TW200404845A - Paper-free prepreg - Google Patents

Abstract

This invention discloses 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; one surface of the reinforcing fiber-matrix layer is laminated with said heavy surface, in which the heavy surface exhibits a peel strength of 200 g/cm or below and the peel resistant 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, an ionic resin or the like, the prepreg can be molded without removing the cover film.

Description

200404845 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a paperless polyester film ' In more detail, a paperless polyester film formed by sticking a heavy-surface and light-surface peeling resin film having different peel resistances on the front and back of the peeling resin film on one side of the reinforcing fiber composite layer. Furthermore, the present invention relates to a paperless polyacetate film in which a coating film and a resin thin film for peeling are adhered to a reinforcing fiber composite layer. In addition, the present invention relates to a paperless polyester film formed by bonding a heavy-faced and light-faced peeling resin film having different peel resistances on the surface of the resin film for peeling to the reinforcing fiber composite layer. The invention relates to a paperless polyester film formed by pasting a thermoplastic resin film on one side of a reinforcing fiber composite layer, and pasting a resin film having a heavy side and a light side on the other side, and the manufacture of the paperless polyester film Method and manufacturing method using paperless polyester film molded body. [Prior art] Conventionally, 'reinforced fiber impregnated with thermosetting resin to form a thin film polyester film is used as a material for fiber-reinforced plastic products in the manufacture of aircraft, golf clubs, fishing rods, etc., especially for reinforcement of reinforced concrete bridges and buildings Wait. When the above-mentioned polyester film is stored or transported, a release paper mainly composed of fibers is adhered to the surface thereof so that the polyester films do not adhere to each other. When used as a polyester film, the release paper is peeled from the surface of the polyester film and becomes waste. -5- (2) (2) 200404845 However, the above-mentioned cellulose-based release paper is relatively hard, which can cause tension after peeling. In particular, it imparts releasability and shows that it is often flame-resistant. Therefore, the release paper generated during the use of the polyester film causes a waste which is difficult to handle. The above-mentioned reasons cause problems such as the handling method of the release paper adhered to the polyester film. In order to solve this problem, Japanese Patent Laid-Open No. 10_2 9 8 3 1 5 is a polyester film composed of long-fiber stretched fabric or fabric impregnated with thermosetting resin, at least in its The resin film is pasted on one side to form a polyester film. When this polyester film is used, the resin film is peeled off. And the resin film after peeling forms waste. After the peeling, the resin film is soft and does not become as tight as the release paper. The conventional paper has a solution to the problem, which is described in the same publication. However, the above-mentioned polyester film still has problems that must be solved in addition to the above problems. That is, the polyester film causes curling when cutting the polyester film. This curling occurs when a necessary shape is cut before the polyester film is laminated to form a molded body. The occurrence of hemming causes a great adverse effect on workability in the step of manufacturing the molded body after manufacturing. Further, generally, a polyester film is cut into a necessary shape before being processed into a molded body. When the polyester film is cut, a large number of polyester films can be cut at a time after the film is peeled off. However, when conventional polyester films are cut at one time, the laminated polyester films cannot be adhered to each other and cannot be separated, which may cause problems in subsequent molding steps. Therefore, the conventional polyester film has a problem that the cutting operation efficiency cannot be improved. (3) (3) 200404845 [Summary of the Invention] The present invention develops a polyester film without a release paper, and first filed a patent application (Japanese Patent Application Laid-Open No. 2002-1 05223). This polyester film is a one-sided adhesive thermoplastic resin film in which a reinforcing fiber composite layer is impregnated with an unhardened composite resin. The thermoplastic resin film has a function of preventing release paper from sticking between the polyester films when the polyester films are stored or transported. When using polyester film, the thermoplastic resin film can be used without peeling. For example, after a plurality of layers of the polyester film are laminated, the thermoplastic resin film has good adhesion to the composite resin layer when it is formed by heating and curing, so it can be firmly adhered or adhered to the composite resin layer to form a molded body. Constitute itself. Therefore, no waste such as release paper or polymer film is generated during use as described above. A first object of the present invention is to provide a paperless polyester film containing cellulose as a main raw material that does not generate peeling waste during use, such as nonflammable waste such as release paper. Another object of the present invention is to provide not only a waste of cellulose-based release paper in the manufacturing step during use, but also a good workability and workability, and a small amount of peeled off waste polymer film during use. None, paper polyester film, its manufacturing method, and its manufacturing method using the same polyester film molded body. It is another object of the present invention to provide a polyester film having excellent dimensional stability without curling during storage, especially after cutting. The present invention for achieving the above object is described below. (1) Reinforced fiber impregnated with unreinforced composite resin reinforced fiber composite t -7- (4) (4) 200404845 layer, and a peeling resin formed by a heavy surface with a large peel resistance and a light surface with a small peel resistance. A film made of a resin film for peeling in which the heavy surface is adhered to one side of the fiber-reinforced composite layer, and the peel resistance 値 of the heavy surface of the resin film for peeling is not more than 200 g / cm, and the heavy surface and the light surface are Paperless polyester film with a peel resistance ratio (heavy side / light side) of 3.0 or more. (2) The paperless polyester film according to (1), in which the peel resistance ratio of the heavy surface to the light surface of the resin film for peeling is 5 or more. (3) The paperless polyester film according to (1), wherein the peel resistance 値 of the heavy surface of the resin film for peeling is 10 to 120 g / cm. (4) The paperless polyester film according to (1), wherein the resin film for peeling has a thermal shrinkage of 1% or less at 150 ° C. (5) The paperless polyester film according to (1), wherein the reinforcing fibers are carbon fibers, glass fibers, or aromatic polyamide fibers. (6) The paperless polyester film of (υ) described in which the composite resin is an epoxy resin composition. (7) A reinforcing fiber composite layer in which the reinforcing fiber is impregnated with an unhardened composite resin; a film adhered to one side of the fiber-reinforced composite layer; and The fiber-reinforced composite layer is formed of a resin film for peeling on which the peeling surface is adhered, and the peeling resistance 値 of the peeling surface of the peeling resin film is 0.5 to 200 g / cm. (8) Peeling resin The paperless polyester film described in (7) has a peel resistance 値 of 10 to 120 g / cm. (9) The resin film for peeling described in (7) has a thermal shrinkage of 1% or less at 150 ° C. (5) 200404845 (1 ο) The paperless polyester film according to (7), wherein the reinforcing fiber is carbon fiber, glass fiber or aromatic polyamide fiber. (1 1) The composite resin is epoxy The paperless polyester film according to (7) of the resin composition.

(1 2) The resin film for peeling is a resin film for peeling which has a heavy surface with a large peel resistance and a light surface with a small peel resistance. The heavy surface is adhered to the other surface of the fiber-reinforced composite layer, and the peeling is performed. The paperless polyester film according to (7), in which the peel resistance 値 of the heavy surface of the resin film is 200 g / cm or less and the peel resistance ratio of the heavy surface to the light surface (heavy surface / light surface) is 3.0 or more. (1 3) The paperless polyester film according to (12), wherein the peel resistance of the heavy surface and the light surface of the resin film for peeling is 5 or more. (14) The paperless polyester film according to (13), wherein the peel resistance 値 of the heavy surface of the resin film for peeling is 10 to 120 g / cm.

(1 5) The paperless polyester film according to (12) having a thermal shrinkage of 1% or less at 150 ° C at a resin film for peeling. (16) The paperless polyester film according to (7), having a peeling resistance 値 of the film of 0.5 to 200 g / cm. (1 7) The paperless polyester film according to (7), which has a peeling resin film having a heavy surface with a large peel resistance and a light surface with a small peel resistance. (18) The film is a paperless polyester film according to (7) formed of a thermoplastic resin film. (1 9) The thermoplastic film is fluorene amine 12 film, ionic resin thin -9- 326 (6) (6) 200404845 film, polyethylene terephthalate (丨8) Paperless polyester film as described. (20) A method for producing a molded article made of a thermoplastic resin film with a space between hardened composite resins, which is characterized by laminating two layers of the paperless polyester film described in (18) after peeling the resin film for peeling and heating. (21) The peel resistance of the heavy surface is less than 550g / crn, and the peel resistance ratio of the heavy surface to the light surface (heavy surface / light surface) is 3 or more. Resin, a step of sandwiching the reinforcing fibers between the two peeling resin films with the heavy surfaces of the two peeling resin films facing each other; heating the sandwiched reinforcing fibers from the outside of the peeling resin film The step of impregnating the reinforcing fibers with the unhardened composite resin under pressure. The method includes peeling any one of the two peeling resin films from the impregnated unhardened composite resin, and heat-bonding the surface of the unhardened composite resin after the peeling. Unreinforced composite resin impregnated with reinforced fiber reinforced fiber composite layers, such as plastic resin films; thermoplastic resin films bonded to one side of the fiber-reinforced composite layer; and peeling resin films to which the other side of the fiber-reinforced composite layer is bonded to its peeling surface The method for producing a paperless polyester film having a peeling resistance 値 of the peeling surface of the resin film for release is not more than 150 g / cm. (22) Peeling resistance of heavy surface '150g / cm or less, and peeling resin film 2' of heavy surface to light surface (heavy surface / light surface) 3 or more of the heavy resin is not coated on one of the heavy surfaces. The hardened composite resin is such that the heavy surface of the peeling resin film coated with the unhardened composite resin and the light surface of the peeling resin film without the uncured composite resin are opposed to each other, sandwiching the reinforcing fibers between these 2 -10- ( 7) 200404845 A step between peeling resin films; a step of impregnating the reinforcing fibers with uncured composite resin under pressure by heating the clamped reinforcing fibers from outside the peeling resin film; having two peeling resin films The peeling resin film with the light side as the inner side is peeled from the uncured composite resin impregnated with the reinforcing fiber, and the uncured composite resin impregnated with the characteristics such as the thermoplastic resin film is pressed against the surface of the uncured composite resin after the peeling. Fiber-reinforced composite layer; thermoplastic resin film pasted on one side of the fiber-reinforced composite layer; and a peeling tree on which the other side of the fiber-reinforced composite layer is pasted on its peeling surface The film or the like constituting the peeling resistance of the resin release film is peeled surface Zhi paperless method of producing a polyester film 150g / cm or less. [Embodiment] (First Form)

