TW202200681A - Resin film, fiber-reinforced resin base material, multilayer body, comosite body, and production methods thereof - Google Patents

Abstract

A resin film which is used for the purpose of producing a fiber-reinforced resin base material, and which is an unstretched film that contains a resin (S) containing a syndiotactic polystyrene resin (A) and a polyarylene ether resin (B) that is modified with a functional group.

Description

Resin film, fiber-reinforced resin substrate, laminate and composite, and method for producing the same

The present invention relates to a resin film, a fiber-reinforced resin substrate, a laminate and a composite, and a method for producing the same.

There is known a technique (Patent Document 1) in which a fiber-reinforced composite sheet is formed by integrating a UD tape (Uni-Directional tape, unidirectional tape) with a thermoplastic resin sheet, the UD tape being a resin Impregnated in fibers arranged in one direction and in the form of ribbons. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-149708

The inventors of the present invention have studied the use of para-polystyrene (hereinafter also referred to as "SPS") resin which is excellent in chemical resistance, water resistance (the property of being difficult to absorb water), and heat resistance, and found the following problems: That is, the thickness of the unstretched film using the SPS resin is difficult to be uniform. As for the reason, there are the following actual situations. That is, since the edge part formed with film formation becomes thicker than the center part, by removing this edge part, the uniform thickness can be aimed at. However, the unstretched film using the SPS resin is prone to film breakage, and cannot be applied with slitting, making it difficult to make the thickness uniform.

In particular, in the case of manufacturing a UD tape, etc., it is required to continuously remove the end portion of the elongated film by slitting, but it is difficult to apply such a process when SPS resin is used. It is considered that even if the slitting process can be applied, film breakage is likely to occur, and it is considered that, for example, the reinforcing effect when applied to a UD tape or the like cannot be sufficiently obtained.

It is known that by increasing the molecular weight of the SPS resin, it is possible to suppress film breakage accompanying slitting to a certain extent.

Therefore, an object of the present invention is to provide a non-stretching resin film, a fiber-reinforced resin substrate, a laminate and a composite, and a method for producing the same, which can have a uniform thickness and have excellent impregnation into fibers.

The inventors of the present invention further conducted intensive research and found that by blending a functional group-modified poly(arylene ether) resin into an SPS resin, it is possible to prevent film breakage accompanying the slitting process. Thereby, the edge part without a stretched film can be removed by slit processing, and the thickness can be made uniform. In addition, it was also found that the non-stretched film has excellent impregnation properties in fibers.

According to the present invention, the following resin films and the like can be provided. 1. A resin film for the manufacture of fiber-reinforced resin substrates, The above-mentioned resin film is a non-stretched film and contains a resin (S), and the resin (S) contains a para-polystyrene resin (A) and a functional group-modified polyarylene ether resin (B). 2. The resin film according to 1, which has an average thickness of 10 μm or more and less than 100 μm. 3. The resin film according to 1 or 2, wherein the MFR (melt mass-flow rate, melt mass flow rate) of the above-mentioned opposite-row polystyrene resin (A) is 5-30 g/10 min. 4. The resin film according to any one of 1 to 3, which comprises the above-mentioned functional group-modified polyarylene ether resin (B) 1- 30 parts by mass. 5. The resin film according to any one of 1 to 4, which is in the shape of a long strip, and the difference between the thickness of the end portion in the width direction and the thickness of the central portion in the width direction is in the range of -10% to 10%. 6. A method for producing a resin film, which is used to produce the resin film according to any one of 1 to 5, comprising: The above-mentioned resin film is obtained by removing the end portion of the non-extended resin film precursor comprising the resin (S), which comprises the opposite row polystyrene resin (A), and the functional group-modified resin film is obtained by slitting. Properties of poly(arylene ether) resin (B). 7. The method for producing a resin film according to 6, wherein both ends in the width direction of the elongated resin film precursor are removed by slitting. 8. The method for producing a resin film according to 6 or 7, wherein the above-mentioned resin film precursor in a long shape is transported by rollers, and the both ends in the width direction of the resin film precursor are continuously removed by slitting. 9. A fiber-reinforced resin substrate comprising fibers and a resin (S) impregnated in the fibers; The above-mentioned resin (S) includes a para-row polystyrene resin (A) and a functional group-modified polyarylene ether resin (B). 10. The fiber-reinforced resin substrate according to 9, wherein the fibers are at least one selected from the group consisting of carbon fibers and glass fibers. 11. The fiber-reinforced resin substrate according to 9 or 10, wherein the above-mentioned fibers are woven, non-woven, or oriented in one direction. 12. The fiber-reinforced resin substrate according to any one of 9 to 11, wherein the above-mentioned fibers are continuous fibers. 13. A method for producing a fiber-reinforced resin base material for producing the fiber-reinforced resin base material according to any one of 9 to 12, comprising: The first step, which heats a fiber-reinforced resin base material precursor, the fiber-reinforced resin base material precursor comprising the resin film as described in any one of 1 to 5, and the fibers superimposed on the resin film; and In the second step, the above-mentioned fiber-reinforced resin base material is obtained by cooling the above-mentioned fiber-reinforced resin base material precursor. 14. The method for producing a fiber-reinforced resin substrate according to 13, wherein in the first step, the fiber-reinforced resin substrate precursor is heated at a temperature equal to or higher than the melting point of the resin film. 15. The method for producing a fiber-reinforced resin base material according to 13 or 14, wherein in the first step, the fiber-reinforced resin base material precursor is heated using a roll. 16. The method for producing a fiber-reinforced resin base material according to any one of 13 to 15, wherein in the first step, the fiber-reinforced resin base material precursor is pressurized using a roll. 17. The method for producing a fiber-reinforced resin substrate according to any one of 13 to 16, wherein in the first step, heating and pressurization of the fiber-reinforced resin substrate precursor are simultaneously performed. 18. The method for producing a fiber-reinforced resin substrate according to any one of 13 to 17, wherein in the second step, the fiber-reinforced resin substrate precursor is cooled at a temperature below 200°C. 19. The method for producing a fiber-reinforced resin base material according to any one of 13 to 18, wherein in the second step, the fiber-reinforced resin base material precursor is cooled using a roll. 20. The method for producing a fiber-reinforced resin base material according to any one of 13 to 19, comprising: a third step of winding up the fiber-reinforced resin at a speed of 1 to 30 m/min after the second step substrate. 21. The method for producing a fiber-reinforced resin substrate according to 20, wherein in one or more steps selected from the group consisting of the first step, the second step, and the third step, the fiber-reinforced resin is A release sheet is overlapped on one or both sides of the substrate precursor. 22. A layered product comprising two or more fiber-reinforced resin substrates according to any one of 9 to 12, layered and integrated. 23. A method for manufacturing a laminate, comprising: Stacking 2 or more of the fiber-reinforced resin substrates of any one of 9 to 12 to form a laminate precursor; and The above-mentioned layered body precursor is press-molded to obtain a layered body in which two or more of the above-mentioned fiber-reinforced resin base materials are laminated and integrated. 24. A complex comprising: The first member, which is the fiber-reinforced resin substrate as in any one of 9 to 12 or the laminate as in 22; and The second member is an injection-molded body integrated with the first member. 25. A method for producing a composite, comprising: injection molding in a state in which the fiber-reinforced resin substrate according to any one of 9 to 12 or the first member of the laminate according to 22 is inserted into a mold to obtain A composite body including the first member and a second member that is an injection-molded body integrated with the first member.

