WO2003102055A1

WO2003102055A1 - Paper-free prepregs

Info

Publication number: WO2003102055A1
Application number: PCT/JP2003/006511
Authority: WO
Inventors: Atsushi Kawakami; Yoshihiro Endo; Hideaki Tominaga; Etsuhiro Hikawa
Original assignee: Toho Tenax Co., Ltd.
Priority date: 2002-05-30
Filing date: 2003-05-26
Publication date: 2003-12-11
Also published as: TW200404845A; AU2003235428A1

Abstract

A paper-free prepreg constituted of a reinforcing fiber-matrix layer prepared by impregnating a reinforcing fiber with a non-cured matrix resin and a releasing resin film which has a heavy surface exhibiting a high peel strength and a light surface exhibiting a low peel strength and adheres to one surface of the reinforcing fiber-matrix layer with the heavy surface being in contact with the reinforcing fiber-matrix layer, wherein the heavy surface exhibits a peel strength of 200 g/cm or below and the peel strength ratio of the heavy surface to the light surface is 3.0 or above; and a paper-free prepreg as described above which has a cover film adhering to the other surface thereof. When the cover film is a specific thermoplastic resin film made from polyamide 12, ionomer or the like, the prepreg can be molded without removing the cover film.

Description

Description: ぺ -free prepreg Technical field

The present invention relates to a paper-free prepreg having no cellulosic release paper, and a method for producing the same. More specifically, the present invention relates to a paper-free prepreg in which a mold release resin film having a heavy surface and a light surface having different peeling resistance values on different sides of the mold release resin film is adhered to one surface of a reinforcing fiber matrix layer. Further, the present invention relates to a paper-free prepreg in which a cover film and a release resin film are adhered to a reinforcing fiber matrix layer. Still further, in the present invention, a cover film and a mold release resin film having a heavy surface and a light surface having different peel resistance values on the front and back of the mold release resin film are adhered to the reinforcing fiber matrix layer. It relates to a paper-free prepredder. Further, the present invention provides a paper-free prepreg comprising a thermoplastic resin film adhered on one surface of a reinforcing fiber matrix layer and a release resin film having a heavy surface and a light surface on the other surface. The present invention relates to a method for producing a paper-free pre-preda and a method for producing a molded article using the paper-free pre-preda. Background art

Conventionally, a prepreg formed by impregnating a thermosetting resin into a reinforcing fiber into a sheet is used as a material for fiber-reinforced plastic products, such as in the manufacture of aircraft, golf shafts, fishing rods, etc., and also for the reinforcement of concrete bridges and buildings. It is used for

Usually, release paper mainly composed of cellulose is adhered to the surface of the pre-preda so that the pre-preda does not adhere to each other during storage or transfer. When using the prepreg, the release paper is peeled off from the prepreg surface. Waste.

However, the release paper made of cellulose as a main raw material is relatively hard, and thus becomes quite bulky after peeling. Furthermore, because of the releasability, many exhibit flame retardancy. For this reason, the release paper generated when using the pre-preda is a waste that is difficult to dispose of. For these reasons, it is a difficult problem to dispose of the release paper affixed to the prepredder.

As a solution to this problem, Japanese Patent Application Laid-Open No. H10-298315 discloses a pre-predder made by impregnating a thermosetting resin into long fibers or fabrics arranged in a sheet. However, there is disclosed a pre-predder having a resin film stretched on at least one surface thereof. The resin film is peeled off when the pre-preda is used. Then, the peeled resin film is discarded. Since the peeled resin film is flexible and not bulky like the release paper, it is described in the publication that the problem of the conventional release paper is solved.

However, there is a problem to be solved in the pre-predder other than the above-mentioned problem. That is, when the pre-preda is cut, the pre-preda curls. This curl occurs when the pre-preda is cut into a required shape before laminating the pre-preda into a molded body. The occurrence of curl has a great adverse effect on workability in the subsequent steps of manufacturing a molded article.

Further, the pre-preda is usually cut into a required shape before being processed into a molded body. When cutting the pre-preda, it is more efficient to peel off the cover film and then stack many pre-predars and cut them all at once. However, when the conventional pre-preda is stacked and cut at a time, the individual pre-predas stacked are stuck to each other and cannot be separated, which may hinder the subsequent molding process. For this reason, there is a problem that the efficiency of cutting work cannot be increased with the conventional pre-preda. Disclosure of the invention

The present inventor has developed a pre-preda having no release paper, and has previously filed a patent application (Japanese Patent Application Laid-Open No. 2002-105223). In this pre-preda, a thermoplastic resin film is adhered to one surface of a reinforcing fiber matrix layer in which reinforcing fibers are impregnated with an uncured matrix resin. The thermoplastic resin film functions as a release paper for preventing the prepregs from sticking to each other while the prepreg is being stored or transported. When using the pre-preda, the pre-preda is used without peeling off the thermoplastic resin film. For example, when a plurality of the pre-predas are laminated and then heated and cured to produce a molded body, the thermoplastic resin film has good adhesion to the matrix resin layer, so that the thermoplastic resin film is firmly fused to or adhered to the matrix resin layer, This is the structure itself. Therefore, no waste such as release paper or polymer film is generated during use as in the conventional pre-preda.

The present invention has been made to develop the above invention and to solve the conventional problems.

A first object of the present invention is to prevent the generation of flame-retardant waste such as release paper mainly made of cellulose which is peeled off and discarded during use. To provide.

Another object of the present invention is that the cell-based release paper is not generated as waste not only in use but also in the manufacturing process, and has good handleability and workability, and is peeled off and discarded in use. To provide a paper-free pre-reader having a small amount of a polymer film and the like, a method for producing the same, and a method for producing a molded article using the pre-predder

It is still another object of the present invention to provide a pre-preda with excellent dimensional stability which does not curl during storage, especially after cutting.

The present invention that achieves the above object is described below. (1) A mold release resin film having a reinforcing fiber matrix layer in which an uncured matrix resin is impregnated into reinforcing fibers, a heavy surface having a large peel resistance value and a light surface having a small peel resistance value. A resin film for release, which is adhered to one surface of the fiber reinforced matrix layer, wherein the release resistance of the heavy surface of the resin film for release is 200 gZcm or less, and the heavy and light surfaces are A paper-free pre-reader with a peel resistance ratio (heavy surface Z light surface) of 3.0 or more.

(2) The paper-free pre-reader according to (1), wherein the release resistance ratio between the heavy surface and the light surface of the release resin film is 5 or more.

(3) The paper-free prepreg according to (1), wherein the release resistance value of the heavy surface of the release resin film is 10 to 120 g / cm.

(4) The paper-free pre-reader according to (1), wherein the resin film for release has a heat shrinkage of 1% or less at 150 ° C.

(5) The paper-free pre-reader according to (1), wherein the reinforcing fibers are carbon fibers, glass fibers, or aramide fibers.

(6) The paper-free pre-reader according to (1), wherein the matrix resin is an epoxy resin composition.

(7) A reinforcing fiber matrix layer in which an uncured matrix resin is impregnated into reinforcing fibers, a cover film stuck on one surface of the fiber reinforced matrix layer, and a release surface on the other surface of the fiber reinforced matrix layer. A paper-free prepreg comprising a resin film for release, the release resistance of the release surface of the resin film for release being 0.5 to 200 g / cm.

(8) The paper-free pre-reader according to (7), wherein the release resistance value of the release resin film is 10 to 120 / cm: Ο.

(9) The paper-free prepreg according to (7), wherein the release resin film has a heat shrinkage of 1% or less at 150X. (10) The paper-free pre-reader according to (7), wherein the reinforcing fibers are carbon fibers, glass fibers, or aramide fibers.

(11) The paper-free bridpreda according to (7), wherein the matrix resin is an epoxy resin composition.

(1.2) The release resin film is a release resin film having a heavy surface having a large peel resistance value and a light surface having a small release resistance value, wherein the heavy surface is the other surface of the fiber reinforced matrix layer. The peeling resistance value of the heavy surface of the release resin film is 200 gZcm or less, and the peel resistance ratio (heavy surface / light surface) between the heavy surface and the light surface is 3 The paper free pre-reader according to (7), which has a value of 0 or more.

(13) The paper-free pre-reader according to (12), wherein the separation resistance ratio between the heavy surface and the light surface of the release resin film is 5 or more.

(14) The paper-free prepreg according to (13), wherein the release resistance value of the heavy surface of the release resin film is from 10 to 120 g / cm.

(15) The paper-free prepreg according to (12), wherein the release resin film has a heat shrinkage of 1% or less at 150 °.

(16) The paper-free pre-reader according to (7), wherein the peel resistance of the cover film is 0.5 to 200 gZcm.

(17) The vapor-free pre-predder according to (7), wherein the cover film is a release resin film having a heavy surface having a large peeling resistance value and a light surface having a small peeling resistance value.

(18) The paper-free pre-reader according to (7), wherein the cover film is formed of a thermoplastic resin film.

(19) The thermoplastic resin film is a polyamide 12 film, an ionomer film, a polyethylene terephthalate film having both surfaces subjected to corona discharge treatment, or a polybutylene terephthalate film having both surfaces subjected to corona discharge treatment (18) The described paper-free pre-preda. (20) The resin-free prepreg according to (18) is laminated and heated after peeling off the resin film for release, and a thermoplastic resin film is interposed between the cured matrix resins. A method of manufacturing a molded body.

