ° C. and a resin temperature of 301 ° C., cooled with cooling water at 20 ° C. A polyamide resin was obtained. The melting point was 255 ° C.

<Synthesis of thermoplastic resin (A3)>
In a reaction vessel having an internal volume of 50 liters equipped with a stirrer, a condenser, a cooler, a thermometer, a nitrogen introducing tube, and a strand die, 8950 g (44.25 mol) of sebacic acid precisely measured, calcium hypophosphite 12 .54 g (0.074 mol) and 6.45 g (0.079 mol) of sodium acetate were weighed and charged. After sufficiently purging the inside of the reaction vessel with nitrogen, the pressure was increased to 0.4 MPa with nitrogen, the temperature was raised from 20 ° C. to 190 ° C. with stirring, and sebacic acid was uniformly melted in 55 minutes. Subsequently, a mixed diamine of 4172 g (30.63 mol) of metaxylylenediamine and 1788 g (13.13 mol) of paraxylylenediamine was added dropwise with stirring. During this time, the internal temperature of the reaction vessel was continuously increased to 293 ° C. In the dropping step, the pressure was controlled to 0.42 MPa, and the generated water was removed from the system through a partial condenser and a cooler. The temperature of the partial condenser was controlled in the range of 145 to 147 ° C. After completion of the dropwise addition of the mixed diamine, the polycondensation reaction was continued for 20 minutes at a reaction vessel internal pressure of 0.42 MPa. During this time, the temperature inside the reaction vessel was raised to 296 ° C. Thereafter, the internal pressure of the reaction vessel was reduced from 0.42 MPa to 0.12 MPa over 30 minutes. During this time, the internal temperature rose to 298 ° C. Thereafter, the pressure was reduced at a rate of 0.002 MPa / minute, the pressure was reduced to 0.08 MPa over 20 minutes, and the amount of the component having a molecular weight of 1,000 or less was adjusted. The temperature in the reaction vessel at the time of completion of decompression was 301 ° C. Thereafter, the inside of the system was pressurized with nitrogen, the temperature in the reaction vessel was 301 ° C., the resin temperature was 301 ° C., the polymer was taken out from the strand die into a strand shape, cooled with 20 ° C. cooling water, pelletized, and about 13 kg. A polyamide resin was obtained. The melting point was 213 ° C.

<Example 1>
A thermoplastic resin (A1) is used on the surface of the above-mentioned continuous reinforcing fiber sheet (C) by using two single-screw extruders, a feed block, and a two-type two-layer multilayer extruder (manufactured by Plastics Engineering Laboratory) having a T-die. ) Is melt-extruded by a single screw extruder having a 30 mmφ screw, and the polyolefin resin (B) is melt extruded by a single screw extruder having a 30 mmφ screw. Through coextrusion. The temperature of the thermoplastic resin (A1) during extrusion was the melting point of the thermoplastic resin (A1) + 30 ° C., and the temperature of the polyolefin resin (B) was the melting point of the polyolefin resin (B) + 30 ° C. Moreover, at this time, it coextruded so that a thermoplastic resin (A1) might become the continuous reinforcement fiber sheet (C) side. The extrusion width was 450 mm, the extrusion thickness of the polyolefin resin (B) was 200 μm, and the extrusion thickness of the thermoplastic resin (A1) was 66 μm.
The laminate of the continuous reinforcing fiber sheet (C), the layered thermoplastic resin (A1), and the layered polyolefin resin (B) was passed between a pair of rolls. The lower rolls of the pair of rolls were heating rolls (made of metal, Hydeck, high-frequency heating heat roll) set to the melting point of the thermoplastic resin (A1) + 20 ° C., and the upper rolls were rubber rolls having a surface at room temperature.
The continuous reinforcing fiber sheet (C) is impregnated with the thermoplastic resin (A1) and cured, and then the layered polyolefin resin (B) is peeled off, and the thermoplastic resin (A1) is impregnated with the continuous reinforcing fiber sheet (C). A composite film was obtained. The thickness of the obtained composite film was 110 μm.
The following evaluation was performed about the obtained composite film.

<< Measurement Method of Void Ratio of Composite Film >>
The void ratio of the composite film was measured according to the following method.
The composite film is cut in the thickness direction, and the cross section and its periphery are embedded with an epoxy resin, and then polished so that the cross section in the thickness direction is exposed, and the cross section is subjected to an ultra-deep color 3D shape measurement microscope VK-9500 (controller part) Photographed using / VK-9510 (measurement unit) (manufactured by Keyence). With respect to the obtained cross-sectional photograph, a void region was selected using image analysis software ImageJ, and its area was measured. Based on the measured value, (void area of cross section of composite film / image cross sectional area) × 100 was calculated. For one composite film, the above measurement is performed at three locations near the first roll of the composite film, near the second roll, and near the center of the composite film. The void ratio (unit:%) was rounded off. It can be said that the lower the void ratio, the better the impregnation.

<< Method for measuring ratio of continuous reinforcing fibers in composite film >>
The ratio of continuous reinforcing fibers in the composite film was measured according to JIS 7075 combustion method. The unit of the ratio of continuous reinforcing fibers is indicated by V / V%.