According to the present invention, a non-stretching resin film, a fiber-reinforced resin substrate, a laminate and a composite, and a method for producing the same can be provided, which can have a uniform thickness and have excellent impregnation properties in fibers.

Hereinafter, the resin film, the fiber-reinforced resin base material, the laminate and the composite of the present invention, and the production method thereof will be described in detail. In addition, in this specification, "x-y" shows the numerical range of "more than x, less than y". The upper limit value and the lower limit value described in the numerical range can be combined arbitrarily. In addition, a form obtained by combining two or more of the forms of the present invention described below is also a form of the present invention.

1. Resin film The resin film of one aspect of the present invention is used to manufacture a fiber-reinforced resin substrate, and the resin film is a non-stretched film and includes a resin (S), the resin (S) includes a pair of polystyrene resin (A), and a Functional group-modified poly(arylene ether) resin (B).

According to this resin film, film breakage that occurs with slitting processing is prevented, and the resin (S) constituting the resin film is excellent in impregnation of fibers. Furthermore, the resin film is excellent in the strength (flexural properties, etc.) of a laminate and a composite produced by using a fiber-reinforced resin base material in which fibers are impregnated with the resin (S) constituting the resin film. the winner. In addition, since the resin film is a non-stretch film, shrinkage at the time of heating and melting can be prevented, and therefore, it is suitable for producing a fiber-reinforced resin base material.

(opposite row polystyrene resin (A)) The opposite-row polystyrene resin (A) (hereinafter also simply referred to as resin (A)) is a crystalline polystyrene-based resin having a highly opposite-row structure. The resin film is lightweight and exhibits excellent strength by including the resin (A).

In this specification, the so-called "parallel arrangement" means that the benzene rings in adjacent styrene units are arranged alternately with respect to the plane formed by the main chain of the polymer block (hereinafter also referred to as "parallel arrangement"). ) is high.

The displacement can be quantitatively identified by nuclear magnetic resonance method ( ¹³ C-NMR method) using carbon isotopes. By the ¹³ C-NMR method, continuous plural structural units can be used, for example, two continuous monomer units can be regarded as a dyad, 3 monomer units can be regarded as a triad, and 5 monomer units can be regarded as a pentagram. A tuple to quantify the ratio of its presence.

The so-called "crystalline polystyrene resin with a highly parallel structure" means a polystyrene having the following parallel structure: in terms of racemic binary group (r), usually 75 mol% or more, preferably It is 85 mol% or more; or in terms of racemic pentad (rrrr), it is usually 30 mol% or more, preferably 50 mol% or more.

The molecular weight of the resin (A) is not particularly limited, but the weight average molecular weight is preferably 1×10 ⁴ or more and 1×10 from the viewpoint of the fluidity of the resin during molding and the mechanical properties of the obtained molded body ⁶ or less, more preferably 50,000 or more and 500,000 or less, still more preferably 50,000 or more and 300,000 or less. When the weight average molecular weight is 1×10 ⁴ or more, a molded article having sufficient mechanical properties can be obtained. On the other hand, if the weight average molecular weight is 1×10 ⁶ or less, there is no problem with the fluidity of the resin during molding.

The MFR of the resin (A) is preferably 5 to 30 g/10 min, more preferably 6 to 25 g/10 min, still more preferably 6 to 15 g/10 min. When the MFR is 5 g/10 min or more, the impregnation property of the resin (S) in the fiber will be more excellent. By setting the MFR to be 30 g/10 min or less, the film breakage that occurs with the slitting process is further prevented. MFR is a value measured under the conditions of a temperature of 300°C and a load of 1.20 kg in accordance with JIS K 7210:2014.

(Polyarylene ether resin (B) modified with functional group) The functional group-modified polyarylene ether resin (B) (hereinafter also simply referred to as resin (B)) can be obtained by reacting the following polyarylene ether with the following modifier. By containing the resin (B), the resin film can suppress film breakage that occurs with slitting and can exhibit excellent strength.