(2 1) Two release resin films with a peel resistance value of the heavy surface of 150 g / cm or less and a peel resistance ratio (heavy surface / light surface) of the heavy surface to the light surface of 3 or more Applying a non-cured matrix resin to the resin film, sandwiching a reinforcing fiber between the two release resin films with the heavy surfaces of the two release resin films facing each other; and Pressurizing the fibers from outside of the release resin film under heating to impregnate the reinforced fibers with the uncured matrix resin, and convert one of the two release resin films into reinforced fibers A reinforcing fiber matrix layer obtained by impregnating reinforcing fibers with an uncured matrix resin, which is characterized in that the uncured matrix resin is peeled off from the impregnated uncured matrix resin and a thermoplastic resin film is pressure-bonded to the peeled uncured matrix resin surface; The fiber reinforced mat A thermoplastic resin film adhered to one surface of the resin layer, and a resin film for release in which the release surface is adhered to the other surface of the fiber reinforced matrix layer, and the release surface of the resin film for release. A method for producing a paper-free prepreg having a peel resistance of 150 g / cm or less.

(2 2) One of two release resin films with a peel resistance value of 150 g / cm or less on the heavy surface and a peel resistance ratio (heavy surface / light surface) of the heavy surface to the light surface of 3 or more. An uncured matrix resin is applied to the heavy surface of the sheet, and the heavy surface of the release resin film coated with the uncured matrix resin and the light surface of the release resin film without the uncured matrix resin are opposed to each other. The reinforcing fiber is sandwiched between these two release resin films, and the sandwiched reinforcing fiber is pressurized from the outside of the release resin film under heating, so that the uncured matrix resin is added to the reinforcing fibers. Impregnating process and two resin film The mold release resin film having the light surface on the inside is peeled off from the uncured matrix resin impregnated with the reinforcing fibers, and a thermoplastic resin film is pressure-bonded to the peeled uncured matrix resin surface. A reinforcing fiber matrix layer in which a cured matrix resin is impregnated into reinforcing fibers, a thermoplastic resin film adhered to one surface of the fiber reinforced matrix layer, and a release surface adhered to the other surface of the fiber reinforced matrix layer. And the release resistance of the release surface of the release resin film is 1

A method for producing a paper-free pre-preda which is 50 g / cm or less. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic perspective view showing an example of a single-price pre-pre-reader according to a first embodiment of the present invention.

FIG. 2 is a process chart showing an example of a method for producing a resin coating film for impregnation in the first embodiment. FIG. 3 is a process chart showing an example of a method for manufacturing the paper-free pre-preda of the first embodiment.

FIG. 4 is a schematic perspective view showing an example of the paper-free pre-predder according to the second embodiment of the present invention.

FIG. 5 is a process chart showing an example of a method for producing a resin coating film for impregnation in the second embodiment. FIG. 6 is a process chart showing an example of a method for producing a paper-free pre-predder of the second embodiment.

FIG. 7 is a schematic perspective view showing an example of the paper-free pre-predder according to the third embodiment of the present invention.

FIG. 8 is a process chart showing an example of a method for producing a resin coating film for impregnation in the third embodiment.

FIG. 9 is a process chart showing an example of a method for manufacturing a paper-free pre-preda according to the third embodiment of the present invention.

FIG. 10 shows an example of a paper-free pre-reader according to a fourth embodiment of the present invention. It is a schematic perspective view shown.

FIG. 11 is a process chart showing an example of a method for producing a resin coating film for impregnation used for producing a paper-free prepreg of the fourth embodiment. FIG. 12 is a process chart showing an example of a method for manufacturing a paper-free pre-preda of the fourth mode.

FIG. 13 is a schematic side view showing an example of a molded body manufactured using the paper-free prepreg of the fourth embodiment.

FIG. 14 is a process chart showing an example of a production process of a paper free pre-preder without curl. FIG. 15 is a process chart showing another example of a production process of a pepper-free prepreg without curls. Reference numerals 1, 201, 301, 401 are pre-predators; 2, 202, 302, 402 are reinforced fiber matrix layers; 4, 204, 304, 04 are uncured matrices 6, 206, 306, 406, 506, 606 are reinforcing fibers; 208, 308, 528, 628 are cover films; 408 is heat Plastic resin film; 10, 10 2, 3 10, 4 10 are resin films for mold release; 12, 3 12, 4 12 are heavy surfaces; 14, 3 14, 4 14 are Light surface; 2 12, 2 14 is the surface of the release resin film; 2, 2 a to 2 d is the reinforcing fiber matrix layer; 8, 8 a to 8 c is the thermoplastic resin film; 300 b is a second pre-predader; 300 c is a third pre-predader; 530 is a replacement film. BEST MODE FOR CARRYING OUT THE INVENTION

(First form)

FIG. 1 is a schematic perspective view showing an example of the pre-preda of the present invention. In FIG. 1, reference numeral 1 denotes a pre-predeer, and the pre-predeer 1 is formed by attaching a release resin film 10 to one surface of a reinforcing fiber matrix layer 2. The mold release resin film 10 has a mold release resin film heavy surface 12 and a mold release resin film light surface 14 having different peeling resistance values on the front and back of the film 10. The release resistance value of the heavy surface 12 is larger than the release resistance value of the light surface 14. The release resin film 10 is adhered to the matrix layer such that its heavy surface 12 is in close contact with the reinforcing fiber matrix layer 2.

The reinforcing fiber matrix layer 2 is formed by impregnating the reinforcing fibers 6 with the uncured matrix resin 4.

As the reinforcing fibers constituting the reinforcing fiber matrix layer, there can be used carbon fibers, glass fibers, aramide fibers, boron fibers, metal fibers, and other reinforcing fibers used in normal pre-preda. Among them, carbon fiber, glass fiber, and aramide fiber are preferable. The form of these reinforcing fibers includes a form aligned in one direction, a form aligned in multiple directions, and a form of a processed product of various reinforcing fibers such as a woven fabric, a knitted fabric, and a nonwoven fabric.

Examples of the uncured matrix resin to be impregnated into the reinforcing fibers include thermosetting resins used in ordinary prepreg production. Specifically, epoxy resin, unsaturated polyester resin, phenol resin, melamine resin, polyurethane resin, silicone resin, maleimide resin, cyanate ester resin, and resin obtained by prepolymerizing maleimide resin and cyanate ester resin, etc. No. Mixtures of these resins can also be used. In particular, when a fiber-reinforced composite material is used for the present pre-preda, an epoxy resin composition having excellent heat resistance, elastic modulus, and chemical resistance is preferable.

Further, these uncured matrix resins may contain a curing agent, a curing accelerator and the like. '

The mold release resin film 10 has a mold release resin film heavy surface 12 and a mold release resin film light surface 14 having different peel resistance values on the front and back of the film 10.

The material of the release resin film is polypropylene, polyethylene Examples thereof include terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyvinyl chloride, polyimide, polyacetate, and polypropionate. Polyvinyl chloride or the like, which may generate toxic substances such as dioxin when incinerated, is not preferred.

Examples of the method for forming the heavy and light surfaces on the front and back surfaces of the release resin film include a method of performing a release treatment on one or both surfaces of the film using a known method. Specifically, a heavy surface and a light surface can be formed on the front and back surfaces of the release resin film 10 by a known release property imparting treatment using a silicone resin, a fluorine resin, an aliphatic wax, or the like. From the viewpoint of heat resistance and versatility, a release treatment using a silicone resin is preferable.

Commercially available products can also be used as the release resin film. Examples of commercially available products include Purex film, Teonex film (all manufactured by Teijin Dubon Film Co., Ltd.), and Santo Tokusou MPRS type (manufactured by Santo Tokus Corporation).

In the pre-preda 1 of the present embodiment, the peeling resistance value of the heavy surface 12 of the release resin film 1 is set to 200 g / cm or less, and preferably 120 g / cm or less. If the peel resistance value of the heavy surface 1 2 exceeds 200 g / cm, the matrix resin 4 will be applied to the surface of the release resin film 10 when the release resin film 10 is released when using the pre-preda. Otherwise, the pre-preda 1 may be torn, making its handling extremely difficult. Further, it is more preferable that the peeling resistance value of the heavy surface 12 is 10 g / cm or more. If the peeling resistance value of the heavy surface 12 is less than 10 g / cm, the adhesion between the reinforcing fiber matrix layer 2 and the heavy surface 12 becomes insufficient, resulting in a floating defect (the surface of the fiber reinforced matrix layer is reinforced. This may cause the fiber to float) or hinder processing such as cutting the pre-predator 1.

The peel resistance ratio of the heavy surface 12 / light surface 14 of the release resin film 10 is set to 3.0 or more, preferably 5 or more. Peeling resistance ratio is 3. If the value is less than 0, the uncured matrix resin 4 will be easily partially transferred to the light surface 14 in the following pre-predder manufacturing process. As a result, it becomes difficult to obtain a resin film in which the uncured matrix resin is uniformly applied on the heavy surface 12. If the peel resistance ratio is 3.0 or more and less than 5, the matrix resin may partially transfer to the light surface 14 depending on the type of the uncured matrix resin 4.

In the present embodiment, the peel resistance is defined as an angle of 180 ° between the tape and the film to be peeled from a film to which a 25 mm-wide adhesive tape (NITTO 3 IB, manufactured by Nitto Denko Corporation) is attached. This refers to the load per tape width of 1 cm when the tape is peeled off at a speed of 300 mm Z at 23 ° C while maintaining.