<< Smoothness >>
According to JIS B 0601-1994, the surface roughness (Ry) on the side in contact with the polyolefin (B) layer was measured. Specifically, the test piece was cut out, and an arbitrary 7 mm in the cross section perpendicular to the film surface on the side in contact with the polyolefin (B) layer of the composite film was roughly roughened using a Keyence shape measurement microscope VHX-1000. It was a curve. The distance between the peak line and the valley line of this roughness curve was measured, and this value (Ry) was expressed in μm. Ry was evaluated as follows.
A: Ry is less than 50 μm B: Ry is 50 μm or more

<Example 2>
In Example 1, the thermoplastic resin (A1) was changed to the thermoplastic resin (A2), and the others were performed in the same manner. Regarding various temperatures, the melting point of the thermoplastic resin (A1) in Example 1 was replaced with the melting point of the thermoplastic resin (A2).

<Example 3>
In Example 1, the thermoplastic resin (A1) was changed to the thermoplastic resin (A3), and the others were performed in the same manner. Various temperatures were also obtained by replacing the melting point of the thermoplastic resin (A1) in Example 1 with the melting point of the thermoplastic resin (A3).

<Comparative Example 1>
In Example 1, the polyolefin resin (B) was not used, only the thermoplastic resin (A1) was melt-extruded in a single layer, and the others were performed in the same manner.

<Comparative example 2>
In Example 2, the polyolefin resin (B) was not used, only the thermoplastic resin (A2) was melt-extruded in a single layer, and the others were performed in the same manner.

The results are shown in Table 1 below.

  As is clear from the above results, in the method for producing a composite film of the present invention, it became possible to impregnate a continuous reinforcing fiber with a thermoplastic resin having a high melting point in spite of a simple method (Example 1 to Example 1). 3). Furthermore, it was found that the obtained composite material had a low void ratio and was well impregnated. In addition, the smoothness of the composite film obtained was also high. On the other hand, in the case of single layer melting, the void ratio of the obtained composite film was high, and the smoothness was also lacking (Comparative Examples 1 and 2).

1 First roll 2 Continuous reinforcing fiber sheet (C)
3 Thermoplastic resin (A)
4 Polyolefin resin (B), polyolefin resin (B) layer 5 Second roll 6 Laminate 7 Continuous reinforcing fiber sheet 8 impregnated with thermoplastic resin Composite material 9 Unimpregnated thermoplastic resin 10 Composite film

Claims (12)

A method for producing a composite film in which a continuous reinforcing fiber sheet (C) is impregnated with a thermoplastic resin (A) having a melting point of 190 ° C. or higher,
To the surface of the continuous reinforcing fiber sheet (C), and the thermoplastic resin (A) and the polyolefin resin (B), layered as the thermoplastic resin (A) side is in contact said continuous reinforcing fiber sheet (C) A method for producing a composite film, comprising co-extrusion and then placing a roll on the continuous reinforcing fiber sheet (C) side and impregnating the continuous reinforcing fiber sheet (C) with the thermoplastic resin (A). The manufacturing method of the composite film of Claim 1 whose temperature of the surface of the said roll is more than melting | fusing point +10 degreeC of a thermoplastic resin (A). Furthermore, after coextruding in the said layer shape, the manufacturing method of the composite film of Claim 1 or 2 which distribute | arranges a 2nd roll also to the said polyolefin resin (B) side. The manufacturing method of the composite film of Claim 3 whose surface temperature of a said 2nd roll is less than melting | fusing point of polyolefin resin (B). The composite film according to any one of claims 1 to 4, wherein the thermoplastic resin (A) is at least one selected from a polyamide resin, a polyphenylene sulfide resin, an aromatic polyether ketone resin, and a polyimide resin. Manufacturing method. The thermoplastic resin (A) is polyamide 46, polyamide 6, polyamide 610, polyamide 66, polyamide 6T / 66, polyamide 6T, polyamide 6T / 6I, polyamide 9T, polyamide 10T, and a structure represented by the following formula (1). A polyamide resin having as a main component a structural unit selected from the structural unit represented by the unit and the following formula (2), and a structural unit derived from diamine and a structural unit derived from diamine, The method for producing a composite film according to any one of claims 1 to 4, wherein 50 mol% or more is at least one selected from polyamide resins derived from xylylenediamine;
Formula (1)

Formula (2)

In formula (2), X is a methylpentamethylene group or a methyloctamethylene group. The thermoplastic resin (A) includes a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, and 50 mol% or more of the structural unit derived from the diamine is selected from polyamide resins derived from xylylenediamine. The manufacturing method of the composite film of any one of Claims 1-4 which is these. The method for producing a composite film according to claim 7, wherein the dicarboxylic acid is at least one of adipic acid and sebacic acid. The method for producing a composite film according to any one of claims 1 to 8, wherein the continuous reinforcing fiber sheet (C) is a woven or knitted fabric of continuous reinforcing fibers. The manufacturing method of the composite film of any one of Claims 1-9 in which the said polyolefin resin (B) contains at least 1 sort (s) selected from a polyethylene resin and a polypropylene resin. The ratio of the thickness of the layered thermoplastic resin (A) and the layered polyolefin resin (B) after the coextrusion is 10: 1 to 10: 500, according to any one of claims 1 to 10. The manufacturing method of the composite film of description. The composite according to any one of claims 1 to 11, further comprising separating the continuous reinforcing fiber sheet (C) impregnated with the thermoplastic resin (A) and the layered polyolefin resin (B). A method for producing a film.

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