The polyarylene ether used as a raw material of the resin (B) is not particularly limited. Examples of poly(arylene ether) include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4- -phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2 -Ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl ether) -1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-phenyl-1,4-phenylene ether), poly(2- chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro- 6-Bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-benzene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo -1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6- Dimethyl-1,4-phenylene ether) and so on. Alternatively, polymers and copolymers described in the respective specifications of US Pat. No. 3,306,874, US Pat. No. 3,306,875, US Pat. No. 3,257,357, and US Pat. No. 3,257,358 are also suitable. Furthermore, the graft copolymer and block copolymer of vinyl aromatic compounds, such as polystyrene, and the said polyphenylene ether, are mentioned, for example. Among them, poly(2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

The degree of polymerization of the polyarylene ether is not particularly limited, and can be appropriately selected according to the purpose of use and the like, and is usually selected from the range of 60 to 400. When the degree of polymerization is 60 or more, the strength of the resin film can be improved. If it is 400 or less, good formability can be maintained.

Examples of modifiers for modifying polyarylene ether include acid modifiers, amine group-containing modifiers, phosphorus compounds, hydroxyl group-containing modifiers, halogen-containing modifiers, epoxy group-containing modifiers Agents, modifiers containing unsaturated hydrocarbon groups, etc. As an acid modifier, dicarboxylic acid and its derivative(s) can be illustrated, for example.

As the dicarboxylic acid used as a modifier, maleic anhydride and its derivatives, and fumaric acid and its derivatives are exemplified. Derivatives of maleic anhydride are compounds having an ethylenic double bond and a polar group such as a carboxyl group or an acid anhydride group in the same molecule. Specifically, for example, maleic acid, maleic acid monoester, maleic acid diester, maleimide, and N-substituted products thereof (for example, N-substituted maleimide, maleic acid monoimide, amine, diamide maleate, etc.), ammonium salt of maleic acid, metal salt of maleic acid, acrylic acid, methacrylic acid, methacrylate, glycidyl methacrylate, etc. As a specific example of a fumaric acid derivative, a fumaric acid diester, a fumaric acid metal salt, a fumaric acid ammonium salt, a fumaric acid halide, etc. are mentioned. Among them, it is particularly preferable to use fumaric acid or maleic anhydride.

Resin (B) can be obtained by reacting polyarylene ether with a modifier. As the functional group-modified polyarylene ether, preferably dicarboxylic acid-modified polyarylene ether, more preferably fumaric acid-modified polyarylene ether or maleic acid-modified polyarylene ether ether. Specifically, (styrene-maleic anhydride)-polyphenylene ether-graft polymer, maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether, glycidyl methacrylate modified modified polyphenylene ether-based polymers such as polyphenylene ether, amine-modified polyphenylene ether, etc. Among them, modified polyphenylene ether is preferred, maleic anhydride modified polyphenylene ether or fumaric acid modified polyphenylene ether is more preferred, and fumaric acid modified polyphenylene ether is particularly preferred.

The modification degree (modification degree or modification amount) of resin (B) can be calculated|required by infrared (IR) absorption spectroscopy or a titration method. When the degree of modification is determined by infrared (IR) absorption spectroscopy, the intensity of the peak representing the absorption of the compound used as a modifier and the corresponding peak intensity representing the absorption of polyarylene ether can be obtained from the spectrum. The intensity ratio is obtained. For example, in the case of ^fumaric acid ^- modified polyphenylene ether, according to the ratio ( β), the modification degree is obtained by the formula of modification degree=(α)/(β). The degree of modification of the resin (B) is preferably 0.05 to 20.

When the modification amount is determined by titration, it can be determined as the acid content based on the neutralization titration amount measured in accordance with JIS K 0070:1992. The modified amount of the resin (B) to be used is preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, still more preferably 1.0 to 10 mass %, particularly preferably 1.0 with respect to the mass of the polyarylene ether. ~5.0 mass %.

As for the resin (B), the poly(arylene ether) can be reacted with various modifiers in the presence or absence of a radical initiator in the presence or absence of a solvent and other resins, whereby the Prepare. As a modification method, solution modification or melt modification is known.

When the above-mentioned fumaric acid or its derivative is used as a modifier, the polyarylether and fumaric acid or its derivative can be made to be in the presence of an aromatic hydrocarbon solvent and other resins optionally. The reaction is carried out in the presence or absence of a free radical initiator, thereby obtaining a fumaric acid-modified polyarylene ether. The aromatic hydrocarbon solvent is not particularly limited as long as it dissolves polyarylene ether, fumaric acid or its derivatives, and a radical initiator that is optionally used, and is inert with respect to the generated radicals. . Specifically, benzene, toluene, ethylbenzene, xylene, chlorobenzene, t-butylbenzene, etc. are mentioned as suitable ones, for example. Among them, benzene, toluene, chlorobenzene, and tert-butylbenzene having a small chain transfer constant are preferably used. The solvent may be used alone or in combination of two or more. The usage ratio of the aromatic hydrocarbon solvent is also not particularly limited, and may be appropriately selected depending on the situation. Generally speaking, it may be selected within the range of 1 to 20 times (mass ratio) with respect to the poly(arylene ether) used.

The usage ratio of fumaric acid or its derivative used as a modifier is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, with respect to 100 parts by mass of poly(arylene ether). When it is 1 part by mass or more, a sufficient modification amount (modification degree) can be obtained. If it is 20 parts by mass or less, post-processing such as purification after modification can be appropriately performed.

The free radical initiator that can be arbitrarily used for the solution modification of polyarylene ether is not particularly limited. Preferably, it has a decomposition temperature suitable for the reaction temperature, and has a large hydrogen abstracting ability, and the above-mentioned hydrogen abstracting ability is large in order to effectively graft the modifier to the poly(arylene ether). Specifically, for example, di-tert-butyl peroxide, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tertiary-butyl) Peroxy)-3,3,5-trimethylcyclohexane, benzyl peroxide, decyl peroxide, etc. The usage ratio of the radical initiator is preferably 15 parts by mass or less with respect to 100 parts by mass of the polyarylene ether. When the amount of the radical initiator is 15 parts by mass or less, it is difficult to generate insoluble components, which is preferable. When the above modification is carried out in the absence of a radical initiator, a polyarylene ether with a low modification amount (modification degree) (eg, a modification amount of 0.3 to 0.5 mass %) is obtained.