The resin film for release 10 used in the present embodiment preferably has a heat shrinkage at 150 ° C. of 1% or less, more preferably 0.5% or less. Examples of the release resin film 10 having such a heat shrinkage ratio include a film made of polyethylene naphtholate, polyimide, or the like. Further, a film having a heat shrinkage in the above range obtained by subjecting polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polypropylene or the like to heat shrinkage treatment can also be used.

2 and 3 show an example of a preferred method of manufacturing the pre-preda 1 of the present embodiment. First, an uncured matrix resin is applied to the heavy surface of a release resin film having a heavy surface and a light surface to produce a resin coating film for impregnation.

(Figure 2 ). The uncured matrix resin of a predetermined thickness attached to the roller 26 is transferred onto the heavy surface of the resin film for release 20 continuously fed from the resin film roll for release 20a, thereby Obtain a resin coating film 22 for impregnation. The uncured matrix resin is adjusted to a predetermined thickness by passing it between rollers 26 and 27. Thereafter, the impregnating resin coating film 22 is cooled through the cooling zone P, and then collected. A resin coating film roll 22a for winding and impregnation is obtained. Here, 29a and 29b are blades for adjusting the resin thickness.

Next, a resin-coated release paper 31 in which an uncured matrix resin is applied to one side of a release paper is prepared in the same manner as the impregnated resin-coated film roll 22a produced by the above method. There is no particular limitation on the release paper.

Next, as shown in Fig. 3, a film 22 is applied from the resin coating film roll 22a for impregnation, and a resin coating release paper 31 is applied from the resin coating release paper roll 31a. The reinforcing fibers 30 are fed continuously while the surfaces are opposed to each other.

In this case, when the impregnating resin coating film 22 coated with the uncured matrix resin is unwound from the roll, the peeling resistance between the heavy and light surfaces of the release resin film is different. The uncured matrix resin does not transfer to the surface.

Next, a laminated film 33 composed of a resin coating film 22 for impregnation sandwiching the reinforcing fibers 30 and a resin-coated release paper 31 is heated on a heating plate 37 provided with a pressure roller 35 on the top, and The uncured matrix resin is sent to a heating roller 38 provided with a pressure port 36 at the upper part, and the uncured matrix resin is impregnated into the reinforcing fibers 30 by pressing the laminated film 33 under heating. After passing through the cooling zone P to cool the laminated film 33, the release paper 32 is peeled from the laminated film 33 to obtain the paper-free prepreg 34 of this embodiment. In this embodiment, the free pre-predator 34 is wound around a pre-predator collecting roller 34a. The release paper 32 is taken up by the release paper recovery roller 32a and collected.

The release paper 32 collected above can be reused. Therefore, release paper is reused in the production process and does not flow out to waste. In the above embodiment, when the uncured matrix resin is impregnated into the reinforcing fibers 30, the resin-coated release paper is laminated and impregnated on the upper surface of the reinforcing fibers 30, but is not limited thereto. The impregnating resin coating film 22 may be laminated on both the upper and lower surfaces of the reinforcing fibers 30 to impregnate the uncured matrix resin. In this case, at the end of the process, the release resin film 20 on the upper surface or the lower surface is recovered in the same manner as the release paper 32 to obtain the pre-preda of the present embodiment.

Further, in the above embodiment, the uncured matrix resin is supplied to the reinforcing fibers 30 from both the upper surface and the lower surface of the reinforcing fibers 30, but the matrix resin may be supplied from only one surface according to the purpose. The supply of the matrix resin from one side can be performed by replacing the resin-coated release paper 31 with a release paper in FIG.

The release resin film 10 can be peeled off at any time after the production of the prepreg 1. Also, it may be peeled off immediately before using the pre-preda 1. Since the release resin film 10 is made of plastic, it can be recycled. When discarded, it can be treated as combustible waste.

Since the paper-free prepreg of this embodiment does not have cellulose-based release paper attached thereto, it does not generate flame-retardant waste when used. The paper-free pre-predder of the present embodiment can recycle the release resin film, and can reduce the amount of waste. When discarding this film, it can be treated as flammable waste.

The release resin film has a heavy surface and a light surface having different peel resistance values. For this reason, in the production of the paper-free pre-predder of the present embodiment, the matrix resin applied to the heavy surface of the film when the film is unwound from the resin coating film roll 22a for impregnation is not transferred to the light surface. Can be manufactured.

Further, the paper-free prepreg of this embodiment can easily peel off the resin film for release when used, and the surface of the reinforced fiber matrix layer when peeled is excellent in smoothness.

Further, when a resin film 10 having a heat shrinkage of 1% or less, preferably 0.5% or less at 150 ° C. is used as the release resin film 10, the obtained paper-free prepreg is cut. The product has high dimensional stability after being made into a product, and has little occurrence of deformation such as curling.

In addition, the paper-free pre-predder of the present embodiment has a structure in which the light surface of the mold release resin film having a heavy surface and a light surface is separated from the other pre-predder even if the cover film is peeled off, stacked, and cut. It reliably prevents adhesion to each other. For this reason, a large number of the pre-preda of the present embodiment can be stacked and cut, and the cutting efficiency increases. (Second form)

FIG. 4 is a schematic view showing a second embodiment of the pre-preda of the present invention. In FIG. 4, reference numeral 201 denotes a pre-predeer, which is formed by attaching a cover film 208 and a release resin film 210 to one surface and the other surface of the reinforcing fiber matrix layer 202, respectively.

The reinforcing fiber matrix layer 202 is formed by impregnating a reinforcing fiber 206 with an uncured matrix resin 204.

As the reinforcing fibers constituting the reinforcing fiber matrix layer 202, the reinforcing fibers described in the first embodiment can be used.

As the uncured matrix resin impregnated in the reinforcing fibers, the uncured matrix resin described in the first embodiment can be used.

The peel resistance has been described in the first embodiment.

The release resin film 210 comes in contact with the reinforcing fiber matrix layer 202. The release resistance of the surface 2 12 of the release resin film 210 is set to 0.5 to 20 Og / cm. If the peeling resistance exceeds 200 gZcm, the matrix resin 204 is partially incorporated into the release resin film 210 when the release resin film 210 is released from the prepreg 201 when using the prepreg. It is transcribed or the pre-predator 201 is torn, making its handling extremely difficult. If the peel resistance is less than 0.5 g / cm, the uncured matrix resin applied impregnating resin coating film is continuously fed out of the rolls in the pre-predator manufacturing process described later. The uncured matrix resin is partially transferred to release paper sandwiched between the resin coating films for impregnation. As a result, it becomes difficult to draw out the resin coating film for impregnation in which the uncured matrix resin is uniformly applied. The peel resistance value is preferably from 10 to 120 gZcm. If the peel resistance is less than 10 gZcm, the adhesion between the release resin film 210 and the reinforced matrix layer 202 will be insufficient, causing a floating defect or a sinking defect (the matrix resin may not adhere to the surface of the matrix layer). This may cause a phenomenon of sinking, which may hinder the molding process using a pre-preda.

The method of adjusting the release resistance value of the release resin film to the above range, the material of the release resin film, the heat shrinkage, and the like are the same as in the first embodiment. The release resistance value of the surface 214 of the mold release resin film 210 where the mold release resin film 210 is not in contact with the reinforcing fiber matrix layer 202 is not particularly limited, and may be any value. .

As the cover film 208, a polymer film having excellent releasability, such as polyethylene and fluororesin, is preferable. Further, a film subjected to a release treatment can be used. A general purpose and inexpensive polyethylene film is particularly preferred.

In this form of pre-predator 201, the cover film 208 is used. The resin film for release may be used. Also in this case, the peel resistance value of the surface of the cover film 208 in contact with the reinforcing fiber matrix layer 202 is set to 0.5 to 200 gZcm.

5 and 6 show an example of a preferred method of manufacturing the pre-preda of the present embodiment. First, an uncured matrix resin is applied to the release surface of the resin film for release to produce a resin coating film for impregnation (Fig. 5). An uncured matrix resin having a predetermined thickness is supplied and applied onto the surface of the release resin film 220 having the above-mentioned peel resistance value which is continuously fed from the release resin film roll 220a. Thereby, the resin coating film for impregnation 222 is obtained. The uncured matrix resin is passed between rollers 222 and 227 to have a predetermined thickness. The resin coating film for impregnation 222 is cooled in the cooling zone P, and then wound up around the collecting port together with the release paper 222 fed from the release paper roll 222a. In this way, a resin coating film roll for impregnation 222 with a release paper sandwiched between the resin coating films is obtained. In addition, 224, 225, 228 is a mouthpiece, 229a, 229b is a plate.

In FIG. 5, the resin coating film roll 22 2 a for impregnation was manufactured by sandwiching the release paper 22 1 between the resin coating film 22 2 for impregnation, but the present invention is not limited to this. Cover film, resin film for release, etc. can be inserted. However, in any case, the resin coating film for impregnation 222 has a lower peel resistance than the uncured matrix resin applied surface, and it is necessary to adhere the surface to the uncured matrix resin. When a cover film or the like is used in place of the release paper, an inexpensive polyethylene film having a low peel resistance value is preferable as the cover film.

Next, the resin coating film roll for impregnation produced by the above method

2 2 2a and release with uncured matrix resin applied on one side in the same way Prepare the pattern paper (resin-coated release paper) 2 3 1. Next, the film 22 2 and the release paper 2 3 1, with the matrix resin application surfaces facing each other, from the resin coating film roll 2 22 a for impregnation and the resin coating release paper port 2 31 a And reinforced fiber 230 is continuously fed in between (Fig. 6).