Fig. 1 is a schematic perspective view showing an example of the polyester film of the present invention. In Fig. 1, 1 is a polyester film. The polyester film 1 is formed by sticking a resin film 10 for peeling on one side of a reinforcing fiber composite layer 2. The peeling resin film 10 has a peeling resin film heavy surface 1 2 and a peeling resin film light surface 1 4 having different peel resistances on the front and back surfaces of the film 10. The peel resistance 値 of the heavy surface 12 is larger than the peel resistance 値 of the light surface 12. The peeling resin film 10 is adhered to the composite layer with its heavy surface 12 to form a tight contact with the reinforcing fiber composite layer 2. The reinforcing fiber composite layer 2 is formed by impregnating a reinforcing fiber with an unhardened composite resin 4. As the reinforcing fiber constituting the reinforcing fiber composite layer, carbon fiber, glass fiber, polyimide fiber, boron fiber, metal fiber, and other general polyester film can be used as the reinforcing fiber. Among them, carbon fiber, glass fiber, and polyamide are preferred. The forms of the reinforced fibers are formed into a single-direction parallel yarn, a multi-directional parallel yarn, and various reinforced fiber processed products such as woven fabrics, knitted fabrics, and non-woven fabrics. Examples of the uncured composite resin impregnated with the reinforcing fiber include a thermosetting resin used in the manufacture of ordinary polyacetate. Specifically, for example, epoxy resins, unsaturated polyester resins, phenolic resins, melamine resins, polyurethane resins, sand-containing resins, cis-butanedimine, cyanate resins, cis-butanedimide and cyanide Ester resin prepolymerized resin and the like. Mixtures of these resins can also be used. Among them, when using a fiber-reinforced composite material as a main polyester film, an epoxy resin composition having excellent heat resistance, elasticity, and chemical resistance is preferred. The uncured composite resin may contain a hardener, a hardening accelerator, and the like. The peeling resin film 10 has different peeling resistances on the surface of the film 10. The peeling resin film heavy surface 12 and the peeling resin film light surface 14 ° The materials of the peeling resin film include, for example, polypropylene, poly Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyvinyl chloride, polyimide, polyacetic acid, polycarbonate, etc. Do not use polyvinyl chloride, which is likely to cause poisons such as dioxin when incinerated. A method for forming a heavy surface and a light surface on the front and back surfaces of the resin film for peeling, for example, a method for performing peeling using a conventional method on one or both sides of the above-mentioned film -12-329 200404845 〇). Specifically, a conventional peelability imparting treatment using a silicon-containing resin, a fluorine-containing resin, an aliphatic paraffin, or the like forms a heavy surface and a light surface on the front and back surfaces of the peeling resin film 10. In terms of heat resistance and general-purpose properties, a silicone-containing peeling treatment is preferred. * A commercially available resin film may be used. Examples of commercially available products include Purex film, Teonex film (above, manufactured by Teijin DuPond film company), and SunTox-MPRS type (manufactured by Sun · Tox).

In the polyester film 1 of this embodiment, the peel resistance 値 of the heavy surface 12 of the resin film 1 for peeling is preferably 200 g / cm or less, but preferably 120 g / cm or less. When the peel resistance 値 of the heavy surface 12 exceeds 2000 g / cm, the resin film for peeling 1 is peeled off when the polyester film is used, and the composite resin 4 is left on the surface of the resin film 1 for peeling when peeling off. Possibly, or tearing the polyester film 1 is extremely difficult to handle.

The peel resistance 重 of the heavy surface 12 is preferably greater than 10 g / cm. When the peel resistance 値 of the heavy surface 12 is less than 10 g / cm, the adhesion between the reinforced fiber composite layer 2 and the heavy surface 12 is insufficient, and defects such as floating are formed. Phenomenon), which may cause processing problems such as cutting of the polyester film 1. The peel resistance 値 of the heavy surface 12 / light surface 14 of the peeling resin film 10 is 3.0 or more, but preferably 5 or more. When the peel resistance 値 is less than 3.0, the following manufacturing steps of the polyester film can easily transfer a part of the uncured composite resin 4 to the light side 14. As a result, it is difficult to obtain a resin film on which the uncured composite resin is uniformly coated on the heavy surface 12. In addition, when the peel resistance 値 3 · 〇 or more is less than 5.0, the composite resin part is transferred to the light surface 14 according to the type of the unhardened composite resin 4. 13- (10) (10) 200404845. In this form, the peeling resistance 値 is a 25 mm wide tape (NITT03 1B, manufactured by Nitto Denko Corporation). The peeling tape and the film are held at an angle of 1 80 ° at 23 ° C at 300 mm / min. The load per lcm of the tape width at the time of stripping the above-mentioned tape was removed at a speed. The peeling resin film 10 used in this embodiment preferably has a thermal shrinkage of 1% or less at 150 ° C, and more preferably 0.5% or less. Examples of the resin film 10 for peeling with the above thermal shrinkage include materials such as polyethylene terephthalate and polyimide. Alternatively, a heat-yield film having the above-mentioned range subjected to a heat-resistant treatment such as polyethylene terephthalate, polycarbonate, and polypropylene can be used. Figures 2 and 3 are examples of a preferred method of manufacturing the polyester film of this embodiment. First, a resin-coated film for impregnation is produced by applying an uncured composite resin to a heavy surface having a heavy- and light-surface peeling resin film (Fig. 2). The heavy surface of the peeling resin film 20 continuously fed from the peeling resin film roller 20a was 'transferred the uncured composite resin of a predetermined thickness adhered to the roller 26' to obtain a resin coating film 22 for impregnation. The unhardened resin is adjusted to a predetermined thickness by lightening between 26 and 27. Subsequently, the impregnated resin-coated film 22 is cooled through the cooling region p, and then wound around a recovery roll to obtain the impregnated resin-coated film 22. 29a and 29b are blades for adjusting the thickness of the resin. Next, "the same method as for manufacturing the resin-coated film 22 for impregnation in the above-mentioned manner" is to prepare a resin-coated release paper 3 1 coated with uncured composite resin on one side of the release paper. ◦ The release paper is not limited here. -14- (11) 200404845 Secondly, as shown in FIG. 3, the film 22 is applied from the resin-coated film roll 22a for impregnation, or the resin-coated release paper roll 3; [a, the resin-coated release paper 3 1 is The composite resin-coated surfaces are fed out while the reinforcing fibers 30 are continuously fed. At this time, when the uncoated composite resin-coated impregnated resin coating film 22 is fed out from the roll, the heavy and light surfaces of the resin film for peeling have different peel resistances. Hardened compound tree

fat.

Next, the laminated film 3 3 composed of the impregnated resin-coated film 22 and the resin-coated release paper 3 1 sandwiching the reinforcing fibers 30 is sent to the heating sheet 37 provided with a pressure roller 36 in the upper part, and then fed The heating roller 38, which is provided with a pressure roller 36 in the upper part, presses the laminated film 33 under heating to impregnate the unreinforced composite resin into the reinforcing fiber 30. After the laminated film 3 3 is cooled in the cooling region P, the release paper 3 2 is peeled off from the laminated film 3 3 to obtain a paperless polyester film 34 in this state. The paperless polyester film 3 4 in this state is wound around a polyester film recovery roller 34a. The release paper 32 is wound around a release paper recovery roller 32a and recovered. The recovered release paper 32 can be reused. Therefore, the release paper is used in the production process and does not flow out and become waste. In the above embodiment, when the reinforcing fiber 30 is impregnated with the unhardened composite resin, the impregnated resin-coated release paper is laminated on the reinforcing fiber 30, but it is not limited to this. The above-mentioned impregnated resin coating film 22 may be laminated on both the upper and lower sides of the reinforcing fibers 30 and impregnated with an unhardened composite resin. At this time, the upper or lower peeling resin film 20 can be peeled off at the end of the step. (15) (12) (12) 200404845 Release paper 3 2 The polyester film in this form can also be recovered. In the above-mentioned embodiment, although the unhardened composite resin is supplied from both the top and bottom of the reinforcing fiber 30 to the reinforcing fiber 30, the composite resin may be supplied only on one side depending on the purpose. The composite resin is supplied from one side as shown in Fig. 3. The resin-coated release paper 31 can be replaced with a release paper. After the resin film 10 for peeling is produced, the polyester film 1 can be peeled off at any time. Also, it can be peeled off immediately before the polyester film 1 is used. The peeling resin film 10 can be recycled because it is a plastic product. Can be disposed of as flammable waste when discarded. The paperless polyester film of this form is not adhered to a cellulose-based release paper, and therefore it does not generate flame-resistant waste during use. The paperless polyester film of this form can recycle the resin for peeling and reduce the amount of waste. When disposing of the film, dispose of it as a flammable waste. In addition, the resin film for peeling has a heavy surface and a light surface with different peel resistances. Therefore, when the paperless polyacetate film made in this form is made from the resin-coated film roll 22a for impregnation, the composite resin coated on the heavy side of the film is not transferred to the light side, and a polyester film can be produced. In addition, the paperless polyester film according to the present embodiment can be easily peeled of the resin film for peeling when used, and the surface of the reinforcing fiber composite layer when peeled has excellent smoothness. In addition, a paperless polyester film-loaded -16- (13) (13) obtained by using a thermal shrinkage of 1% or less at 150 ° C of 1% 'preferably 0.5% or less at 10 o'clock' is obtained. 200404845 High dimensional stability after breaking into products, the incidence of deformation such as curling is low. In addition, the paperless polyester film of this embodiment can reliably prevent adhesion between the light side of the resin film for peeling having a heavy surface and a light surface and other polyester films even after laminating and cutting. Therefore, a large number of polyester films of this form can be laminated and cut to improve cutting efficiency. (Second mode) Fig. 4 is a schematic perspective view showing a second mode of the polyester film of the present invention. In Fig. 4, 201 is a polyester film, and one side and the other side of the reinforcing fiber composite layer 202 are formed by adhering a cover film 208 and a peeling resin film 210. The resin film 210 for peeling is impregnated with the reinforcing fiber 206 into an unhardened composite resin 204. The reinforcing fibers constituting the reinforcing fiber composite layer 202 are the reinforcing fibers described in the first figure. As the unhardened composite layer resin impregnated with the reinforcing fiber, the unhardened composite resin described in the first figure can be used. The peel resistance 値 is as described in the first aspect. The peeling resistance 値 of the surface 212 of the peeling resin film 210 which is in contact with the reinforcing fiber composite layer 202 and the peeling resin film 210 is 0.5 to 20 g / cm. When the peel resistance 値 is greater than 200 g / cm, when the polyester film is used, when the resin film for peeling is peeled off from the polyester film 201, the composite resin 204 is partially transferred to the resin film for peeling 2 1 0, or It is extremely difficult to tear the polyester film 201. And when the peel resistance 値 is less than 0.5 g / cm, at (14) 200404845