In the case of solution modification of poly(arylene ether), specifically, poly(arylene ether) and, as a modifier, such as fumaric acid or a derivative thereof, are dissolved in an aromatic hydrocarbon solvent. When a radical initiator is used after homogenization, the radical initiator is added at any temperature where the half-life of the radical initiator is 1 hour or less, and the reaction is carried out at this temperature. As for the temperature where the half-life of the free radical initiator used exceeds 1 hour, it is not preferable because a longer reaction time is required. The reaction time can be appropriately selected, but in order to make the radical initiator work effectively, the modification reaction is preferably carried out at a specific reaction temperature for three times or more of the half-life of the radical initiator. After the reaction is completed, the reaction solution is added to a poor solvent for polyarylether, such as methanol, and the precipitated modified polyarylether is recovered and dried to obtain the target polyarylether modified by functional groups. ether.

In the case of melt modification of poly(arylene ether), in the presence or absence of free radical initiator, an extruder can be used to modify poly(arylene ether), and as modifier. For example, fumaric acid or its derivatives are melt-kneaded to obtain functional group-modified poly(arylene ether). The usage ratio of fumaric acid or its derivative is preferably 1 to 5 parts by mass, more preferably 2 to 4 parts by mass, with respect to 100 parts by mass of the polyarylene ether. If it is 1 part by mass or more, a sufficient modification amount (modification degree) can be achieved, and if it is 5 parts by mass or less, the modification efficiency of fumaric acid and its derivatives can be maintained well, and residues in the particles can be suppressed. The amount of fumaric acid and so on.

The free radical initiator used for the melt modification of poly(arylene ether) preferably has a half-life temperature of 300°C or higher for 1 minute. As for the one-minute half-life temperature below 300°C, such as peroxides and azo compounds, the modification effect of poly(arylene ether) is not sufficient. Specific examples of the radical initiator include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 3-diethyl-2,3-diphenylhexane, 2,3-dimethyl-2,3-bis(p-methylphenyl)butane, etc. Among them, 2,3-dimethyl-2,3-diphenylbutane having a half-life temperature of 330°C for 1 minute can be suitably used. The usage ratio of the radical initiator is preferably selected within the range of 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, with respect to 100 parts by mass of the polyarylene ether. If it is 0.1 parts by mass or more, a high modification effect is obtained, and if it is 3 parts by mass or less, the poly(arylene ether) can be modified efficiently and insoluble components are hardly generated.

As a method of melt-modifying poly(arylene ether), for example, a method of uniformly dry blending poly(arylene ether), fumaric acid or a derivative thereof, and a radical initiator at room temperature may be exemplified. After that, the melting reaction is carried out in the range of 300 to 350° C. which is substantially the kneading temperature of the poly(arylene ether). When the temperature is 300°C or higher, the melt viscosity can be appropriately maintained, and when the temperature is 350°C or lower, the decomposition of the polyarylene ether can be suppressed.

In the resin (B) obtained by the method described in detail above, in the case of the particularly preferred fumaric acid-modified poly(arylene ether), the modification amount (modifier content) obtained by the above-mentioned titration method Preferably it is 0.1-20 mass %, More preferably, it is 0.5-15 mass %, More preferably, it is 1-10 mass %, Especially preferably, it is 1.0-5.0 mass %. When the modification amount is 0.1 mass % or more, a polyarylene ether having sufficient mechanical properties and heat resistance can be obtained. It is sufficient that this modification amount is 20 mass % or less.

In one Embodiment, the resin film system contains 1-30 mass parts of resin (B) with respect to 100 mass parts of opposite-row polystyrene resin (A). When the resin (B) is 1 part by mass or more, film breakage accompanying slitting processing can be further prevented. When the resin (B) is 30 parts by mass or less, the impregnation property of the resin (S) in the fibers is more excellent. The content of the resin (B) in the resin film is preferably 2 to 25 parts by mass, more preferably 5 to 22 parts by mass, and still more preferably 10 to 20 parts by mass relative to 100 parts by mass of the opposite polystyrene resin (A). parts by mass.

(other resins) The resin (S) may further contain other resins other than the resin (A) and the resin (B) described above. As another resin, thermoplastic resin is mentioned, for example.

As other resins, for example, poly(hydrocarbon-substituted styrene), poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene), poly(vinyl benzoate), the Hydrogenated polymers or mixtures of these, or copolymers with these as the main components.

Examples of the above-mentioned poly(hydrocarbon-substituted styrene) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(t-butylstyrene), poly( phenyl) styrene, poly (vinyl naphthalene) and poly (vinyl styrene) and the like. Examples of poly(halogenated styrene) include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), and examples of poly(halogenated alkylstyrene) include poly(chloromethylstyrene) styrene) etc. As poly(alkoxystyrene), poly(methoxystyrene), poly(ethoxystyrene), etc. are mentioned.

Among the above-mentioned particularly preferred ones, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-methylstyrene), chlorostyrene), poly(p-fluorostyrene). Furthermore, the copolymer of styrene and p-methylstyrene, the copolymer of styrene and p-tert-butylstyrene, the copolymer of styrene and divinylbenzene, etc. are mentioned.

Moreover, as another resin, the resin with high affinity (it is also called compatibility) with resin (A) is suitably used. Examples of such resins include polyphenylene ether (abbreviated as "PPE", which is not modified with functional groups), acrylonitrile/styrene copolymer (abbreviated as "AS"), acrylonitrile/butadiene/benzene Ethylene copolymer (abbreviated as "ABS"), acrylonitrile/ethylene-propylene-diene/styrene copolymer (abbreviated as "AES"), acrylonitrile/acrylate/styrene copolymer (abbreviated as "AAS"), methyl Methyl acrylate/butadiene/styrene copolymer (referred to as "MBS"), styrene/butadiene copolymer (referred to as "SBR"), styrene/butadiene styrene copolymer (referred to as "SBS") , Styrene/ethylene/butadiene/styrene copolymer ("SEBS"), etc.