When the impregnated resin coating film 222 coated with the uncured matrix resin is unreeled from the roll, the surface of the release paper 222 interposed between the impregnated resin coating film 222 and the surface in contact with the uncured matrix resin The peel resistance value is lower than the peel resistance value of the release resin film 220. Therefore, the film can be unwound without transferring the matrix resin to the release paper 222.

Next, a laminate 242 of the impregnating resin coating film 222 sandwiching the reinforcing fiber 230 and the resin coating release paper 231 is provided, and a pressure roller 235 is provided on the upper part. The heating plate 237 is then fed to a heating roller 238 provided with a pressure port 2336 at the top, and pressed under heating. By this operation, the uncured matrix resin is impregnated into the reinforcing fibers 230. <After cooling through the cooling zone P to cool the laminate 2 42, the release paper 2 32 is peeled off from the laminate 2 42. Release paper collecting roller 1 2 3 2 Take up and collect on a. Thereafter, the cover film 2 33 pulled out from the cover film roll 2 3 3 a is pressure-bonded at room temperature to the surface from which the release paper 2 32 has been peeled off, to obtain a paper-free prepreg 2 3 4 of this embodiment. To the pre-preda recovery port.

In addition, reference numeral 223 denotes a release paper, reference numeral 223 b denotes a release paper collection roller, and reference numeral 239 b denotes a press opening port.

Here, a resin film for release may be used instead of the cover film 233. In this case, the surface to be pressed against the reinforcing fiber matrix layer is the same as the uncured matrix resin coated surface of the resin coating film for impregnation. It is preferable to have a lower peel resistance value.

The collected release paper can be reused. Therefore, the release paper is reused in the production process and does not flow out.

In the above example, when the uncured matrix resin is supplied to the reinforcing fibers, the resin-coated release paper 231 is stacked on the upper surface of the reinforcing fibers 230, but the resin coating film for impregnation is stacked. May be. In this case, after passing through the cooling zone P, it is possible to obtain a prepreg in which a release resin film is adhered to both surfaces of the trick layer between the reinforcing fibers without being replaced with the cover film 233.

Further, in the above example, the uncured matrix resin is supplied from both the upper surface and the lower surface of the reinforcing fiber. However, only one surface may be supplied according to the purpose. In the manufacturing method shown in FIG. 6, the uncured matrix resin is provided only on one side by using a release paper or a release resin film to which the uncured matrix resin has not been applied, instead of the resin-coated release paper roll 2311a. Can be paid.

The release resin film and the cover film can be peeled at any time after the production of the prepreg. It may be peeled off immediately before using the pre-preda. Since these films are made of plastic, they can be recycled and can be disposed of as flammable waste when they are discarded.

Since the paper-free prepreg of this embodiment does not have cellulose-based release paper attached thereto, it does not generate flame-retardant waste when used.

This paper-free pre-preda can recycle the cover film and the release resin film, and can reduce the amount of waste. When discarding these films, they can be treated as flammable waste. Furthermore, the paper-free prepreg of this embodiment can easily release the release resin film, and the surface of the reinforcing fiber matrix layer when peeled is excellent in smoothness.

Further, when a resin film 210 having a heat shrinkage of 1% or less, preferably 0.5% or less at 150 ° C. is used as the mold release resin film 210, the obtained paper-free pre-reader is: High dimensional stability after cutting into a product to minimize deformation such as curling.

(Third form)

FIG. 7 shows an example of the configuration of the pre-predder of the third embodiment. In FIG. 7, reference numeral 310 denotes a pre-predeer, which is formed by attaching a cover film 308 and a release resin film 310 to one surface and the other surface of the reinforcing fiber matrix layer 302, respectively.

The release resin film 310 has a heavy surface 312 and a light surface 314 with different peel resistance values on the front and back, and the heavy surface 312 is attached to the reinforcing fiber matrix layer 302. Have been.

The reinforcing fiber matrix layer 302 is obtained by impregnating a reinforcing fiber 303 with an uncured matrix resin 304.

The reinforcing fibers constituting the reinforcing fiber matrix layer 302 and the uncured matrix resin impregnated in the reinforcing fibers are the same as those used in the first embodiment.

The material and heat shrinkage of the release resin film 310, the method for forming the heavy and light surfaces of the release resin film, and the like are the same as those described in the first embodiment.

Similarly, a commercial product can be used as the release resin film.

In the pre-preparer of the third mode, the heavy surface of the release resin film 310 The peel resistance value of 312 is set to 200 g / cm or less, and preferably 120 g / cm or less. If the peel resistance value of the heavy surface 312 exceeds 200 g / cm, a part of the matrix resin will be released when the release resin film 310 is peeled off when using the pre-predator 301. May be transferred onto the resin film 310 for use, or the pre-predeer 301 may be torn, making handling very difficult.

Further, it is more preferable that the peel resistance value of the heavy surface 312 is 10 g / cm or more. If the peel resistance value of the heavy surface 312 is less than 10 g / cm, the adhesion between the heavy surface 312 and the reinforcing fiber matrix layer 302 will be impaired, which may cause floating points or molding. In this case, pre-preda processing may be affected.

The peel resistance ratio of the heavy surface 312Z light surface 314 of the release resin film 310 is set to 3.0 or more, preferably 5 or more. When the peel resistance ratio is less than 3.0, the unhardened matrix resin is partially transferred to the light surface 314 in the pre-predator manufacturing process described later. As a result, it is not possible to obtain a resin coating film for impregnation in which the uncured matrix resin is uniformly applied on the heavy surface 312. If the peel resistance ratio exceeds 3.0 even if it exceeds 3.0, it may be partially transferred to a light surface depending on the type of uncured matrix resin.

As the cover film, a polymer film having excellent releasability, such as polyethylene and fluororesin, is preferable. In addition, any film that has been subjected to a release treatment can be used, but a general-purpose and inexpensive polyethylene film is preferable.

In the pre-preda of this embodiment, the above-described resin film for release may be used as a cover film. In this case, the surface in contact with the reinforcing fiber matrix layer may be either a heavy surface or a light surface. However, in consideration of workability, a light surface is preferable. Third Embodiment FIGS. 8 and 9 show an example of a preferred method of manufacturing a pre-preda.

First, an uncured matrix resin is applied to the heavy surface of the release resin film 320 to produce a resin coating film for impregnation (FIG. 8). After passing between the rollers 132 and 327 on the heavy surface of the resin film for release 320 continuously fed out from the resin film roll for release 320a, it has not been adjusted to a predetermined thickness. The cured matrix resin is supplied and applied, thereby obtaining a resin coating film for impregnation 322. After the impregnating resin coating film 32 2 passes through the cooling zone P, it is wound around a collecting roller 1 and the impregnating resin coating film roll 32 2 a is collected. In addition, 324, 325, 328 is a mouthpiece, 329a, 329b is a heating plate. Next, a release paper (resin-coated release paper) with an uncured matrix resin applied to the release surface in the same manner as the resin coating film opening for impregnation 32 2a manufactured by the above method To manufacture. The resin coating film for impregnation 3 2 2 from the resin coating film roll 3 3a for impregnation, and the resin coating release paper 3 3 1 for the resin coating release paper roll 3 3 1a from the matrix The resin is applied with the resin-coated surfaces facing each other, and the reinforcing fibers 330 are continuously fed between them (FIG. 9). When the impregnated resin coating film 322 coated with the uncured matrix resin is unwound from the roll 322a, the release resistance of the heavy and light surfaces of the release resin film is different. The resin coating film for impregnation 322 can be unwound from the roll 322a without transferring the uncured matrix resin to the surface.

Next, a laminated body 342 composed of the resin coating film for impregnation 322 sandwiching the reinforcing fiber 330 and the resin-coated release paper 331 is heated by a heating plate provided with a pressure roller 1335 at the top. 3 3 7 and then to a heating roller 3 3 8 with a pressure roller 3 3 6 on top to heat them Press down. By this operation, the uncured matrix resin is impregnated into the reinforcing fibers 330. After cooling the laminated body 342 through the cooling zone P, the release paper 332 is peeled off, and the release paper 3332 is taken up by the release paper collection roller 3332a and collected. After that, the cover film 33 pulled out from the cover film opening 3 33 a is pressure-bonded to the laminated body 3 42 from which the release paper 3 3 2 has been peeled off at room temperature, and the paper-free pre-prepder 3 3 4 is obtained, and then it is wound around the pre-preda recovery port 3 3 4a.

Incidentally, 339a and 339b are pressure rollers, and 340 is a roller.

The release paper 332 collected in the above manufacturing process can be reused. Therefore, the release paper 332 is reused in the production process and does not flow out. Further, the above-mentioned resin film for release may be used instead of the cover film. In this case, the surface to be attached to the reinforcing fiber matrix layer may be light or heavy.

In the above example, as shown in FIG. 9, when the uncured matrix resin is impregnated into the reinforcing fibers 330, the resin coating release paper 331 is pressed on the upper surface of the reinforcing fibers 330. The uncured matrix resin was impregnated. However, the present invention is not limited to this method, and the upper and lower surfaces of the reinforcing fibers 330 may be pressed with the impregnating resin coating film to impregnate the uncured matrix resin. In this case, without replacing the release paper with a cover film, it is possible to obtain a pre-predder having both sides bonded with a release resin film.

Further, in the above example, the uncured matrix resin is supplied from both the upper surface and the lower surface of the reinforcing fiber, but the uncured matrix resin may be supplied from only one surface according to the purpose. In the case of single-sided supply, instead of the impregnated resin coating release paper roll indicated by 331a in Fig. 9, a release paper or a release resin film not coated with uncured matrix resin is used. Good.