In the polyester film manufacturing process described later, when the uncured composite resin-coated impregnated resin coating film is continuously fed from a roller, the uncured composite layer resin is partially transferred to be sandwiched between the impregnated resin-coated film. . As a result, it becomes difficult to deliver the impregnated resin-coated film which uniformly applies the uncured composite resin. The peeling resistance 値 is preferably 10 to 120 g / cm. When the peel resistance 値 is less than 10 g / cm, the adhesiveness between the peeling resin film 2 1 0 and the reinforced composite layer 2 2 2 is insufficient, such as a defect of formation of floating, or a depression (a phenomenon in which the composite resin sinks on the surface of the composite layer). The reason for this is the hindrance during the molding process using polyester film. The method of adjusting the peel resistance 値 of the resin film for peeling to the above-mentioned range, and the material, heat shrinkage rate, and the like of the resin film for peeling are the same as those of the first embodiment. The peeling resistance 値 of the surface 2 1 4 of the peeling resin film 2 1 0 which is not in contact with the reinforcing fiber composite layer 202 is not limited, and may be any value.

The coating film 20 8 is preferably a high-molecular film having excellent peelability such as polyethylene and a fluororesin. In particular, a film subjected to a peeling treatment can be used. Especially, it is preferable to use a cheap polyethylene film for general use. As the polyester film 201 of this embodiment, the above-mentioned peeling resin film can be used as the cover film 208. At this time, the peel resistance 値 of the surface of the film 208 that is in contact with the reinforcing fiber composite layer 202 is also set to 0.5 to 200 g / cm. Figures 5 and 6 show an example of a preferred method for producing a polyester film in this form. First, apply an unhardened composite layer to the release surface of the release resin film -18- (15) 200404845

Resin-coated resin-coated film (Figure 5). An uncured composite resin having a predetermined thickness is supplied and applied to the surface having the peeling resistance film 値 of the peeling resin film 220 continuously fed from the peeling resin film roll 220 to obtain a resin coating film 222 for impregnation. The unhardened composite resin is passed between rollers 226 and 227 to a predetermined thickness. The impregnated resin coating film 222 is cooled in the cooling area P, and is then wound around a recovery roll at the same time as the release paper 22 1 sent out by the release paper roll 22 1 a. An impregnated resin-coated film roll 222a holding a release paper can be obtained between the resin-coated films. In addition, 224, 225, and 228 are rollers, and 229a and 229b are blades.

Fig. 5 illustrates the production of the impregnated resin-coated film roll 222a by sandwiching the release paper 221 between the impregnated resin-coated film 222, but it is not limited to this. Instead of the release paper 221, a film, a resin film for peeling, etc. may be sandwiched. However, in any case, the peeling resistance of the unhardened composite layer resin-coated surface of the impregnated resin coating film 2 2 2 is higher than that of the unhardened composite layer resin, and this surface must be adhered to the unhardened composite layer resin. When a film or the like is used instead of the release paper, a polyethylene film having a low peel resistance and a low cost is preferred as the film. Next, a release paper (resin-coated release paper) 2 3 1 coated with an uncured composite resin on one side in the same manner as the resin-coated film roll 2 2 2 a manufactured by the above method was prepared. Next, the film 222 and the release paper 23 1 are fed out in a state where the respective resin coating surfaces of the composite layer formed by the resin-coated film roll 2 2 a for impregnation and the resin-coated release paper roll 2 3 1 a are opposed to each other, and the continuous Feed reinforcing fibers 23 0. When the impregnated resin-coated film 2 2 2 coated with the uncured composite resin is fed from a roll, and the release paper is held between the impregnated resin-coated film 2 2 2-19- (16) 200404845 22 1 The peel resistance 値 of the surface on which the composite resin contacts is lower than the peel resistance 値 of the peeling resin film 220. Therefore, the composite resin is not transferred to the δH peeling paper 2 2 1 and sent out of the film. Subsequently, the laminated body 242 of the impregnated resin-coated film and the resin-coated release paper 23 1 sandwiching the reinforcing fibers 23 0 is fed into the heating plate 23 7 provided with a roller 2 3 5 in the upper part, followed by the pressure roller 2 3 described above. Add 6 2 3 8 and press under heat. By the above operation, the uncured composite resin is impregnated and strengthened 230. After the laminated body 242 is cooled in the cooling region ρ, the release paper 2 3 2 is peeled off from the laminated body and wound on a release paper recovery roll 2 3 2 a to be recovered, and then the surface after the release paper 2 3 2 is removed is pressed at room temperature. The cover film 23 3 sent from the cover roller was obtained to obtain a paperless polyester film 234 in this form, and this was wound around a polyester film to recover light 2 3 4 a. In addition, 223 micro release paper and 223b are release paper recovery rollers, and are lightly pressed. Among these, when a resin film for peeling is used instead of the coating film 23 3, it is preferable that the surface of the pressure-bonded reinforcing fiber composite layer has a lower peel resistance than the uncured composite resin coating surface of the resin coating film for impregnation. The recovered release paper can be reused. Therefore, it is peeled off for reuse in the production step without flowing out. In the above example, when the uncured composite resin is supplied to the reinforcing fibers, the resin-coated release paper 231 is laminated on the upper surface of the fibers 230, but the resin-coated film for impregnation is also laminated. At this time, after passing through the cooling zone, there is no need to replace the coating film 23 3, and the special layer between the reinforcing fibers can be printed on the 222 pressurized heat roller fibers 242. With 2 3 3 a after 23 9b. This coated paper can be strengthened. Both sides of the domain P can be strengthened. -20- (17) 200404845 A polyester film made of a resin film for adhesive peeling can be obtained. In the above example, although the uncured composite resin is supplied from both the upper and lower sides of the reinforcing fiber, it may be supplied from one side only depending on the purpose. In the manufacturing method shown in Fig. 6, an uncured composite resin-uncoated release paper or a release resin film can be used instead of the resin-coated release paper roll 2 3 1 a, and the uncured composite resin can be supplied on one side.

The peeling resin film and film can be peeled off at any time after the polyester film is manufactured. Or it can be peeled off immediately before using the polyester film. Since these films are plastic products, they can be recycled and discarded as flammable waste. Since the paperless polyester film of this form is not adhered to the fiber-based release paper, no flame retardant waste is generated during use. This paperless polyester film can be recycled for laminating and peeling resin films, reducing waste. Also, these films can be disposed of as flammable waste when discarded.

In addition, the paperless polyester film of this form can easily peel the resin film for peeling, and the surface of the reinforcing fiber composite layer at the time of peeling has excellent smoothness. In particular, when used as a resin film for peeling 2 10, the thermal shrinkage of 150 ° C is 1% or less, and preferably 0.5% or less. The dimensional stability of the obtained paperless polyester film after being cut into products High, less occurrence of deformation such as curling. (Third aspect) Fig. 7 shows an example of the configuration of a third aspect polyester film. In Fig. 7-21-(18) 200404845, 301 is a polyester film, and one side and the other side of the reinforcing fiber composite layer 302 are formed by pasting a coating film 3 0 8 and a resin film 3 10 for peeling. The peeling resin film 3 1 0 has peel resistance on the inside and outside of the surface. The heavy surface 3 1 2 and the light surface 3 1 4 and the heavy surface 3 1 2 are adhered to the reinforcing fiber composite layer 3 02. The reinforcing fiber composite layer 3 02 is formed by impregnating the unreinforced composite resin 3 0 4 with the reinforcing fiber 3 06.

The reinforcing fibers constituting the reinforcing fiber composite layer 320 and the uncured composite resin impregnated with the reinforcing fibers are the same as those used in the first embodiment. The method of forming the material, heat shrinkage ratio, and the heavy and light sides of the resin film for peeling 3 1 10 is the same as that described in the first embodiment. As a resin film for peeling, the same thing as a commercial item can be used.

In the polyester film of the third aspect, the peel resistance 的 of the heavy surface 312 of the peeling resin film 3 10 is not more than 200 g / cm, and may be not more than 120 g / cm. When the peel resistance of the heavy surface 312 is greater than 200 g / cm, a polyester film 3 1 is used when the peeling resin film 3 1 0 is peeled off, and a part of the composite resin is transferred to the peeling resin film 3 1 0, or tearing the polyester film 301, the operation is extremely difficult. In addition, the peel resistance 値 of the heavy surface 312 is more preferably 10 g / Cm or more. When the peel resistance 値 of the heavy surface 312 is less than 10 g / Cm, the adhesion between the heavy surface 3 1 2 and the reinforcing fiber composite layer 302 is impaired. The reasons for the shortcomings of floating are the obstacles to the processing of polyester film during molding. In addition, the peeling of the heavy film 3 1 2 / light surface 3 1 4 of the resin film 3 1 0 -22- (19) 200404845 The separation resistance 値 is 3.0 or more, but preferably 5 or more. When the peel resistance 値 is less than 3.0, the uncured composite resin is partially transferred to the light surface 3 1 4 in the polyester film manufacturing step described later. As a result, an impregnated resin-coated thin film on which the uncured composite resin is uniformly coated on the heavy surface 3 1 2 cannot be obtained. In addition, when the peel resistance 値 is greater than 3.0 and less than 5, it may be partially transferred to the light surface depending on the type of the uncured composite resin.