The above-mentioned resins exemplified as other resins (among them, polyarylene ethers such as polyphenylene ethers are excluded) are preferably modified resins, especially acid-modified resins. Modified resins can be obtained by copolymerizing chemical species having modified groups, such as graft polymerization. When an acid-modified resin is to be obtained, as the chemical species, an unsaturated carboxylic acid or a derivative thereof is suitably used. As an example of an acid modification method, a styrene/maleic anhydride copolymer (abbreviated as "SMA") is obtained by grafting carboxylic acid or carboxylic acid anhydride to polystyrene.

As the unsaturated carboxylic acid used for acid modification, for example, a compound having a polymerizable double bond containing a carboxyl group such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid can be used. In addition to the carboxyl group, other functional groups such as a hydroxyl group, an amino group, and an epoxy group can be introduced into these compounds as necessary. Examples of derivatives of unsaturated carboxylic acids used for acid modification include acid anhydrides, esters, amides, amides, metal salts, and the like of the above-mentioned compounds. Specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate Esters, Monoethyl Maleate, Diethyl Maleate, Monomethyl Fumarate, Dimethyl Fumarate, Acrylamide, Methacrylamide, Monoamide Maleate, Maleic Acid Diamide, monoamide fumarate, maleimide, N-butylmaleimide, sodium methacrylate, etc. Among them, preferred are fumaric acid and maleic anhydride.

Other resins are not limited to those having high affinity with the resin (A) described above, and may be resins having low affinity depending on the purpose, application, and the like. In the case of using a resin with low affinity, the compatibility with the resin (A) can be improved by combining with various compatibilizers as necessary. Examples of resins with low affinity with the resin (A) include aliphatic polyamides such as PA6, PA66, and PA610; aromatic polyamides having aromatic rings in the main chain such as PA6T, PA9T, and MXD6; Polyesters such as ethylene terephthalate (referred to as "PET"), polybutylene terephthalate (referred to as "PBT"); polyarylene sulfides with aryl groups in the main chain; Polyether ketone with sulfonyl bond; polyether ether ketone ("PEEK") with ketone group in the main chain; such as polypropylene ("PP"), high density polyethylene ("HDPE"), straight Chain Low Density Polyethylene ("LLDPE"), Ethylene-Butene Copolymer ("EBR"), Ethylene-Octene Copolymer ("EOR"), Ethylene-Hexene Copolymer ("EHR") ), polyolefins (or olefin-based elastomers) such as ethylene-propylene copolymers (abbreviated as "EPR"), etc.

In one embodiment, the resin (S) is 20% by mass or more, 25% by mass or more, 50% by mass or more, 70% by mass or more, 80% by mass or more, 95% by mass or more, 99% by mass or more, 99.5% by mass or more Or substantially 100 mass % are resin (A) and resin (B). Moreover, in one embodiment, 80 mass % or more, 90 mass % or more, 95 mass % or more, 97 mass % or more, 99 mass % or more, 99.5 mass % or more, or substantially 100 mass % of the resin (S) are resins (A), resin (B), and 1 or more types selected from the said other resin. In addition, in the case of "substantially 100 mass %", unavoidable impurities may be included.

(other ingredients) The resin film may further contain other components other than the resin (S) described above. Examples of other components include generally used rubber elastomers, antioxidants, crosslinking agents, crosslinking aids, nucleating agents, mold release agents, plasticizers, compatibilizers, colorants, antistatic agents, and the like. .

As the rubber elastic body, various rubber elastic bodies can be used. For example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polysiloxane rubber, epichlorohydrin Rubber, styrene-butadiene block copolymer ("SBR"), hydrogenated styrene-butadiene block copolymer ("SEB"), styrene-butadiene-styrene block copolymer (referred to as "SBS"), hydrogenated styrene-butadiene-styrene block copolymer (referred to as "SEBS"), styrene-isoprene block copolymer (referred to as "SIR"), hydrogenated styrene- Isoprene block copolymer (referred to as "SEP"), styrene-isoprene-styrene block copolymer (referred to as "SIS"), hydrogenated styrene-isoprene-styrene block copolymer (referred to as "SEPS"), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene free Regular copolymer, ethylene propylene rubber ("EPR"), ethylene propylene diene rubber ("EPDM"), or acrylonitrile-butadiene-styrene-core-shell rubber ("ABS"), methacrylic acid Methyl methacrylate-butadiene-styrene-core-shell rubber (abbreviated as "MBS"), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (abbreviated as "MAS"), octyl acrylate-butadiene - Styrene-core-shell rubber (referred to as "MABS"), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (referred to as "AABS"), butadiene-styrene-core-shell rubber (referred to as "AABS") "SBR"), core-shell particulate elastomers such as siloxane-containing core-shell rubbers including methyl methacrylate-butyl acrylate siloxane, or modified rubbers, etc. Among them, it is particularly preferable to use SBR, SBS, SEB, SEBS, SIR, SEP, SIS, SEPS, core-shell rubber or modified rubbers thereof.

Examples of the modified rubber elastomer include styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (abbreviated as "SBR"), hydrogenated styrene-butadiene block copolymer ("SEB"), styrene-butadiene-styrene block copolymer ("SBS"), hydrogenated styrene-butadiene-styrene block copolymer ("SEBS"), benzene Ethylene-isoprene block copolymer ("SIR"), hydrogenated styrene-isoprene block copolymer ("SEP"), styrene-isoprene-styrene block copolymer (referred to as "SIS"), hydrogenated styrene-isoprene-styrene block copolymer (referred to as "SEPS"), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer compound, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene propylene rubber (referred to as "EPR"), ethylene propylene diene rubber (referred to as "EPDM"), etc. by having The polar group modifier has been modified rubber, etc.