The release resin film and the cover film can be peeled off at any time after the production of the prepreg. It may be peeled off immediately before using the pre-preda. Since these films are made of plastic, they can be recycled and can be disposed of as flammable waste.

Since the paper-free prepreg of this embodiment does not have cellulose-based release paper attached thereto, it does not generate flame-retardant waste when used. In the present embodiment, the cover free film and the resin film for mold release can be recycled, and the amount of waste can be reduced. When discarding these films, they can be treated as combustible waste.

Also, since the release resin film has a heavy surface and a light surface with different peel resistance values, it is necessary to manufacture a pre-preda without transferring the matrix resin applied on the film to the light surface when the film is unwound from a roll. Can be. Further, the paper-free pre-preda of the present embodiment can easily release the release resin film, and the surface of the reinforcing fiber matrix layer when peeled is excellent in smoothness.

Further, when a resin film 310 having a heat shrinkage of 1% or less, preferably 0.5% or less at 150 ° C. is used as the release resin film 310, the obtained paper-free pre-reader is cut. The product has high dimensional stability after being made into a product, and has little deformation such as curling.

Furthermore, the light surface of the release resin film, which has a heavy surface and a light surface, adheres to the other pre-predder even if the paper-free pre-predder of this embodiment peels off the cover film, cuts and stacks. To ensure that For this reason, a large number of the pre-preda of the present embodiment can be stacked and cut, and the cutting efficiency increases. (Fourth form)

The pre-preda of the fourth mode is a thermoplastic resin film on one side of a reinforcing fiber matrix layer obtained by impregnating an uncured matrix resin into a reinforcing fiber. The heavy side of the mold resin film is stuck. The thermoplastic resin film and the release resin film prevent the prepregs from adhering to each other and prevent the matrix resin from sinking while the prepreg of the present embodiment is being stored or transported. Further, these films function as a protective paper for protecting the reinforcing fiber matrix layer and preventing the reinforcing fiber matrix layer from being scratched or adhering of foreign matter.

Further, when the pre-preda of the present embodiment is used, the release resin film is peeled off, but the thermoplastic resin film can be used without peeling. For example, when laminating a plurality of pre-predeers of the present form from which the release resin film has been peeled off and then heating and curing to produce a molded product, the thermoplastic resin film has good adhesion to the matrix resin layer, so it should be strongly It fuses or adheres to the matrix resin layer to form the molded article itself.

FIG. 10 is a schematic diagram showing an example of a pre-predder of the fourth embodiment. In FIG. 10, reference numeral 401 denotes a pre-predader, which is formed by attaching a thermoplastic resin film 408 to one surface of a reinforcing fiber matrix layer 402 and a release resin film 410 to the other surface.

The reinforcing fiber matrix layer 402 is obtained by impregnating a reinforcing fiber 406 with an uncured matrix resin 404.

As the reinforcing fibers 406 constituting the reinforcing fiber matrix layer 402, those described in the first embodiment can be used.

As the uncured matrix resin 404 impregnated in the reinforcing fibers 406, a thermosetting resin used for ordinary production of a pre-preda can be used. Specifically, epoxy resin, unsaturated polyester resin, polyurethane resin, etc. Can be shown. From the viewpoint of the affinity with the thermoplastic resin film, an epoxy resin is particularly preferable.

The proportion of the uncured matrix resin 404 impregnated in the reinforcing fibers 406 is preferably 10 to 50% by mass, more preferably 15 to 30% by mass, based on the reinforcing fiber matrix layer 402.

It is preferable that the thermoplastic resin film 408 adhered to one surface of the reinforcing fiber matrix layer 402 has the following properties. (1) The glass transition temperature (T g) is 80 ° C or less, the vibration loss coefficient is large at the actual operating temperature (5-35 "C),

(2) The water absorption is 1% by mass or less,

(3) Low heat shrinkage at the curing temperature (90-180 ° C)

(4) The thickness is preferably from 10 to 100 m.

Specific examples of the thermoplastic resin film 408 having the above properties include nylon 12, ionomer, polyethylene terephthalate (PET) having both surfaces subjected to corona discharge treatment, and polyethylene terephthalate having both surfaces subjected to corona discharge treatment. (P BT).

The corona discharge treatment conditions for the thermoplastic resin film vary depending on the width, thickness, and treatment speed of the film, but can be generally expressed by a power value per unit time and per unit area. The discharge amount is preferably from 30 to 50 W / m ² 'min.

By subjecting the surface of the thermoplastic resin film to corona discharge treatment, polar groups (for example, 10H groups, 1COOH groups, and = C〇 groups) are formed on the film surface. Chemical affinity is increased. This increases the adhesiveness between the thermoplastic resin film and the epoxy resin. The release resin film 410 has a heavy surface 412 and a light surface 414 having different peeling resistance values on the front and back sides. The peel resistance of the heavy surface 4 12 is higher than that of the light surface 4 14, and the heavy surface 4 12 side of the release resin film is adhered to the reinforcing fiber matrix layer 402.

The material of the release resin film, the method for forming the heavy and light surfaces of the release resin film, the preferable heat shrinkage, and the specific examples of the release resin film have been described above.

In the pre-preda of the present embodiment, the release resistance value of the heavy surface 4 10 of the release resin film 4 10 is set to 150 g / cm or less, preferably 130 g / cm or less, and 120 g / cm or less is more preferable. If the peel resistance value of the heavy surface exceeds 150 g Z cm, the matrix resin is partially transferred onto the release resin film when the release resin film is peeled when using the pre-preda. Also, when manufacturing a thin pre-preda with a reinforcing fiber weight of 50 g / m ² or less and a resin content of about 26 mass%, the pre-preda may be torn when the resin film for release is peeled off. And makes handling extremely difficult.

Further, it is more preferable that the peeling value of the heavy surface 4 12 is 10 g / cm or more. If the peel resistance value of the heavy surface 4 12 is less than 10 g Z cm, the adhesion between the heavy surface 4 12 and the reinforcing fiber matrix layer 402 is undefined, which may cause a floating defect or a prepreg Processing may be hindered.

The peel resistance ratio of the heavy surface 4 12 / light surface 4 14 of the mold release resin film 410 is 3 or more, and is more preferably 5 or more. If the peeling resistance ratio is less than 3, the resin on the heavy surface 4 12 when the unmolded matrix resin applied to the release resin film is unwound from the roll in the pre-prepder manufacturing process described below. Is partially transferred to the light surface 4 1 4. If the peel resistance ratio is 3 or more and less than 5, depending on the type of the uncured matrix resin, it may be partially transferred to a light surface. FIGS. 11 and 12 show an example of a preferred method of manufacturing the pre-preda of the fourth embodiment.

First, an uncured matrix resin is applied to the heavy surface of the release resin film to produce a resin coating film for impregnation (Fig. 11). An uncured matrix resin having a predetermined thickness is applied on the heavy surface of the resin film for release 420 continuously fed from the resin film roll for release 42 0a, and the resin coating film for impregnation 42 1 Get. The thickness of the uncured matrix resin can be adjusted by passing it between mouths 426 and 427. After the impregnating resin coating film passes through the cooling zone P, the impregnating resin coating film 21 is wound around a mouth to obtain an impregnating resin coating film roll 421a. In FIG. 11, 424, 425, and 428 are rollers, and 29a and 29b are heating plates.

Next, a resin coating film roll for impregnation 42′a ′ is manufactured in the same manner as the resin coating film roll for impregnation 42la. As shown in FIG. 12, the resin coating film for impregnation 42 1, 21 1 ′ and the resin coating film for impregnation 42 1, 21 1 ′ are formed from the resin coating film roll 42 1 a for impregnation and Are fed in a state where they face each other, and during this time, the reinforcing fibers 430 are continuously fed in and pressurized by the pressing roller 434.

When the resin coating film for impregnation 42 1, 42 1, is pulled out from the rolls 42 1 a, 42 1 a ′, the peel resistance values of the heavy and light surfaces of the release resin film are different. The film can be unwound without transferring the uncured matrix resin to the light surface.

Next, a laminated body 442 composed of the impregnating resin coating films 421, 421, sandwiching the reinforcing fiber 430, is heated to a heating plate 436 having a pressure roller 435 on the upper side, and then to the upper part. To a heating roller 438 provided with a pressure roller 437 and press under heating. With this operation The reinforcing fibers are impregnated with the activated matrix resin. After passing the pressurized laminated body 424 through the cooling zone P, the release resin film 420 on the upper surface of the laminated body 442 is peeled off, wound around a collecting roller 422, and collected. After that, the thermoplastic resin film 4 23 drawn out from the thermoplastic resin film roll 4 2 3 a is placed on the upper surface of the laminate 4 4 2 from which the release resin film 4 2 By crimping at 39, a fourth form of paper-free prepreg 431 is obtained. The obtained fourth form of pre-predator is wound around a mouthpiece 431a to form a pre-predator roll. In addition, 440 is a roller.

In the above example, the uncured matrix resin was applied to both the two release resin films to be adhered to the upper surface and the lower surface of the reinforcing fiber 430, but the present invention is not limited to this, and either one The unhardened matrix resin may be applied only to the release resin film.

The release resin film 420 collected by winding it around the roller 422 can be reused. Therefore, the release resin film 420 is reused in the production process and does not flow out.

The release resin film 410 adhered to the other surface of the pre-preda can be peeled off at any time after the pre-preda is manufactured. Moreover, you may peel off immediately before using a prepredder. These films can be recycled because they are made of plastic, and can be disposed of as flammable waste when disposed.