The film is preferably a polymer film having excellent peelability such as polyethylene and a fluororesin. In addition, any film can be used as long as it is subjected to a peeling treatment, but a general-purpose and inexpensive polyethylene film is preferred. The polyester film of this embodiment may use the above-mentioned resin film for peeling as a coating film. In this case, either the heavy surface or the light surface may be in contact with the reinforcing fiber composite layer. However, when workability is considered, it is better to use the light side. Figures 8 and 9 are diagrams showing an example of a preferred method for manufacturing the polyester film of the third embodiment.

First, an uncured composite resin is coated on the heavy surface of the peeling resin film 320 to produce a resin film for impregnation (Fig. 8). The heavy surface of the peeling resin film 3 20 continuously fed from the peeling resin film roll 3 2 0a is supplied and coated with a predetermined thickness of uncured composite resin between the rolls 326 and 327 to obtain the resin coating film 3 for impregnation. twenty two. After the impregnated resin coating film 3 22 passes through the cooling area P, it is wound around a recovery roll to recover the impregnated resin coating film roll 322a, and 324, 325, and 328 are rolls, and 329a and 329b are heating sheets. Next, a release paper (resin-coated release paper) 3 3 1 coated with an uncured composite resin on the release surface was produced in the same manner as the impregnated resin-coated film roll -23- (20) 200404845 3 22a. The resin coating film 3 2 2 from the resin coating film for impregnation 3 3 2 a, and the resin coating release paper 3 3 from the resin coating release paper 3 3 1 a were light-coated, and the composite resin coating was applied separately. The covering surfaces are sent out while facing each other, and the reinforcing fibers 3 3 0 are continuously fed in between (Fig. 9).

Light 3 2 2 a When feeding the uncoated composite resin-coated thin coating for impregnation fe 3 2 2 'The peel resistance between the heavy and light sides of the resin film for peeling is different.' An impregnated resin-coated film 3 22 on which a hardened composite resin is transferred on a light surface.

Next, the laminated body 3 42 formed by holding the impregnated resin-coated film 3 22 and the resin-coated release paper 331 for reinforcing the first dimension 3 3 0 is sent to a heating sheet 3 3 7 provided with a pressure roller 3 3 5 on the upper side. Next, the heating roller 3 3 8 including the pressure roller 3 3 6 is pressed under heating. With this operation, the unhardened composite resin is impregnated with the reinforcing fibers. After the laminated body 3 4 2 is cooled in the cooling area P, the release paper 3 3 2 is peeled off. This release paper 3 3 2 is wound around a release paper recovery roller 3 3 2 a and recovered. Subsequently, the cover film 3 3 3 sent out by the cover roller 3 3 3 a is crimped to the laminated body 3 42 after peeling off the release paper 3 3 2 at normal temperature to obtain a paperless polyester film 3 3 4 in this form. Then, this is wound on a polyester film recovery roller 3 3 4a. In addition, 3 3 9a and 339b are pressure rollers, and 3 40 are rollers. The release paper 3 3 2 recovered in the above manufacturing steps can be reused. Therefore, the release paper 3 3 2 can be reused in the production step without flowing out. -24- 41 (21) 200404845 Furthermore, the above-mentioned peeling resin film may be used instead of the coating film. At this time, the surface to which the reinforcing fiber composite layer is adhered may be a light surface or a heavy surface. In the above example, Fig. 9 shows that when the reinforcing fiber 3 3 0 is impregnated with the unhardened composite resin, the upper surface of the reinforcing fiber 3 3 0 is pressure-bonded with the resin-coated release paper 3 3 1 and impregnated with the unhardened composite resin. However, the method is not limited to this method, and the impregnated resin-coated film may be impregnated onto the upper and lower surfaces of the reinforcing fibers 3 300 at the same time to impregnate the uncured composite resin. In this case, it is not necessary to replace the release paper with a cover film 'and a polyester film composed of a resin film for double-sided adhesive peeling can be obtained. Further, in the above example, the unhardened composite resin is supplied from both the upper and lower sides of the reinforcing fiber, but the unhardened composite resin may be supplied only on one side depending on the purpose. In the case of single-sided supply, an uncured composite resin uncoated release paper or a resin film for release may be used in place of the resin-coated release paper roll for impregnation shown in Fig. 9 3a.

The peeling resin film and film can be peeled off at any time after the polyester film is manufactured. Also, it can be peeled off immediately before the polyester film is used. These films are plastic products that can be recycled and disposed of as flammable waste when discarded. Since the paperless polyester film of this form is not adhered to a cellulose-based release paper, it does not generate a flame retardant waste during use. The paperless polyester film of this form can be used for the recovery of the cover film and the peeling resin film, and the amount of waste can be reduced. These films can be disposed of as flammable waste when discarded. In addition, the peeling resin film has a peeling resistance, a different heavy surface, and a light surface of -25- (22) 200404845. Therefore, the composite resin applied to the film when fed out from the roller is not transferred to the light surface, and polyester can be produced. film. In addition, the paperless polyester film of this embodiment can easily peel the resin film for peeling, and the surface of the reinforcing fiber composite layer at the time of peeling has excellent smoothness. In addition, when using a thermal shrinkage of 150 ° C of 1% or less, preferably 0.5% or less, as the resin film for peeling 3, 10, the obtained paperless polyester film has a partial cut to form a product with a stable size. 'And less crimping. In addition, the paperless polyester film of this embodiment can reliably prevent the light surface of the resin film for peeling having a heavy surface and a light surface from contacting with other polyester films after laminating and cutting. Therefore, a large number of polyester films in this form can be laminated for cutting, and cutting efficiency can be improved. (Fourth Form)

The fourth aspect of the polyester film is a thermoplastic resin film adhered to one side of a reinforcing fiber composite layer composed of unreinforced composite resin impregnated with a reinforcing fiber, and the other side is adhered to a resin film for peeling with a heavy surface and a light surface having different peel resistances. Consisting of multiple faces. The thermoplastic resin film and the resin film for peeling can prevent the polyester films from being fixed to each other or the composite resin from sinking during storage or transfer of the polyester film in this form. In particular, these films have a protective paper function for protecting the reinforcing fiber composite layer from the occurrence of damage to the reinforcing fiber composite layer and the adhesion of foreign matter. In addition, when the polyester film of this form is used, the resin film for peeling and peeling can be peeled off, but it can be used without peeling the thermoplastic resin film. For example, when the polyester film in multiple forms after peeling off the resin film for lamination is laminated and peeled, the thermoplastic resin film and the composite resin layer have good adhesion when heat-molded to produce a molded body, and can be firmly melt-adhered or adhered to the composite resin. On the layer, the structure itself of the molded body is formed.

FIG. 10 is a schematic view showing an example of the polyester film of the fourth embodiment. In Fig. 10, 401 is a polyester film, and a thermoplastic resin film 40 8 is adhered to one side of the reinforcing fiber composite layer 402 and a resin film 4 1 0 is peeled to the other side. The reinforcing fiber composite layer 402 is formed by impregnating a reinforcing fiber 406 with an unhardened composite resin 4 0 4. As the reinforcing fiber 406 constituting the reinforcing fiber composite layer 402, the article described in the first aspect can be used.

As the uncured composite resin 404 impregnated with the reinforcing fibers 406, a thermosetting resin used in the manufacture of general polyester film can be used. Specific examples include epoxy resin, unsaturated polyester resin, and urethane resin. From the viewpoint of the affinity with the thermoplastic resin film, an epoxy resin is particularly preferred. The proportion of the unhardened composite resin 404 impregnated with the reinforcing fibers 406 is preferably 10-50 mass% relative to the reinforcing fiber composite layer 402, and more preferably 15-30 mass%. The thermoplastic resin film 408 adhered to one side of the reinforcing fiber composite layer 402 preferably has the properties described below. (1) The glass transition temperature (Tg) is below 80 ° C, the actual use temperature is -27- (24) 200404845 (5-3 5 ° C) has a large vibration loss coefficient; (2) the water absorption is below 1% by mass ; (3) less heat shrinkage at the curing temperature of the polyester film (90-180 T :); (4) the thickness is preferably 10-100 // m.

Specific examples of the thermoplastic resin film 4 0 8 having the above properties include nylon 1, 2, ionic resin, polyethylene terephthalate (PET) after corona discharge treatment on both sides, and corona discharge treatment on both sides. Polybutylene terephthalate (PBT), etc. Corona discharge treatment conditions for thermoplastic resin films vary depending on the width, thickness, and processing speed of the film, but they can generally be expressed in terms of electricity per unit time and unit area. The discharge capacity is preferably 30-50 W / m2 · min.

The corona discharge treatment of the thermoplastic resin film forms polar groups (for example, -OH group, -COOH group, = CO group, etc.) on the surface of the film, which can improve the chemical affinity of the epoxy resin for the thermoplastic resin film. This can improve the adhesion between the thermoplastic resin film and the epoxy resin. The peeling resin film 4 1 0 has a heavy surface 4 1 2 and a light surface 4 1 4 having different peel resistances 表 on the front and back surfaces. The peeling resistance 値 of the heavy surface 4 1 2 is higher than that of the light surface 4 1 4 ′ and the reinforcing fiber composite layer 4 0 2 is bonded to the heavy surface 4 1 2 side of the resin film for peeling. The method of forming the material of the peeling resin film, the heavy and light sides of the peeling resin film, the preferred heat shrinkage rate, and specific examples of the peeling resin film have been described above. In the polyester film of this form, the peeling surface of the resin film 4 1 0-28- (25) 200404845 412 has a peel resistance 设定 of 150 g / cm or less, but preferably 130 g / cm or less. It is preferably less than 120 g / cm. When the peel resistance of the heavy surface is more than 150 g / cm, when the resin film for peeling is peeled off when using a polyester film, the composite resin is partially transferred onto the resin film for peeling. In addition, when manufacturing a thin polyester film having a reinforcing fiber weight of 50 g / cm2 or less and a resin content of about 26% by mass, the polyester film is torn when peeling off the peeling resin film, which is extremely difficult to handle.