(式中，R³⁰ 及R³¹ 分別獨立地表示碳數1～20之烷基、碳數3～20之環烷基或者碳數6～20之芳基)There are various antioxidants as antioxidants, but especially monophosphites such as tris(2,4-di-tert-butylphenyl)phosphite and tris(mono- and di-nonylphenyl)phosphite Phosphorus-based antioxidants such as diphosphite and phenol-based antioxidants are preferred. As the diphosphite, a phosphorus-based compound represented by the following general formula (1) is preferably used. [hua 1]

(In the formula, R ³⁰ and R ³¹ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

Specific examples of the phosphorus-based compound represented by the above general formula include distearyl pentaerythritol diphosphite, dioctyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, bis(2,4 -Di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite Wait.

As the phenolic antioxidant, known ones can be used, and specific examples thereof include 2,6-di-tert-butyl-4-methylphenol, 2,6-diphenyl-4-methoxyl Phenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis-(6-tert-butyl-4-methylphenol) , 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl) Phenyl)butane, 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methyl) Phenyl)-4-n-dodecylmercaptobutane, bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoic acid]ethylene glycol ester, 1,1-bis( 3,5-Dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane, 4,4'-thiobis(6-tert-butyl-3-methylphenol) ), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,2-bis(3,5-di -Dioctadecyl tert-butyl-4-hydroxybenzyl)malonate, n-octadecyl 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate , tetra[methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, etc. In addition to the above-mentioned phosphorus-based antioxidants and phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and the like may be used alone, or a plurality of types may be mixed and used.

The compounding amount of the antioxidant is not particularly limited, but may be, for example, 0.005 parts by mass or more, 0.01 parts by mass or more, or 0.02 parts by mass relative to 100 parts by mass of the resin (S) or 100 parts by mass of the resin (A) and the resin (B) in total. The mass part or more may be 5 mass parts or less, 4 mass parts or less, or 3 mass parts or less.

As the nucleating agent, metal salts of carboxylic acids such as aluminum bis(p-tert-butylbenzoate), methylenebis(2,4-di-tert-butylphenol) acid phosphoric acid can be selected arbitrarily. Metal salts of phosphoric acid including ester sodium, talc, and phthalocyanine derivatives are selected and used. Specific trade names include: ADK STAB NA-10, ADK STAB NA-11, ADK STAB NA-21, ADK STAB NA-30, ADK STAB NA-35, ADK STAB NA-70 manufactured by ADEKA Co., Ltd. ; PTBBA-AL manufactured by Dainippon Ink Chemical Industry Co., Ltd. These nucleating agents may be used alone or in combination of two or more.

The compounding amount of the nucleating agent is not particularly limited, but may be, for example, 0.01 part by mass or more or 0.04 part by mass or more with respect to 100 parts by mass of the resin (S) or 100 parts by mass of the resin (A) and the resin (B) in total, Moreover, it may be 5 parts by mass or less or 2 parts by mass or less.

As a mold release agent, well-known thing, such as a polyethylene wax, a polysiloxane oil, a long-chain carboxylic acid, a long-chain carboxylic acid, can be selected arbitrarily, and can be used. These release agents may be used alone or in combination of two or more.

The compounding amount of the release agent is not particularly limited, but may be, for example, 0.1 parts by mass or more or 0.2 parts by mass or more with respect to 100 parts by mass of the resin composition or 100 parts by mass of the resin (A) and the resin (B) in total, and , can be 3 parts by mass or less or 1 part by mass or less.

In one embodiment, 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, 95 mass % or more, 97 mass % or more, 99 mass % or more, 99.5 mass % or more or substantially 100% by mass is resin (S), or It is a resin (S) and one or more kinds selected from the above-mentioned other components. In addition, in the case of "substantially 100 mass %", unavoidable impurities may be included.

(thickness of resin film) In one embodiment, the average thickness of the resin film may be 10 μm or more, and may be less than 100 μm. The average thickness of the resin film is a value measured by the method described in the examples. When the average thickness is 10 μm or more, the occurrence of wrinkles in the resin film can be suppressed during the production of the continuous fiber base material, and the breakage of the resin film can be suppressed. In addition, when the average thickness is less than 100 μm, the slitting processability is improved, and the thickness of the obtained fiber-reinforced resin base material can be precisely controlled. In order to further significantly exert this effect, the average thickness of the resin film may be 99 μm or less, 98 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 70 μm or less, or 60 μm or less.

In one Embodiment, the resin film is elongated, and the difference of the thickness of the width direction edge part with respect to the thickness of the width direction center part exists in the range of -10% - 10%. For example, when the thickness of the central portion in the width direction is T μm, the thickness of the end portion in the width direction is in the range of T×0.9 μm to T×1.1 μm. By making the difference of the said thickness in the range of -10% - 10%, the difference in intensity|strength of the fiber-reinforced resin base material produced using the resin film can be suppressed. The above-mentioned difference in thickness is a value measured by the method described in the examples.

2. Manufacturing method of resin film A method for producing a resin film according to an aspect of the present invention comprises: removing an end portion of a resin film precursor containing a resin (S) by slitting to obtain the resin film, the resin film being a non-stretched film, the resin (S) S) comprises a para-row polystyrene resin (A) and a functional group-modified polyarylene ether resin (B). The manufacturing method of the resin film can be used to manufacture the resin film of one aspect of the present invention.

"Resin film precursor" means the resin film before removal of the ends. The "end portion" removed in the resin film precursor is preferably an end portion (also referred to as "film-forming end portion") formed along with the film formation of the resin film precursor. The film-forming end portion usually has a thickness different from that of the film central portion due to the surface tension of the resin (S) temporarily melted for film-forming, or the like. Therefore, the thickness of the obtained resin film can be made uniform by removing the film-forming edge.