Furthermore, when a resin film for release having a heat shrinkage at 150 ° C. of 1% or less, preferably 0.5% or less is used as the release resin film 410, the obtained paper-free pre-reader is High dimensional stability after cutting into a product to minimize deformation such as curling.

Next, a case where a molded product is manufactured using the pre-predader of the fourth embodiment will be described. Figure 13 shows the release resin film or the thermoplastic resin film attached to the surface of the pre-predaur of the fourth embodiment, and a plurality of pre-predas (four in this figure). A molded article produced by laminating and then heat-molding the laminated product is shown.

A first pre-prepainter 300a comprising a reinforcing fiber matrix layer 2a and a thermoplastic resin film 8a is prepared, and a reinforcing fiber matrix layer 2b and a thermoplastic resin film 8b are sequentially formed thereon. The third pre-predeer 300c composed of the second pre-predeer 300b, the reinforcing fiber matrix layer 2c and the thermoplastic resin film 8c is laminated.

Lastly, a pre-precoater 400 composed of only the reinforcing fiber matrix layer 2d from which the release resin film and the thermoplastic resin film have been peeled off is laminated. By heating this laminate, a molded article can be obtained.

Heating depends on the type of matrix resin, but usually 90-180 ° C is preferred. By heating to this temperature, when the thermoplastic resin film is a film having a relatively low melting point such as nylon 12, it is fused and strongly bonded to the reinforcing fiber matrix layer. When the thermoplastic resin film is a film having a relatively high melting point, such as polyethylene terephthalate or polybutylene terephthalate, the surface is subjected to a corona discharge treatment, so that it adheres firmly to the reinforced fiber matrix layer.

In heating, it is preferable to depressurize and press while degassing. By doing so, it is possible to prevent the generation of a defective molded body containing bubbles inside.

The degree of decompression is preferably in the range of (100.87) to (0.101) MPa. In addition, in the example of the present molded article, a pre-predeer 400 to which a thermoplastic resin film was not attached was used as a pre-predeer to be laminated last, but the thermoplastic resin film was exposed on the surface of the obtained molded article. For applications that may be acceptable, stack the pre-predator 400 with a thermoplastic resin film attached. Can be layered.

When the pre-preda of the present embodiment is used to reinforce a structure or the like, the pre-preda of the present embodiment can be sequentially laminated on the reinforcing portion and can be reinforced by heating.

The molded body produced as described above has a complete fracture mode of bending failure and a plastic deformation mode of interlaminar shear strength test.

In the paper-free prepreg of this embodiment, a thermoplastic resin film and a release resin film are adhered to a reinforcing fiber matrix layer. In use, the release resin film is peeled off and removed. The plastic resin film is laminated and cured with the reinforcing fiber matrix layer without being removed. The pre-preda of the present embodiment does not adhere to the cellulose-based release paper and does not use the cellulose-based release paper in the manufacturing process, so that no flame-retardant waste is generated. The release resin film peeled from the pre-preda of the present embodiment can be recycled, so that the amount of waste can be reduced, and even when treated as waste, it can be treated as combustible waste.

Further, the pre-preda of the present embodiment can easily release the release resin film, and the surface of the reinforcing fiber matrix layer when peeled is excellent in smoothness.

Further, the pre-preda of the present embodiment reliably prevents the light surface of the mold release resin film having the heavy surface and the light surface from adhering to other pre-predas even when they are cut and stacked. For this reason, a large number of pre-preda of the present embodiment can be stacked and cut, and the cutting efficiency is increased. (Curl elimination method)

The resin coating film for impregnation used for the pre-preda manufactured by the above method is exposed to heat and tension during the manufacturing process, so that shrinkage stress is generated in the resin coating film for impregnation. For this reason, the obtained pre-preda may curl if the pre-preda is cut into a required shape during molding due to the influence of the residual stress of the film.

Hereinafter, a method for producing a non-force-free pure prepreg applicable to the first to fourth embodiments will be described.

(First method)

The first method is a method in which the release resin film used for preparing the impregnating resin coating film is replaced with another release resin film at the end of the prepreg manufacturing process.

In FIG. 14 ', 502 and 504 are impregnated resin coating films each having an uncured matrix resin applied to its heavy surface, with the matrix resin application surfaces facing each other. Reference numeral 506 denotes a reinforcing fiber, which is sandwiched between the resin coating films for both impregnations 502, 504 and sent between the rolls 508, 510, where it is pressed to form a laminate 51. It becomes 2. The laminated body 512 is then pressed by the heating controller 514 and the pressure roller 516, and then cooled by the cooling unit 518.

After that, the release resin films 520 and 522 on the upper surface and the lower surface of the laminated body 512 are peeled off and wound around the rollers 524 and 526.

Next, a cover film 528 made of polyethylene or the like is provided on the upper surface of the laminate from which the release resin films 520 and 522 have been peeled off, and a replacement film 530 such as a release film is provided on the lower surface. Affixed. Thereafter, the product pre-preda 5 32 is wound up on a roll.

Here, the cover film 528 and the replacement film 530 do not shrink because they have not been subjected to heating, tension, etc. in the previous process. You. As the cover film 528, a film usually used without any particular limitation can be used. The replacement film 530 can be used without particular limitation as long as it satisfies the restrictions described in the above embodiments (restrictions on the peel resistance ratio between the heavy surface and the light surface, the peel resistance value, etc.). Further, the thickness of the cover film and the replacement film is preferably from 10 to 200 mm, more preferably from 25 to 100 microns. According to the first method, since the release resin film is replaced with another film at a later stage of the pre-preda manufacturing process, the obtained pre-preda is less likely to curl even if it is subjected to cutting or the like.

(Second method)

FIG. 15 shows a second method for preventing curling.

Reference numerals 62 and 604 denote impregnating resin coating films in which an uncured matrix resin is applied to the heavy surface, with the matrix resin surfaces facing each other. The resin film for release of the resin coating film for impregnation 602 preferably has a heat shrinkage at 150 of 1% or less, more preferably 0.5% or less.

Reference numeral 606 denotes a reinforcing fiber, which is sandwiched between the resin coating films for impregnation 602, 604 and pressed by the rolls 608, 610 to form a laminate 612. The laminate 612 is then pressed by the heating plate roller 614 and the pressure roller 616, and then cooled by the cooling unit 618.

After that, the release resin film 620 on the upper surface of the laminate 612 is peeled off and wound around the roller 624.

Next, a cover film 628 such as a polyethylene film is adhered to the upper surface of the laminate from which the release resin film 620 has been peeled off. After that, the product pre-predator 632 is wound on a roll.

6 3 4 is a control roller. The control roller 634 detects the supply tension of the resin coating film for impregnation 604 and adjusts it to a predetermined tension or less. Resin coating for impregnation The tension applied to the lum is preferably 60 gZcm or less.

In the second method, the resin coating film for impregnation 602 having a heat shrinkage of 1% or less at 150 ° C. is used and the resin coating film for impregnation 6 Since the tension of 04 is controlled to be equal to or lower than a predetermined value, the obtained pre-preda hardly curls even when cutting or the like is performed. Example

(Example of the first embodiment)

Example 1

70 parts by mass of phenol nopolak type resin (ARAL DI TE EPN 1 1 3 8: Asahi Kasei Epoxy), 30 parts by mass of bisphenol A type epoxy resin (ARAL DI TE AER 6002: Asahi Kasei Corporation) Parts, 3 parts by weight of dicyan diamide, and 3 parts by weight of 1,3-dimethylurea with 5 parts by weight of 1,1-dimethylurea using a one-piece mill, and a one-part curing epoxy A resin composition was obtained. Using this one-component curable epoxy resin composition, a film resin for release (polypropylene film, Santox-MPRS 0 A resin coating film as shown in Table 1 was prepared by coating the resin on the heavy surface side of 2.60 ^ m: manufactured by Santox Corporation.

Continuous carbon fiber bundle (BESFI GHT UT 500-12 K: manufactured by Toho Tenax Co., Ltd., filament count: 12, 100, tensile strength: 4.8 MPa, tensile modulus: 240 GPa) 7 8 After the bundle is formed into a continuous carbon fiber aggregate in the form of a sheet arranged parallel to each other in one direction, the bundle is inserted between the upper and lower sides of the continuous carbon fiber aggregate with the hot-opener so as to be sandwiched by the resin coating film for impregnation. The resin was sealed under the conditions of temperature 100, pressure 0.29 MPa. The sheet-like continuous carbon fiber aggregate was impregnated. After cooling, the release paper was wound up, and a one-way prepreg shown in Table 1 was wound up in a roll shape by a take-up roller.

The obtained pre-preda had good resin impregnation between carbon fibers, and did not disturb the fibers. Furthermore, the release resin film could be easily peeled off from the prepreg, and the prepreg surface after peeling the release resin film was extremely excellent in smoothness.

Examples 2 to 5, and Comparative Examples 1 and 2

The pre-preda shown in Table 1 was obtained by performing the same operation as in Example 1 except that a polyethylene terephthalate film (Purex film · 50 jLim: manufactured by Teijin Dupont Film Co., Ltd.) was used as the resin film for release. In Examples 4 and 5 and Comparative Examples 1 and 2, carbon fibers were impregnated with resin using a resin-coated release paper coated with a one-component curing type epoxy resin composition of Example 1 on the upper surface. A method of peeling off the release paper after cooling was used.