The peel resistance 重 of the heavy surface 412 is preferably 10 g / Cln or more. When the peeling resistance 値 of the heavy surface 412 is less than 10 g / cm, the adhesion between the heavy surface 412 and the reinforcing fiber composite layer 402 is insufficient, which leads to an obstacle in the processing of the polyester film due to the formation of floating defects.

The peel resistance 値 of the heavy surface 4 1 2 / light surface 4 1 4 of the resin film 4 1 0 for peeling is preferably 3 or more, but preferably 5 or more. When the peeling resistance 値 is less than 3, in the production step of the polyester film described later, when the peeling resin film coated with the unhardened composite resin is fed from the roller to the heavy surface 4 1 2, the resin portion on the heavy surface 4 1 2 is sent. Transfer on the light side 4 1 4. In addition, when the peel resistance 値 is greater than 3 and less than 5, it may be partially transferred to the light surface due to the type of the uncured composite resin. Figures 11 and 12 show an example of a preferred method for manufacturing the polyester film of the fourth embodiment. First, an uncured composite resin is coated on the heavy surface of the peeling resin film to produce a resin coating film for impregnation (Fig. 11). An uncured composite resin having a predetermined thickness was coated from the heavy surface of the peeling resin film 420 continuously fed from the peeling resin film roll 420a to obtain a resin coating film for impregnation • 29-346 (26) 200404845 421. The thickness of the unhardened composite resin can be adjusted between rollers 426 and 427. After passing the resin coating film for impregnation through the cooling area P, the resin coating film for impregnation 21 is wound on a roll to obtain a resin coating film roll 421a for impregnation. In Fig. 11, 424, 425, and 428 are light, and 29a and 29b are heating plates. Next, the impregnated resin-coated film roll 421a is manufactured by the same method as the impregnated resin-coated film roll 42a.

As shown in FIG. 12, the impregnating resin film roll 42 ″ a and the impregnating resin coating film roll 4 2 1 a ′ are used, and the impregnating resin coating film 4 2 1 and 42 1 ′ are coated with a composite resin. The reinforcing fibers 43 are fed in a state of being opposed to each other, and the reinforcing fibers 43 0 are continuously fed in between, and pressed by a pressure roller 43 4. When the impregnated resin coating films 421 and 421 'are fed out from the rollers 421a and 421a', the peel resistance of the resin film for peeling differs between the heavy surface and the light surface, so the unhardened composite resin is not transferred to the light surface and is sent out. film.

Next, the laminated body 442 composed of the impregnated resin coating films 421 and 421 'holding the reinforcing fibers 4 3 0 is fed into the heating plate 4 3 6 provided with a pressure roller 435 on the upper side, and then the pressured roller is provided on the upper portion. 4 3 7 The heating roller 4 3 8 is pressed under heating. By this operation, the unhardened composite resin is impregnated with the reinforcing fibers. After the pressurized laminated body 442 passes through the cooling area P, the peeling resin film 420 on the upper surface of the laminated body 442 is peeled off and wound around a recovery roll 422 for recovery. Subsequently, the thermoplastic resin film 423 sent from the thermoplastic resin film roller 423 a was crimped on the upper surface of the laminated body 442 of the resin film 420 for peeling by a pressure roller 43 9 at room temperature to obtain a paperless polyester film of a fourth form. 43 1. The obtained polyester film in the fourth form is wound around a roller 43 1 a -30- (27) 200404845 to form a polyester film roller. In addition, 4 4 0 is a roller. In the above example, although the uncured composite resin is applied to both the upper and lower two peeling resin films to which the reinforcing fibers 4 3 0 are adhered, the present invention is not limited to this, and the peeling resin film may be applied to only one side Apply unhardened composite resin.

The peeling resin film 420 wound around the roller 422 can be reused. Therefore, the peeling resin film 420 can be reused in the production process without flowing out. The peeling resin film 4 1 0 adhered to the other side of the polyester film is peeled off at an arbitrary time after the polyester film is manufactured. It can also be peeled off immediately before using the polyester film. These films are plastic and therefore recyclable. They can also be disposed of as flammable waste when discarded. In addition, when the thermal shrinkage rate of 150 ° C is 1% or less, and preferably 0.5% or less, the resin film for peeling 4 10 is used. The obtained paperless polyester film has high dimensional stability after being cut into a product, Occurrence of edge deformation is low.

Next, a description will be given of a case where a molded body is produced using the polyester film of the fourth embodiment. Figure 13 shows the peeling resin film or thermoplastic resin film on the surface of the polyester film of the fourth embodiment, and the peeled polyester film is laminated with a plurality of sheets (four in this figure), followed by The laminated film is heat-molded to produce a molded body. A first polyester film 300a composed of a reinforced fiber composite layer 2a and a thermoplastic resin film 8a is prepared, and a second polyester film composed of a reinforced fiber polyester film 2b and a thermoplastic resin film 8b is sequentially laminated on the top.-31- (28) 200404845% 3 0 0 b, the third polyester film 3 00 c composed of the reinforcing fiber composite layer 2 c and the thermoplastic resin film 8 c. Finally, a polyester film 400 composed of the reinforcing fiber composite layer 2d after the peeling resin film and the thermoplastic resin film are laminated and peeled off. This laminate is heated to obtain a molded body.

Heating is performed according to the type of composite resin, usually 90-180 ° C is preferred. When heated at this temperature, a thermoplastic resin film such as nylon 12 has a lower melting point, and the reinforcing fiber composite layer is fusion-bonded firmly. In addition, when the thermoplastic resin film is a high-melting-point film of polyethylene terephthalate or polybutylene terephthalate, the surface is treated with corona discharge, which can be firmly adhered to the reinforcing fiber composite layer. Pick up. In addition, it is preferable to press while decompressing and degassing while heating. The above can prevent the formation of defective molded bodies due to the inclusion of air bubbles inside. The degree of decompression is preferably (-0.08 7) to (-O.lOl) MPa. In addition, in the example of the molded article, although the last laminated polyester film is a polyester film 400 composed of a non-adhesive thermoplastic resin film, it is used in applications where the thermoplastic resin film can be exposed on the surface of the obtained molded article. Polyester film 400 can be laminated with a thermoplastic resin film. In addition, when the polyester film of the present embodiment is used for the reinforcement of the structure, etc., the polyester film of the present embodiment can be sequentially laminated on the reinforcing portion, and then it can be reinforced by heating. The above-mentioned molded body is completely broken by bending failure, and plastically deforms the failure pattern of the interlaminar shear strength test. The paperless polyester film of this form is composed of a thermoplastic resin film and a peeling resin film adhered to a reinforcing fiber composite layer. When used, it is not necessary to peel off -32- 349 (29) (29) 200404845. After removing the thermoplastic resin film, it can be laminated and cured simultaneously with the reinforcing fiber composite layer. The polyester film of this form is not adhered to the cellulose-based release paper, and the cellulose-based release paper is not used in the production process, and no flame-resistant waste is generated. The amount of waste can be reduced by recycling the peeling resin film peeled from the polyester film of this form, and it can be treated as a flammable waste even when it is treated as waste. In addition, the polyester film of this embodiment can easily peel off the resin film for peeling, and the surface of the reinforced fiber composite layer after peeling has excellent smoothness. In addition, when a thermal shrinkage of 150 ° C is 1% or less, and preferably 0.5% or less, the resin film for peeling 4 10 is used. The obtained paperless polyester film has high dimensional stability after being cut into a product. Occurrence of edge deformation is low. In addition, even when the polyester film of this embodiment is laminated and cut, adhesion between the light surface of the resin film for peeling having a heavy surface and a light surface and other polyester films can be reliably prevented. Therefore, it is possible to laminate and cut a large number of polyester films in this form, thereby improving cutting efficiency.

(Hemming elimination method) The resin-coated film for impregnation of the polyester film produced by the above method is more exposed to heat or tension during the manufacturing process. Therefore, the resin-coated film for impregnation generates shrinkage stress. Therefore, under the influence of the residual stress of the film, the obtained polyester film may be curled when the polyester film is cut into a necessary shape during molding. The following describes the side-to-side method of the unrolled paperless polyester film that can be applied to the first to fourth embodiments. -33- (30) 200404845 (First method) The table 1 method is a method in which the resin film used for the impregnation is made of a peeling resin film and the other resin film for peeling is finally replaced in the production step of the polyester film.

In Fig. 14, reference numerals 502 and 504 represent resin coating films for impregnation, in which the uncured composite resin is applied on the heavy surface, and the composite resin coating surfaces face each other. 5 0 6 is a reinforcing fiber 'sandwiched between two impregnated resin-coated films 5 0 2 and 5 4 and sent to a roller 5 0 8 and 5 1 0, and pressed there to form a laminated body 5 2 2. The laminated body 5〗 2 is then pressurized by the heating sheet roller 5 1 4 and the pressure roller 5 1 6 and then cooled in the cooling section 5 1 8. Subsequently, the peeling resin films 5 20 and 522 on the upper and lower sides of the laminated body 5 1 2 are peeled off and wound on rolls 524 and 526.