In the slitting process, the width of the edge removal is not particularly limited. For example, when the length in the width direction of the resin film precursor is set to 100%, the part that is 1 to 10% away from the end of the film precursor can be used. Removed as ends.

In this aspect, the resin (S) includes the resin (A) and the resin (B), and thereby, even if the resin film precursor is subjected to slit processing, the film can be prevented from breaking. On the other hand, when the resin (A) is used alone, the film cannot be prevented from being broken, and cracks are generated in the periphery of the slitting portion. Therefore, according to this aspect, slitting is preferably used, whereby the end portion of the resin film precursor can be removed efficiently, preferably continuously.

In one embodiment, both ends in the width direction of the elongated resin film precursor are removed by slitting. In this case, the long resin film precursor can be rolled and continuously removed in the width direction of the resin film precursor by slitting.

For the slitting process, one or more kinds selected from a cutting tool and a laser beam can be used, for example. The slitting process can be performed by relatively moving the resin film precursor with respect to the slitting tools. For example, the slitting process can be continuously performed by fixing a slitting tool at a specific position and rolling the resin film precursor in a specific direction.

3. Fiber-reinforced resin substrate The fiber-reinforced resin substrate of one aspect of the present invention includes fibers (T) and resin (S) impregnated in the fibers (T), and the resin (S) includes resin (A) and resin (B).

In one embodiment, the fiber (T) contained in the fiber-reinforced resin substrate is at least one selected from the group consisting of carbon fiber (C) and glass fiber (D).

(Carbon Fiber (C)) The carbon fiber (C) is not particularly limited, and various carbon fibers can be used, such as PAN-based raw material polyacrylonitrile, pitch-based raw material of coal tar pitch in petroleum or coal, and phenol-based carbon fiber using thermosetting resin such as phenol resin as raw material. . The carbon fiber (C) may be obtained by a vapor phase growth method, or may be a recycled carbon fiber (RCF). Thus, the carbon fiber (C) is not particularly limited, but is preferably selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenol-based carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). 1 or more.

Among the carbon fibers (C), there are those whose degree of graphitization has changed depending on the quality of the raw materials and the sintering temperature at the time of production, but they can be used regardless of the degree of graphitization.

(glass fiber (D)) The type of glass fiber (D) is not particularly limited, and can be selected according to the purpose and application, and glass fibers of various compositions such as E glass, low dielectric glass, and silica glass can be used.

(other fibers) The fibers (T) are not limited to the carbon fibers (C) and glass fibers (D) described above. Examples of other fibers other than carbon fibers (C) and glass fibers (D) include organic synthetic fibers, natural plant fibers, and the like. As a specific example of an organic synthetic fiber, a wholly aromatic polyamide fiber, a polyimide fiber, etc. are mentioned. These other fibers may be used alone or in combination with one or more selected from the group consisting of carbon fibers (C) and glass fibers (D).

In one embodiment, the fiber (T) is 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, 95 mass % or more, 97 mass % or more, 99 mass % or more, 99.5 mass % or more or substantially 100% by mass of one or more selected from the group consisting of carbon fibers (C) and glass fibers (D), or One or more kinds selected from the group consisting of carbon fibers (C) and glass fibers (D), and one or more kinds selected from the other fibers described above. In addition, in the case of "substantially 100 mass %", unavoidable impurities may be included.

(shape and form of fiber) The shape of the fiber (T) is not particularly limited, and may have a roving selected from the following sizing agent-modified strands (sizing agent-adhered strands) spooled and wound up, and cut rovings. One or more shapes from the group consisting of cut strands, woven fabrics (cloths) made of rovings, and non-woven fabrics.

In one embodiment, the fibers (T) are woven, non-woven, or oriented in one direction. A fiber-reinforced resin substrate containing fibers in a form aligned in one direction is also referred to as a "unidirectional material".

When the fibers (T) are in the form of woven, non-woven or aligned in one direction, monofilament fibers with an average fiber diameter of preferably 3 to 20 μm, more preferably 5 to 20 μm can be used, or monofilament fibers can be used. A roving in which silk fibers are bundled in one direction. For example, products with 3,000 (3K), 6,000 (6K), 12,000 (12K), 24,000 (24K) or 60,000 (60K) monofilament fibers can be directly used, or the bundles can be further assembled. and use. The fiber bundle may be any of untwisted yarn, twisted yarn, and untwisted yarn. The fiber bundle may be contained in the fiber-reinforced resin base material in an open state, or may be contained in the fiber-reinforced resin base material as a fiber bundle in an unopened state.

In one embodiment, the fibers contained in the fiber-reinforced resin substrate are continuous fibers. In addition, the so-called "continuous fiber" means a fiber in a state of being continuous from one end to the other end of the fiber-reinforced resin substrate. Therefore, the length of the continuous fibers varies depending on the size of the fiber-reinforced resin substrate, for example, 3 cm to 10,000 m.

The thickness of the fiber-reinforced resin base material is not particularly limited, and may be, for example, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, or 90 μm or more. 500 μm or less, 400 μm or less, 300 μm or less, 250 μm or less, 200 μm or less, 150 μm or less, or 120 μm or less. The thickness of the fiber-reinforced resin base material (and the thickness of the laminate described below) is a value measured by a micrometer-type thickness meter.

4. Manufacturing method of fiber-reinforced resin substrate The manufacturing method of the fiber-reinforced resin substrate of one aspect of the present invention includes: The first step is to heat a fiber-reinforced resin base material precursor, the fiber-reinforced resin base material precursor comprising the resin film of one aspect of the present invention and the fibers superimposed on the resin film; and In the second step, the above-mentioned fiber-reinforced resin base material is obtained by cooling the above-mentioned fiber-reinforced resin base material precursor. The manufacturing method of the fiber-reinforced resin base material can be used to manufacture the fiber-reinforced resin base material of one aspect of the present invention.