In Example 3, when the carbon fiber was impregnated with the resin, a release paper coated with no epoxy resin was used on the upper surface, the resin was supplied only from the lower surface, and then the release paper was peeled off.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2

Tree

Thickness (6Π1) 60 50 50 50 50 50 Oil 50

G Light surface peel resistance (g / cm) 4 4 8 4 2 4 8

A Heavy surface peel resistance (g / cm) 40 40 40 200 10 4 280

Heavy surface / Light surface Peeling resistance ratio 10 10 5 50 5 1 35 m

Amount of resin on heavy surface (gZm ² ) 22.5 22.5 45 22.5 22.5 22.5 22.5 Reinforcement fiber 'Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Ash fiber Fiber carbon fiber Fiber reinforcement (GZm ² ) 125 125 125 125 125 125 125 Uncured matrix resin Epoxy Epoxy Epoxy Epoxy Epoxy Epoxy

U Uncured matrix resin

26 26 26 26 26 26 26 Content (% by mass)

Les

Gu prepreda

Puripureda Appearance Good Good Good Good Good Good Good Good Good Good bad manufacturing not ¹⁾

Film detachability Slightly heavy Very light Very heavy Excellent in smoothness Excellent in smoothness Excellent in smoothness Excellent in smoothness Excellent in form Remaining appearance after film peeling

To be done to be done.

1) When pulling out the resin coating film for impregnation, the resin on the heavy surface was partially transferred to the light surface.

(Example of the second embodiment)

Example 6

70 parts by mass of phenol nopolak type resin (ARALD I TE EPN 1 1 3 8: Asahi Kasei Epoxy), 30 parts by mass of bisphenol A type epoxy resin (A RALD I TE AER 6002: Asahi Kasei Corporation) Parts, 3 parts by weight of dicyan diamide, and 5 parts by weight of 3- (3,4-dichlorophenyl) —1,1-dimethylurea are uniformly mixed using a roll mill, and a one-component curing type epoxy resin is used. A composition was obtained. Using this one-part curing type epoxy resin composition, a film for releasing resin (polypropylene film, Santo Tokusou MP RS 026.000: Santo Tokus Co., Ltd.) Resin was coated on the surface having the peel resistance value shown in Table 1 so that the amount of resin was as shown in Table 1, and release paper was sandwiched between the films to produce a resin coating film for impregnation.

Continuous carbon fiber bundle (BESFI GHT UT 500--12 K: manufactured by Toho Tenax Co., Ltd., number of filaments: 1,200, tensile strength: 48, 1 OMPa, tensile modulus: 240 GPa) 7 After forming the sheet-like continuous carbon fiber aggregate in which the eight bundles are arranged in parallel in one direction, the impregnating resin coating film drawn out from the impregnation resin coating film roll from above and below the sheet-like continuous carbon fiber aggregate. The sheet-like continuous carbon fiber aggregate was impregnated with a resin at a temperature of 100 ° C. and a pressure of 0.29 MPa by being sandwiched between the hot-holes. After cooling, a unidirectional prepreg shown in Table 1 having a width of 500 mm and being wound up in a roll by a winding roller was obtained.

The obtained pre-preda had good resin impregnation between carbon fibers, and did not disturb the fibers. Furthermore, the resin film for release could be easily peeled off from the pre-preda, and the surface of the pre-reader after peeling off the resin film for release was very excellent in smoothness. Examples 7 to; L 0, and Comparative Examples 3 and 4

The same procedure as in Example 6 was carried out except that a polyethylene terephthalate film (Purex film '50: manufactured by Teijin Dupont Film Co., Ltd.) was used as a resin film for release, to obtain a pre-preda shown in Table 2. In Examples 9 and 10 and Comparative Examples 3 and 4, the method shown in FIG. 6, that is, the resin coating obtained by coating the one-part curable epoxy resin composition of Example 6 with the same amount as the resin coating film for impregnation was used. The carbon fiber was impregnated with resin using a single release paper on the upper surface, and after cooling, the release paper was peeled off and the cover film shown in Table 2 was pressed.

In Example 8, when carbon fibers were impregnated with a resin, release paper without epoxy resin was used on the upper surface, and the resin was supplied only from the lower surface. Thereafter, the release paper was peeled off and the cover films shown in Table 2 were pressed.

Table 2

CO

00

1) When pulling out the resin coating film for impregnation, a part of the resin was transferred to the sandwiched release paper.

(Example of Third Embodiment)

Example 1 1

70 parts by mass of phenol nopolak type resin (ARALD I TE EPN 1 13 8: Asahi Kasei Epoxy Co., Ltd.), bisphenol A type epoxy resin (ARAL DI TE AER 6002: Asahi Kasei Co., Ltd.) 30 Parts by weight, 3 parts by weight of dicyan diamide, and 3 parts by weight of 3_ (3,4-dichlorophenyl) -1.1-dimethylurea are mixed evenly using a mouth mill to cure one part. An epoxy resin composition was obtained. Using this one-component curable epoxy resin composition, a film resin device (polypropylene film, Santox-MPRS0) was used with a film coater so that the resin content of the pre-preda shown in Table 3 was obtained. A resin coating film for impregnation was prepared by coating the resin in the amount shown in Table 3 on the heavy side of 2 · 60 / im: manufactured by Santox Corporation. The release resistance of the heavy surface of the release resin film was 40 g / cm, the release resistance of the light side was 4 g / cm, and the peel resistance ratio was 10.

Continuous carbon fiber bundle (BESFI GHT UT 500-12 K: manufactured by Toho Tenax Co., Ltd., number of filaments: 1,200, tensile strength: 48, 1 OMPa, tensile modulus: 240 GPa) 7 8 After forming the sheet-like continuous carbon fiber aggregates in which the bundles are arranged in parallel in one direction, the sheet-like continuous carbon fiber aggregates are sandwiched from above and below by a resin coating film for impregnation from above and below. The sheet-like continuous carbon fiber aggregate is impregnated with resin under the condition of a temperature of 100 ° (pressure: 0.29 MPa), and then cooled and taken up by a winding roller. To obtain a unidirectional prepreg wound in a roll.

The obtained prepredder had a width of 500 mm, a CF weight of 125 g / m ² , and a resin content of 26% by mass. In addition, this pre-preda had good resin impregnation between carbon fibers, and did not cause fiber turbulence. Further, the resin film for release can be easily peeled off from the prepreg. The surface of the prepreg after peeling off the oil film was very excellent in smoothness, Examples 12 to 15 and Comparative Examples 5 and 6.

The same procedure as in Example 1 was performed except that a polyethylene terephthalate film (Purex film '50 zm: Teijin Dupont Film Co., Ltd.) was used as the release resin film to obtain the pre-preda shown in Table 3. Was. In Examples 14 and 15 and Comparative Examples 5 and 6, the method shown in FIG. 9, that is, a resin coating release paper coated with the one-part curable epoxy resin composition of Example 11 was used. The method used was to impregnate the carbon fiber with a resin using the upper surface, release the release paper after cooling, and press-bond the cover film shown in Table 3.

In Example 13, when carbon fibers were impregnated with a resin, release paper not coated with epoxy resin was used on the upper surface, and the resin was supplied only from the lower surface. Thereafter, the release paper was peeled off, and the cover films shown in Table 3 were pressed.

Table 3

I- ¹

1) Resin for impregnation When pulling out the tinting film, the resin on the heavy surface partially transferred to the light surface.

(Example of the fourth embodiment)

(Example 16)

ARALD I TE (trade name EPN 1 1 3 8 phenol nopolak type epoxy resin manufactured by Asahi Kasei Epoxy Co., Ltd.) 70 parts by mass, ARALD I TE (trade name AE R 6002 bisphenol A type epoxy resin Asahi Kasei Epoxy 30 parts by mass), 3 parts by mass of dicyandiamide, and 5 parts by mass of 3- (3,4-dichlorophenyl) -1,1-dimethylurea are uniformly mixed using a roll mill. Thus, a one-part curable epoxy resin composition was obtained.

Using the one-component curing type epoxy resin composition, a predetermined amount of resin is coated on the surface of the release resin film with a film coater so as to have a resin content of the prepreg shown in Table 4. Thus, a resin film for impregnation was prepared.

Continuous carbon fiber bundle BESFI GHT (trade name: UT500--12K, manufactured by Toho Tenax Co., Ltd., number of filaments: 1,200, tensile strength: 500 MPa, tensile modulus: 40 GPa ) 78 sheets were arranged in parallel in one direction to form a continuous carbon fiber sheet aggregate.

Thereafter, a resin film was introduced from above and below by sandwiching the sheet-like continuous carbon fiber aggregate between the two resin films whose resin-coated surfaces were opposed to each other.

After passing these through a hot roller, the sheet-like continuous carbon fiber aggregate is impregnated with resin at a temperature of 100 ° C. and a pressure of 0.29 MPa, and then the release resin film on the upper surface is removed. The film was peeled off and the film was wound around a mouth roll. Almost at the same time as the release resin film of the resin film on the upper surface was peeled off, the thermoplastic resin film shown in Table 4 was continuously adhered to the upper surface.

Next, the mold release resin film, the sheet-like continuous carbon fiber aggregate impregnated with the resin, and the thermoplastic resin film are sent to a pair of mouth rollers. At a room temperature to obtain a unidirectional pre-predder having a width of 500 mm. The obtained prepredder had a carbon fiber weight of 125 g / m ² and a resin content of 26% by mass. In addition, this pre-preda had good resin impregnating property between carbon fibers, and did not disturb the fibers. The resin film for release was easily peeled off from the pre-preda, and the surface of the reinforcing fiber matrix layer after peeling the resin film for release was very excellent in smoothness.