Next, the laminated body after peeling the peeling resin films 520 and 5 22 is coated with a film such as polyethylene 5 2 8 or a replacement film 5 3 0 is bonded with a peeling film or the like. The polyester film 5 3 2 of the article is then wound on a roll. Among them, the coating film 5 2 8 and the replacement film 5 3 0 do not shrink without being affected by the heating and tension of the previous step. The coating 5 2 8 is not particularly limited, and a general article can be used. As long as the replacement film 5 3 0 satisfies the restrictions described in the above embodiments (limitations of peel resistance 値, peel resistance 重 for heavy and light surfaces), etc., it is not limited to use. The thickness of the coating film and the replacement film is preferably from 10 to 200 m, and more preferably from 25 to 100 // m. According to the first method, the resin film for peeling is replaced with another film at a later stage in the production step of the polyester film, so even if the obtained polyester film is subjected to

-34- (31) 200404845 A small amount of hemming can still be obtained by cutting. (Second method) Fig. 15 shows a second method for preventing curling. 6 02 and 604 are impregnated resin coating films on which the uncured composite resin is applied on the heavy surface so that the composite resin surfaces face each other.

The resin film for peeling of the resin coating film for impregnation 602 is preferably 1% or less of the thermal shrinkage of 150, and more preferably 0.5% or less. 606 is a reinforcing fiber, and is sandwiched between two resin coating films 602 and 604 for impregnation with rollers 60 8 and 610 to form a laminated body 612. The laminated body 6 1 2 is then pressurized by the heating sheet roller 6 1 4 and the pressure roller 6 1 6 and then cooled in the cooling portion 6 1 8. Subsequently, the peeling resin film 620 on the upper surface of the laminated body 6 1 2 is peeled off and wound on a roller 624.

Next, a laminate film 628 such as a polyethylene film is adhered on the laminated body from which the peeling resin film 620 is peeled. The finished polyester film 63 2 is then wound on a car. 6 3 4 is the control roller. The control roller 6 3 4 detects the supply tension of the resin coating film 604 for impregnation and adjusts it to a predetermined tension or less. The tension of the resin-coated film for impregnation is preferably 60 g / cm or less. In the second method, while using a product for impregnating resin coating film 602 with a peeling resin film with a thermal shrinkage of 1% or less at 150 ° C, the tension of the resin coating film 604 for impregnation is controlled to a predetermined value or less. Cutting and the like of the obtained polyester film can reduce curling. -35- (32) 200404845 [Embodiment] (Example of the first aspect) Example 1

Using a rolling mill device, uniformly mix 70 mass parts of resol phenolic resin (ARALDITE EPN1 138: manufactured by Asahi Kasei Epoxy Co., Ltd.), 30 mass parts of double epoxy resin (ARALDITE AER60 02: manufactured by Asahi Kasei Co., Ltd.), and 3 mass parts of dicyandiamide. And 3,3,4-dichlorobiphenyl) -1, 5 parts by mass of dimethyl urea, to obtain a one-liquid curable epoxy resin composition. Using this one-liquid curable epoxy resin composition, the resin content of the polyester film shown in Table 1 was formed, and the resin film for peeling (polypropylene film, SunTox-MP RS02 · 60 // m was applied with a film coating apparatus). · Tox Co., Ltd.) coated resin on the heavy surface side to prepare a resin coating film for impregnation shown in Table 1.

Continuous carbon fiber bundles (BESFIGHT UT5 00- 1 2K: made by Toho Tenax Corporation, 12,000 long fiber bundles, tensile strength 4810Mpa, tensile modulus of elasticity 240Gpa) 78 bundles are formed in one direction to form a continuous sheet of continuous carbon fiber parallel to each other After the body ', the sheet-like continuous carbon fiber assembly was sandwiched between the upper and lower sides of the sheet-shaped continuous carbon fiber assembly and passed through a hot roller between the resin coating films for impregnation, and the resin was impregnated with the sheet-shaped continuous carbon fiber assembly at a temperature of 100 t and a pressure of 0.2 9 Mpa. . Subsequently, the roll-off peeling paper was cooled to obtain a unidirectional polyester film of the first direction shown in FIG. The obtained polyester film had good resin impregnation properties between carbon fibers and did not cause scattering of fibers. In addition, the resin film for peeling can be easily peeled from the polyester film. The polyester film after peeling the resin film for peeling -36- (33) (33) 200404845 The surface has extremely excellent smoothness. Examples 2 to 5 and Comparative Examples 1 and 2 were the same as in Examples except that a polyethylene terephthalate film (film · 50 0 // m: manufactured by Teijin DuPond film) was used as the resin film for peeling. 1 Perform the same operation to obtain the polyester film shown in Table 1. In addition, in Examples 4, 5 and Comparative Examples 1 and 2, the resin was impregnated with carbon fiber using the resin-coated release paper coated with the one-liquid curable epoxy resin composition of Example 1 above, and peeled off after peeling and cooling. Paper method. In Example 3, when carbon fiber was impregnated with resin, a release paper having no epoxy resin coated thereon was used, and the resin was supplied only from below, followed by peeling off the release paper.

-37- (34) 200404845 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Type PP PET PET PET PET PET PET Thickness 60 50 50 50 50 50 50 (// m ) Light surface peeling 4 4 8 4 2 4 8 Impregnation resistance stain (g / cm) Heavy surface peeling 40 40 40 200 10 4 280 Tree resistance grease (g / cm) Heavy surface / light surface 10 10 5 50 5 1 35 The amount of resin (g / m2) with thin peeling resistance and the specific weight of the film 22.5 22.5 45 22.5 22.5 22.5 22.5 Reinforced fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber reinforced fiber Lightning 125 125 125 125 125 125 125 Resin Epoxy Resin Epoxy Resin Epoxy Resin Epoxy Resin Epoxy Resin Uncured Composite Resin Contains 26 26 26 26 26 26 26 26 Polyester (mass%) Polyester film Good Good Good Good Good Can't produce bad film appearance Polyester film 1) The peelability of the film is light and slightly heavy and very light-very Heavy Film Peeling Excellent Smoothing Excellent Smoothing Excellent Smoothing Excellent Smoothing

1) When the resin coating film for dipping is pulled out, the resin portion on the heavy surface is transferred to the light surface.

-38- (35) 200404845 (Example of the second aspect) Example 6

Using a rolling mill, uniformly mix 70 mass parts of resol phenolic resin (ARALDITe EPNU38: manufactured by Asahi Kasei Epoxy Co., Ltd.), double epoxy resin (ARALDITE AER6002: manufactured by Asahi Kasei Co., Ltd.), 30 mass 咅 p, bisamine 3 mass And 3- (3,4-dichlorobiphenyldimethylurea 5 mass) to obtain a one-liquid curable epoxy resin composition. Using the one-liquid curable epoxy resin composition, a thin film coating apparatus was used in A resin film for peeling (polypropylene film, SunTox_MP RS02 · 60 // m: made by Sun · Tox Co., Ltd.) is coated on the surface without peel resistance 値 to form the resin amount in Table 1 and sandwiched between the films. Paper is used to make a resin-coated film for impregnation.

Continuous carbon fiber bundles (BESFIGHT UT5 00- 1 2K: made by Toho Tenax Corporation, 12,000 long fiber bundles, tensile strength 4810Mpa, tensile elastic modulus 240 Gpa) 78 bundles were formed in one direction to form parallel continuous carbon fibers side by side. After the assembly, the impregnated resin-coated film sent from the impregnated resin-coated film roll was sandwiched between the upper and lower sides of the sheet-like continuous carbon fiber assembly and passed through a heat roller at a temperature of 100 ° C and a pressure of 29 MPa. The sheet-like continuous carbon fiber aggregate was impregnated with resin under conditions. After cooling, the unidirectional polyester film shown in Table 1 having a roll width of 500 mm was wound on a roll. The obtained polyester film had good resin impregnation properties between carbon fibers and did not cause scattering of fibers. In addition, the resin film for peeling can be easily peeled from this polyester film, and the surface of the polyester film after peeling the resin film for peeling has very excellent smoothness. -39- (36) (36) 200404845 Examples 7 to 10 and Comparative Examples 3 and 4 Except for the use of polyethylene terephthalate film (Purex film · 50 // m: manufactured by Teijin DuPond film) Except for the resin film for peeling, the same procedure as in Example 6 was performed to obtain the polyester gums shown in Table 2. In addition, in Examples 9, 10 and Comparative Examples 3 and 4, the method shown in FIG. 6 was used. That is, the resin-coated release paper after the one-liquid hardening epoxy resin composition of Example 6 was coated with the same amount as the resin coating film for impregnation, the resin was impregnated with carbon fibers, and the release paper after the cooling was peeled off and crimped The coating method shown in Table 2. In Example 8, the resin was impregnated with carbon fibers using a release paper uncoated with epoxy resin on the top surface. The resin was supplied only from the bottom surface. Subsequently, the release paper was peeled off and crimped to the film shown in Table 2.

-40-(37) 200404845 Table 2 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 3 Comparative Example 4 Impregnation type PP PET PET PET PET PET PET Stain thickness 60 50 50 50 50 50 50 ( " m) 40 40 40 200 10 0.4 0.4 280 Grease peel resistance (g / cm) Resin application amount (g / m2) 22.5 22.5 45 22.5 22.5 22.5 22.5 Tree peeling type Tree PE PE PE PE PE Membrane lipid film lipid film reinforced fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber reinforced fiber weight 125 125 125 125 125 125 125 (g / m2) uncured composite tree epoxy epoxy epoxy epoxy epoxy ring Oxygen epoxy resin resin resin resin resin resin poly uncured composite tree 26 26 26 26 26 26 26 ester content (% by mass) rubber polyester film appearance good good good good good can not make bad film polyester film 1) The peelability of the film is slightly light and very light-very heavy After peeling excellent smoothness Excellent Excellent smooth smooth smooth Excellent Excellent smooth - appearance can not be maintained sexual form of property 1) out of the coating film is impregnated with the resin, the resin portion sandwiched between the transfer

On paper.

-41-(38) (38) 200404845 (Example of the third aspect) Example Π 70 mass part of phenol resin (ARALDITE EPN1 138: manufactured by Asahi Kasei Epoxy Co., Ltd.) was uniformly mixed using a rolling mill device, and a bisphenol A ring Oxygen resin (ARALDITE AER6 0 02: manufactured by Asahi Kasei Co., Ltd.) 30 mass department, dicyanurate female 3 quality star department, and 3- (3,4-monogas biphenyl) -1,1-dimethylurea 5 mass department To obtain a one-liquid curable epoxy resin composition. Using this one-liquid curable epoxy resin composition, the resin content of the polyester film shown in Table 3 was formed, and the resin film for peeling (polypropylene film, SunTox-M PRS 0 2 · 6 0 // was used in a film coating apparatus. m: S u η · TO (made by X company) heavy-side coating resin to prepare a resin coating film for impregnation shown in Table 3. The peeling resistance 重 of the heavy surface of the peeling resin film was 40 g / cm, the peeling resistance 値 of the light side was 4 g / cm, and the peeling resistance ratio was 10. Continuous carbon fiber bundles (BESFIGHT UT5 00- 1 2K: manufactured by Toho Tenax Corporation, 12,000 long fiber bundles, tensile strength 48 1 OMpa, tensile modulus of elasticity 240Gpa) 78 bundles were formed in one direction in a continuous sheet parallel to each other After the carbon fiber assembly, the impregnated resin coating film was sandwiched between the upper and lower sides of the sheet-shaped continuous carbon fiber assembly and passed through a heat roller, and the resin was impregnated under the conditions of a temperature of 100 ° C and a pressure of 0.29 M pa. The sheet-like continuous carbon fiber assembly was then cooled, and the polyester film wound in a roll-shaped unidirectional manner was roll-rolled. The obtained polyester film had a width of 500 mm, a CF weight of 125 g / m2, and a resin content of 26% by weight. In addition, this polyester film has good resin impregnation properties between carbon fibers, and does not cause scatter of fibers. In addition, the polyester film can be easily peeled from -42- (39) 200404845. The surface of the polyester film after peeling the peeling resin film has very excellent smoothness. Example 1 2 to 15 and Comparative Examples 5 and 6 except that a polyethylene terephthalate film (Purex film · 50 // m: manufactured by Teijin DuPond film) was used as a resin film for peeling, and The same operation was performed in Example 1 to obtain the polyester gum shown in Table 3.

sheet. In addition, in Examples 14 and 15 and Comparative Examples 5 and 6, the method shown in FIG. 9 was used, that is, the one-liquid curable epoxy resin of Example 11 was coated with the same amount as the resin coating film for impregnation. The resin-coated release paper after the composition was impregnated with carbon fibers from the resin, and the coated film shown in Table 3 was pressure-bonded using the release paper after cooling and peeling.

Example 13 3 When a carbon fiber was impregnated with resin, a release paper having no epoxy resin applied thereon was used for the resin supply only from below. Subsequently, the release paper was peeled off and pressure-bonded to the film shown in Table 3. • 43- (40) 200404845 Table 3 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 5 Comparative Example 6 Type of resin coating film for impregnation PP PET PET PET PET PET PET Thickness (/ ητ〇60 50 50 50 50 50 50 Light surface peel resistance 値 (g / cm) 4 4 8 4 2 4 8 Heavy surface peel resistance 値 (g / cm) 40 40 40 200 10 4 280 Heavy surface / light face peel resistance ratio 10 10 5 50 5 1 35 Amount of resin on heavy surface (g / m2) 22.5 22.5 45 22.5 22.5 22.5 22.5 Type of coating Resin film for peeling Resin film for peeling PE PE PE PE PE Polyester film reinforced fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber Carbon fiber reinforced fiber weight (g / m2) 125 125 125 125 125 125 125 Uncured composite resin epoxy resin epoxy resin epoxy resin epoxy resin epoxy resin epoxy resin uncured composite resin content (% by mass) 26 26 26 26 26 26 26 Polyester film looks good Good Good Good Good Cannot manufacture polyester film 1) Poor film peelability Lightly slightly Slightly heavy Very light-very heavy film Appearance after peeling Outstanding smoothness Outstanding smoothness Outstanding smoothness Outstanding smoothness Outstanding smoothness — Unsustainable Form 1) When the resin coating film for dipping is pulled out, the resin portion on the heavy side is transferred to the light side. -44- (41) (41) 200404845 (Example of the fourth aspect) ARALDITE (trade name EPN1 138 A-stage carboxaldehyde epoxy resin manufactured by Asahi Kasei Epoxy Co., Ltd.) was uniformly mixed using a rolling mill device. 70 Quality Department, ARALDITE (trade name AER 6 0 0 2 bisphenol A epoxy resin manufactured by Asahi Kasei Epoxy Co., Ltd.) 30 mass part, dicyandiamide 3 mass part, and 3 gas 3,4_dichlorobiphenyl) 1-1 -5 parts by mass of dimethyl urea to obtain a one-liquid curable epoxy resin composition. Using this one-liquid curable epoxy resin composition, the resin content of the polyester film shown in Table 4 was formed, and a predetermined amount of resin was coated on the heavy surface of the peeling resin film by a film coating apparatus to prepare a resin coating film for impregnation. Continuous carbon fiber bundles (BESFIGHT UT500_12K: made by Toho Tenax Co., Ltd., long fiber bundles of 12,000, tensile strength of 5,000 MPa, and tensile modulus of elasticity of 240 Gpa) 78 bundles were formed in a continuous sheet-like manner in parallel and side by side. Carbon fiber aggregate. Subsequently, the sheet-like continuous carbon fiber assembly was sandwiched from above and below by introducing two resin films with the resin coating surfaces facing each other. The sheet was passed through a hot roll, and the resin was impregnated with the sheet-shaped continuous carbon fiber assembly at a temperature of 100 ° C and a pressure of 0.29 Mp a. Then, the upper resin film for peeling was peeled off, and the film was wound on a roll. At about the same time as the resin film for peeling the upper resin film was peeled off, the thermoplastic resin film shown in Table 4 was continuously stuck on it. Next, the above-mentioned resin film for peeling; a sheet-like continuous six-press fiber assembly impregnated with resin; and a thermoplastic resin film are fed into a pair of rollers, and the pressure-bonding between the rollers at room temperature to obtain a unidirectional polyester film with a width of 500 mm . (42) 200404845 The carbon fiber weight of the obtained polyester film was 125 g / cm2, and the resin content was 26% by weight. In addition, this polyester film has good resin impregnation properties between carbon fibers, and does not cause scattering of fibers. In addition, the resin film for peeling can be easily peeled from this polyester film, and the surface of the reinforcing fiber composite layer after peeling the resin film for peeling has very excellent smoothness. (Examples 17-22, Comparative Examples 7-10)

Polyester films having the structures shown in Tables 4 and 5 were obtained in the same manner. However, in Example 18, a resin film for peeling (uncoated epoxy resin) was used for impregnating a carbon fiber resin on top, and the resin was supplied only from below. Subsequently, the above-mentioned peeling resin film was pressure-bonded to the thermoplastic resin film shown in Table 4. The thermoplastic resin film used is shown below.

Nylon 12 film: Daiamido 240 manufactured by Dicel Chemical Industry Co., Ltd. 1. Thickness 30 // m, melting point 80 ~ 1 15 ° C, double-sided corona discharge treated polyethylene terephthalate film: manufactured by UNITIK Process > 7, 7 Polybutylene terephthalate film: THERMOLIGHT 28 manufactured by Dicel The corona discharge treatment is performed under the conditions of a discharge capacity of 80 to 100 Wm2 · min. -46- (43) 200404845 Table 4 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Peeling type PP PET PET PET PET PET PET With a thickness of 60 50 50 50 50 50 50 ( " m) Tree light side peeling resistance 4 4 8 2 8 8 8 Lipid strength 値 g / cm) Thin heavy side peeling resistance 40 40 40 10 80 120 140 Film strength 値 g / cm) Heavy side / light side 10 10 5 5 10 15 17.5 Peel resistance Specific heat type Nylon 12 PET PBT Nylon 12 Nylon 12 Nylon 12 Nylon 12 Plastic resin thickness (/ / Π1) 30 50 50 50 30 30 30 Surface treatment M ^ \\\ Double-sided corona double-sided electrical Halo M Μ Μ Μ film discharge discharge reinforced fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber reinforced fiber reinforced fiber weight (g / m2) 125 125 125 125 50 125 125 composite layer composite resin epoxy resin epoxy resin epoxy resin Epoxy resin epoxy resin composite resin containing 26 26 26 26 26 26 26 26 (mass%) polyester film appearance good good good good good Good peeling resin film Light Light Light Very Light Light Light Light Heavier Peelability Appearance after peeling off Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness

-47- (44) 200404845 (44)

Table 5 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Kind of PP PET PET PET Thickness (// Π1) 50 50 50 50 Peeling light surface peeling resistance 値 4 8 3 8 (g / cm) Resin film peeling with heavy surface Resistance 値 (g / cm) 4 280 6 160 Heavy / light peeling resistance 1 35 2 20 Specific heat capacity type—Nylon 12 Nylon 12 Nylon 12 Plastic resin film thickness (// m) — 30 30 30 Surface treatment — Μ j \\\ Μ JV \\ Μ j \ \\ reinforced fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber reinforced fiber weight 125 125 125 50 strong (g / m2) compound resin epoxy resin epoxy resin epoxy resin fiber composite resin Content 26 26 26 26 Dimensions (mass%) Polyester film appearance cannot be produced 1) Defective cannot be produced 1) Good resin film for peeling-very heavy-Slightly heavy layer peeling resin film for peeling-unable to maintain shape-produced Appearance of the partially cracked surface 1) When the resin film is pulled out, the resin portion on the heavy surface is transferred to the light surface. -48- (45) (45) 200404845 Example 2 3 -26, Comparative Example 1 1-12 B The production steps shown in Fig. 14 were used to produce a polyester film. Use a polyethylene film with a thickness of 2 5 // m. The physical properties of the obtained polyester film are shown in Table 6.