(Example 17-7-22, Comparative Example 7-10)

In the same manner, pre-predas having the configurations shown in Tables 4 and 5 were obtained.

However, in Example 18, the carbon fiber was impregnated with the resin by using a release resin film (not coated with epoxy resin) on the upper surface and supplying the resin only from the lower surface. Thereafter, the mold release resin film on the upper surface was peeled off, and a thermoplastic resin film shown in Table 4 was pressed.

The following thermoplastic resin films were used.

Nylon 12 film: Daicel Chemical Industries Co., Ltd. Diamid 2401, thickness 30 mm, melting point 80-115 ° C, no corona discharge treatment on both sides Polybutylene terephthalate film: Daicel Chemical Industries Thermo Light 2 8 1 0

The corona discharge treatment was performed under the condition of a discharge amount of 80 to 100 Wm ² · min.

Table 4 Example 16 Example 17 Example 18 Example 19 Example 19 Example 20 Example 21 Example 22 Types PP PET. PET PET PET PET PET Peeling thickness (m) 60 50 50 50. 50 50 50

Light surface peel resistance (g / cm) 4 4 8 2 8 8 8

Fat Heavy surface peeling resistance (g / cm) 40 40 40 10 80 120 1 0 Heavy surface / Light surface Peeling resistance ratio 10 10 5 5 10.15 17.5 Fat Heat Nylon 12 PET PB Nylon 12 Nylon 12 Nylon 12 Nylon 12 f acceptable

Thickness (im) 30 50 50 50 30 30 30

樹 Tree Surface treatment None Double-sided corona Double-sided corona None None None None Reinforced fiber Ash fiber Fiber carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Ash fiber High

Reinforced fiber weight (g / m ² ) 125 125 125 125 50 125 125

Matrix resin Epoxy Epoxy Epoxy Epoxy Epoxy Epoxy Epoxy

Matrix resin content

26 26 26 26 26 26 26 (% by mass)

Pre-preg appearance Good Good Good Good Good Good Good Good Good Good Good Peelability of mold release resin film Very light Light Slightly heavy Heavy peelability of mold release resin film Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent appearance

Table 5

1) The resin on the heavy surface partially transferred to the light surface when the resin film was pulled out. Example 23-26, Comparative Example 1 1 1 1 2

A pre-preda was manufactured by the manufacturing process shown in FIG. A 25 m thick polyethylene film was used as the cover film. Table 6 shows the physical properties of the obtained prepredder. Table 6

Example 23 Example 24 Example 25 Example 26 Comparative Example 11 Comparative Example 12

Resin film for mold release PET PET PEN PEN PET PEN Heat shrink treatment Yes Yes No No No No Thickness (/ 501) 50 50 50 50 50 50 Light surface peel resistance (g / cm) 4 4 8 8 2 8 Heavy surface peeling resistance (g / cm) 40 40 40 160 10 280 Heavy surface Z light surface Peeling resistance ratio 10 10 5 20 5 35 Reinforced fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Ash? ^ Fiber Carbon fiber Reinforced fiber weight (gZm ² ) 125 125 125 125 125 125 Matrix resin Epoxy Epoxy Epoxy Epoxy Epoxy Epoxy Matrix resin content (% by mass) 26 26 26 26 26 26 Curl No No No No No Yes Prepreda Appearance Good Good Good Good Good Good Good Peelability of mold release resin film Light Light Light Light Slightly heavy Very light Very heavy Surface with mold release resin film peeled Excellent smoothness Excellent smoothness Excellent smoothness Excellent appearance due to excellent smoothness

Claims

The scope of the claims

1. A mold release resin film having a reinforcing fiber matrix layer in which an uncured matrix resin is impregnated into reinforcing fibers, a heavy surface having a large peel resistance value, and a light surface having a small peel resistance value. A release resin film adhered to one surface of the fiber reinforced matrix layer, wherein the release surface of the release resin film has a peel resistance of 200 g Z cm or less and is lighter than the heavy surface. Paper-free pre-reader with a peel resistance ratio (heavy side / light side) of 3.0 or more.

2. The paper-free pre-reader according to claim 1, wherein the release resistance ratio between the heavy surface and the light surface of the release resin film is 5 or more.

3. The paper-free pre-reader according to claim 1, wherein the release resistance value of the heavy surface of the release resin film is from 10 to 120 gZcm.

4. The paper-free prepreg according to claim 1, wherein the release resin film has a heat shrinkage of 1% or less at 150.

5. The paper-free pre-reader according to claim 1, wherein the reinforcing fibers are carbon fibers, glass fibers, or aramide fibers.

6. The paper-free pre-reader according to claim 1, wherein the matrix resin is an epoxy resin composition.

7. A reinforcing fiber matrix layer in which an uncured matrix resin is impregnated into reinforcing fibers, a cover film attached to one surface of the fiber reinforced matrix layer, and a release surface attached to the other surface of the fiber reinforced matrix layer. A paper-free prepreg comprising a resin film for release, the release resistance of the release surface of the resin film for release being 0.5 to 200 g / cm.

8. The paper-free prepreg according to claim 7, wherein the release resistance value of the release resin film is 10 to 120 g / cm.

9. The paper-free prepreg according to claim 7, wherein the release resin film has a heat shrinkage of 1% or less at 150 ° C.

10. The paper-free pre-reader according to claim 7, wherein the reinforcing fibers are carbon fibers, glass fibers, or aramide fibers.

1 1. The paper-free pre-reader according to claim 7, wherein the matrix resin is an epoxy resin composition.

1 2. The release resin film is a release resin film having a heavy surface having a large peel resistance value and a light surface having a small peel resistance value, wherein the heavy surface is provided on the other surface of the fiber reinforced matrix layer. The peeling resistance value of the heavy surface of the release resin film is 200 gZcm or less and the peeling resistance ratio (heavy surface Z light surface) between the heavy surface and the light surface is 3.0. The single-purity prepreg according to claim 7, which is as described above.

1 3. The paper-free pre-reader according to claim 12, wherein the release resistance ratio between the heavy surface and the light surface of the release resin film is 5 or more.

14. The paper-free prepreg according to claim 13, wherein the release resistance of the heavy surface of the mold release resin film is 10 to 120 g / cm.

15. The paper-free prepreg according to claim 12, wherein the release resin film has a heat shrinkage of 1% or less at 150 ° C.

1 6. The paper-free pre-reader according to claim 7, wherein the peel resistance of the cover film is 0.5 to 200 g / cm.

1 7. The paper-free prepreg according to claim 7, wherein the cover film is a release resin film having a heavy surface having a large peeling resistance value and a light surface having a small peeling resistance value.

1 8. The paper-free pre-reader according to claim 7, wherein the cover film is formed of a thermoplastic resin film.

1 9. Thermoplastic resin film is polyamide 12 film, ionomer film, polyethylene terephthalate with both sides treated by corona discharge The paper-free pre-predator according to claim 18, which is a film, or a polybutylene terephthalate film having both surfaces subjected to corona discharge treatment,

20. A thermoplastic resin film is interposed between the cured matrix resins, wherein two or more of the paper-free prepregs according to claim 18 are heated after laminating the resin film for release. A method for producing a molded body.

2 1. Resin film for mold release with a peel resistance value of 150 gZcm or less on the heavy surface and a peel resistance ratio (heavy surface / light surface) of the heavy surface to the light surface of 3 or more. Applying an uncured matrix resin, sandwiching the reinforcing fibers between the two release resin films with the surfaces of the two release resin films facing each other, and removing the reinforcing fibers between the two release resin films. A step in which the reinforcing fiber is impregnated with the uncured matrix resin by applying pressure from outside to the release resin film under heating; and a step in which one of the two release resin films is impregnated in the reinforcement fiber. A reinforcing fiber matrix layer obtained by impregnating a reinforcing fiber with an uncured matrix resin, wherein the reinforcing fiber matrix layer is peeled from the cured matrix resin and a thermoplastic resin film is pressure-bonded to the surface of the peeled uncured matrix resin; Matri A thermoplastic resin film adhered to one surface of the release layer, and a release resin film having the release surface adhered to the other surface of the fiber reinforced matrix layer, wherein the release resin film is released. A method for producing a paper-free prepreg having a surface peel resistance of 150 g / cm or less.

2 2. One of two release resin films with a peel resistance value of 150 g / cm or less on the heavy surface and a peel resistance ratio (heavy surface Z light surface) of the heavy surface to the light surface of 3 or more. The uncured matrix resin is applied to the heavy surface of the mold release resin film coated with the uncured matrix resin and the light surface of the uncured matrix resin uncoated mold release resin film faces each other. Interposing a reinforcing fiber between two release resin films; and the interposed reinforcing fiber. Pressurizing the uncured matrix resin into the reinforcing fibers by applying pressure from outside the resin film for release to the reinforcing fiber, and the release resin with the light side of the two resin films facing inside A reinforced fiber impregnated with an uncured matrix resin, characterized by peeling the film from the uncured matrix resin impregnated with the reinforcing fibers and pressing a thermoplastic resin film on the surface of the peeled uncured matrix resin. A fiber matrix layer, a thermoplastic resin film adhered to one surface of the fiber reinforced matrix layer, and a release resin film adhered to the other surface of the fiber reinforced matrix layer. A method for producing a paper-free prepreg, wherein the release resistance of the release surface of the release resin film is 150 g / cm or less.