-49- (46) 200404845 Table 6 Example 23 Example 24 Example 25 Example 26 Comparative Example 11 Comparative Example 12 Resin film for peeling PET PET PEN PEN PET PEN There is a heat-resistant shrinkage treatment. There is M j \\\ Μ j \ \\ Μ j \ \\ and j \ \\ thickness (// m) 50 50 50 50 50 50 light surface peel resistance 値 (g / cm) 4 4 8 8 2 8 heavy surface peel resistance 値 (g / cm) 40 40 40 160 10 280 Heavy / light peel resistance ratio 10 10 5 20 5 35 Reinforced fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber carbon fiber reinforced fiber weight (g / m2) 125 125 125 125 125 125 composite resin epoxy resin epoxy resin Epoxy resin epoxy resin epoxy resin composite resin content (% by mass) 26 26 26 26 26 26 26 Hemming Μ Μ J \ ΝΝ Μ j \\\ Ｍ 有 和 j \\\ Polyester film looks good Good Good Good Good Peelability of the resin film for peeling Lightly slightly Slightly very light Very heavy Peeling resin for peeling Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness Excellent smoothness The appearance of the surface after the film cannot be maintained (47) (47) 200404 845 [Brief description of the drawings] Fig. 1 is a schematic perspective view showing an example of a paperless polyester film according to a first embodiment of the present invention. Fig. 2 is a flowchart showing an example of a method for producing a resin-coated film for impregnation in the first embodiment. Fig. 3 is a flowchart showing an example of a method for producing a paperless polyester film according to the first embodiment. Fig. 4 is a schematic perspective view showing an example of a paperless polyester film according to a second aspect of the present invention. Fig. 5 is a flowchart showing an example of a method for producing a resin-coated film for impregnation in the second embodiment. Fig. 6 is a flowchart showing an example of a method for producing a paperless polyester film according to a second embodiment. Fig. 7 is a schematic perspective view showing an example of a paperless polyester film according to a third embodiment of the present invention. Fig. 8 is a flowchart showing an example of a method for manufacturing a resin-coated film for impregnation in the third embodiment. Fig. 9 is a flowchart showing an example of a method for producing a paperless polyester film according to a third embodiment. Fig. 10 is a schematic perspective view showing an example of a paperless polyester film according to a fourth embodiment of the present invention. Fig. 11 is a flowchart showing an example of a method for producing a resin-coated film for impregnation used in the production of a paperless polyester film according to a fourth aspect of the present invention. Fig. 12 is a flowchart showing an example of a method for producing a paperless polyester film according to a fourth embodiment. Fig. 13 is a schematic side view showing an example of a (48) (48) 200404845 type manufactured using a paperless polyester film according to the fourth embodiment. Fig. 14 is a process chart showing an example of the manufacture of a paperless polyester film without curling. Fig. 15 is a flowchart showing another example of the production of a paperless polyester film without curling. [Symbol description] 1, 201, 301, 401 are polyester film; 2, 202, 302, 402 are reinforced fiber composite layers; 4, 204, 3 04, 404 are unhardened composite layers; 6, 206, 306, 406 , 506, 606 are reinforcing fibers; 208, 308, 528, 628 are coatings; 408 is a thermoplastic film; 10, 102, 3 1 0, 4 1 0 are resins for peeling; 1 2, 3 1 2 , 4 1 2 are heavy surfaces; 1, 4, 314, 414 are light surfaces; 212, 214 are resin surfaces for peeling; 2, 2a to 2d are reinforcing fiber composite layers; 8, 8a to 8c are thermoplastic resin films; 3 〇〇a is the first polyester film; 300b is the second polyester film; 300c is the third polyester film; 530 is a replacement film.

Claims (1)

(1) (1) 200404845 Scope of application and patent application 1. An endless polyester film, characterized in that the reinforcing fiber is impregnated with a reinforcing fiber composite layer impregnated with an unhardened composite resin, and has a heavy surface with a large peeling resistance and a peeling resistance. The peeling resin film made of a small light surface is composed of a peeling resin film in which the heavy surface is adhered to one side of the fiber-reinforced composite layer, and the peeling resistance of the heavy surface of the peeling resin film is 200 g / A paperless polyester film having a thickness of less than cm and a peel resistance ratio between a heavy surface and a light surface (heavy surface / light surface) of 3.0 or more. 2. The paperless polyester film according to item 1 of the scope of patent application, wherein the peel resistance ratio of the heavy surface to the light surface of the resin film for peeling is 5 or more. 3. The paperless polyester film according to item 1 of the patent application scope, wherein the peel resistance 値 of the heavy surface of the resin film for peeling is 10 to 120 g / cm. 4. The paperless polyester film described in item 1 of the patent application scope, wherein the resin film for peeling has a thermal shrinkage of 1% or less at 150 ° C. 5. The paperless polyester film according to item 1 of the scope of patent application, wherein the reinforcing fiber is carbon fiber, glass fiber or aromatic polyimide fiber. 6. The paperless polyester film according to item 1 of the patent application scope, wherein the composite resin is an epoxy resin composition. 7. A paperless polyester film, characterized in that the reinforcing fiber is impregnated with a reinforcing fiber composite layer of an unhardened composite resin; a film is adhered to one side of the fiber-reinforced composite layer; and the other side of the fiber-reinforced composite layer is adhered to its peeling surface The peeling resistance 値 of the peeling surface of the peeling resin film constituted by the resin film for peeling is 0.5 to 20 g / cm. 8. The paperless polyester film according to item 7 of the scope of the patent application, wherein -53- (2) 200404845 the peel resistance 値 of the resin film for peeling is 10 to 120 g / cm. 9. The paperless polyester film according to item 7 of the scope of patent application, wherein the resin film for peeling has a thermal shrinkage of 1% or less at 150 ° C. 10. The paperless polyester film according to item 7 of the scope of patent application, wherein the reinforcing fiber is carbon fiber, glass fiber or aromatic polyimide fiber. 11. The paperless polyester film according to item 7 in the scope of the patent application, wherein the composite resin is an epoxy resin composition. 12. The paperless polyester film according to item 7 in the scope of the patent application, wherein the resin film for peeling is a resin film for peeling made of a heavy surface having a large peel resistance and a light surface having a small peel resistance. The heavy surface is adhered to the other side of the fiber-reinforced composite layer. The peel resistance 値 of the heavy surface of the resin film for peeling is 200 g / cm or less and the peel resistance ratio (heavy surface / light surface) of the heavy surface to the light surface is 3.0 or more. . 13. The paperless polyester film according to item 12 of the patent application scope, wherein the peel resistance ratio of the heavy surface to the light surface of the resin film for peeling is 5 or more. 14. The paperless polyester film according to item 13 of the scope of patent application, wherein the peel resistance 的 of the heavy surface of the resin film for peeling is 10 to 120 g / cm. 15. The paperless polyester film according to item 12 of the patent application, wherein the resin film for peeling has a thermal shrinkage of 1% or less (TC). 16. The paperless polymer according to item 7 of the patent application Ester film, in which the peel resistance 値 of the coating is 0.5 to 200 g / cm. 1 7. The paperless polyester film according to item 7 of the patent application scope, wherein the coating has a heavy surface with a large peel resistance and peel resistance. -54- (3) (3) 200404845 1 8-The paperless polyester film described in item 7 of the patent application scope, wherein the film is made of a thermoplastic resin film 19 • The paperless polyester film as described in item 18 of the scope of application for patent, wherein the thermoplastic film is amine 12 film, ionic resin film, and polyethylene terephthalate after corona discharge treatment on both sides Glycol ester. 20 · —A method for producing a molded body, which is formed by curing a composite resin with a thermoplastic resin film spaced apart, and is characterized in that the paperless polyester film described in the patent application scope No. 18 is being stripped. After peeling the resin film, two layers are laminated 21. A method of manufacturing a paperless polyester film, characterized in that the peel resistance of the heavy surface is less than 150 g / cm, and the peel resistance ratio of the heavy surface to the light surface (heavy surface / light surface) An unhardened composite resin is applied to the heavy surfaces of two or more peeling resin films, and the heavy surfaces of the two peeling resin films are opposed to each other, and the reinforcing fibers are sandwiched between the two peeling resin films. Step: a step of impregnating the reinforcing fibers with the unreinforced composite resin under pressure by heating the clamped reinforcing fibers from the outside of the peeling resin film; having any one of the two peeling resin films from the unimpregnated reinforcing fiber At the same time as the hardened composite resin is stripped, the surface of the unhardened composite resin after the peeling is pressure-bonded with a non-hardened composite resin such as a thermoplastic resin film to impregnate the reinforced fiber-reinforced composite layer of the reinforcing fiber, and the above-mentioned fiber-reinforced composite layer— ' A thermoplastic resin film; and a resin film for peeling on which the other side of the fiber-reinforced composite layer is pasted, and a peeling surface of the resin film for peeling; The resistance 値 is less than 150 g / cm. 22. A method for manufacturing a paperless polyester film, characterized in that: the peel resistance of the heavy surface -55- (4) (4) 200404845 is less than 1 50 g / cm, and the weight One of the two peeling resin films with a peel resistance ratio (heavy side / light side) of 3 or more is coated with an unhardened composite resin on one of the two heavy surfaces, and the peeled resin film coated with the unhardened composite resin is applied. The step of sandwiching the reinforcing fibers between the two peeling resin films with the heavy surface of the uncoated composite resin and the light surface of the uncoated peeling resin film uncoated; The step of impregnating the reinforcing fibers with an unhardened composite resin under pressure and heating under the outer side of the resin film; having a peeling resin film with the light side as the inner side of the two peeling resin films, peeling off the unhardened composite resin impregnated with the reinforcing fibers At the same time, on the surface of the uncured composite resin after the peeling, the unreinforced composite resin, such as a thermoplastic resin film, is impregnated with a reinforcing fiber composite layer of reinforcing fibers; Plastic resin film; and the other surface of said fiber reinforced composite adhesive layer with a release surface peeling of the resin film constituting the peeling resistance of the release surface of the release resin film is Zhi 1 5 0 g / c m or less.