(Step 1) In the first step, the fiber-reinforced resin base material precursor formed by overlapping the resin film and the fibers is heated. At this time, the fibers can be overlapped on the resin film in a state in which the entire plurality of fibers spread in a planar shape. For example, in the case of manufacturing a fiber-reinforced resin substrate comprising a woven or non-woven fabric, the woven or non-woven fabric can be superimposed on the resin film. Also, for example, in the case of manufacturing a fiber-reinforced resin substrate containing fibers in a form aligned in one direction, for example, when a fiber bundle unwound from a roving (winding body of fiber bundles) is formed by a plurality of fibers as a whole After the fibers are opened in the form of expansion, the opened fibers (maintaining the shape aligned in one direction) can be overlapped on the resin film. The fiber opening can be performed, for example, by blowing air (air flow) to the fiber bundle.

In one embodiment, in the first step, the fiber-reinforced resin substrate precursor is heated at a temperature equal to or higher than the melting point of the resin film. Thereby, the resin (S) constituting the resin film can be preferably impregnated into the fibers. Here, the melting point of the resin film means the melting point (melting point alone) of the resin (A) contained in the resin film. The melting point of the resin film is, for example, in the range of 200 to 300° C., and the heating temperature in the first step can be set, for example, in the range of 200 to 350° C. and higher than the melting point of the resin film.

In one embodiment, in the first step, the fiber-reinforced resin base material precursor is heated using a roller. Thereby, the resin (S) which comprises a resin film can be heated efficiently. In this case, the temperature of the roll (heat roll) can be set to the above-mentioned heating temperature. In addition, in the first step, the fiber-reinforced resin base material precursor may be heated by a heater such as an infrared heater. Heating by a heater can also be implemented as a step (preheating step) before heating by a roll.

In one embodiment, in the first step, the fiber-reinforced resin base material precursor is pressurized using a roller. Thereby, the resin (S) constituting the resin film can be preferably impregnated into the fibers. In this case, pressurization can be performed by pinching the fiber-reinforced resin base material precursor between a pair of rolls. The pressure of pressing is not particularly limited, and can be appropriately set by adjusting the distance (interval) between a pair of rolls.

In one embodiment, in the first step, heating and pressing of the fiber-reinforced resin substrate precursor are performed simultaneously. Thereby, the resin (S) which comprises a resin film can be impregnated in a fiber more preferably. In this case, the pressure can be applied by sandwiching the fiber-reinforced resin base material precursor between a pair of heating rolls. In addition, the so-called "simultaneous heating and pressurization" is not necessarily limited to the case where heating and pressurization are started at the same time. For example, heating and pressurization may be performed simultaneously at a certain point in time, even if heating and pressurization are started at different points in time.

(Step 2) In the second step, the fiber-reinforced resin substrate precursor heated in the first step is cooled to obtain a fiber-reinforced resin substrate.

In one embodiment, in the second step, the fiber-reinforced resin substrate precursor is cooled at a temperature below 200°C. Thereby, the resin (S) which comprises a fiber-reinforced resin base material precursor can be cooled efficiently. The cooling in the second step may be a temperature below the melting point of the resin film.

In one embodiment, in the second step, the fiber-reinforced resin base material precursor is cooled using a roll. Thereby, the resin (S) which comprises a fiber-reinforced resin base material precursor can be cooled efficiently. In this case, the temperature of the roll (cooling roll) can be set to the above-mentioned cooling temperature.

(Step 3) The manufacturing method of the fiber-reinforced resin base material may further include the following third step, or may not include the following third step. In one embodiment, the manufacturing method of the fiber-reinforced resin base material includes a third step of winding the fiber-reinforced resin base material after the second step. In the third step, the fiber-reinforced resin substrate is wound up. Thereby, the roll of the fiber-reinforced resin base material was obtained.

In one embodiment, in the third step, the fiber-reinforced resin substrate is wound at a speed of 1 to 30 m/min. By making the winding speed 1 m/min or more, the production efficiency can be improved, and the heating time of the resin film in the first step can be shortened, thereby suppressing thermal degradation of the resin. Furthermore, by making the winding speed 30 m/min or less, sufficient heating and cooling can be achieved in the first step and the second step, and the fiber can be preferably impregnated with the resin (S).

In one embodiment, the long fiber-reinforced resin base material precursor is roll-conveyed, and the first step, the second step, and the third step are continuously performed on the fiber-reinforced resin base material precursor. In this case, the above-mentioned winding speed in the third step may be equivalent to the roller conveyance speed in the first step and the second step.

(release sheet) In one embodiment, in one or more steps selected from the group consisting of the first step, the second step, and the third step, the fiber-reinforced resin base material precursor is superimposed on one side or both sides of the precursor. profiled sheet. Thereby, resin (S) is prevented from adhering to the manufacturing apparatus (roll etc.), and each process can be implemented stably.

In one embodiment, in the first step and the second step, the release sheet is overlapped on one side or both sides of the fiber-reinforced resin substrate precursor, and before the third step, the release sheet is reinforced from the fiber. Resin substrate peeling and recycling. Thereby, the roll of the fiber-reinforced resin base material which does not contain a release sheet is obtained.

In one embodiment, the fiber-reinforced resin base material is directly supplied to the third step in a state where the release sheet is stacked. Thereby, the roll of the fiber-reinforced resin base material containing a release sheet was obtained.

The release sheet is not particularly limited, but may contain, for example, one or more selected from the group consisting of fluororesins such as polytetrafluoroethylene, thermosetting polyimide resins, and the like. These resins can also be reinforced by fibers. As such a fiber, glass cloth etc. are mentioned, for example, It is not limited to this.

Moreover, as a release sheet, what laminated|stacked the resin containing the said resin on a support layer can also be used. The resin layer can be laminated on one side or both sides of the support layer. The support layer is not particularly limited, and, for example, an expanded graphite sheet or the like can be mentioned. The expanded graphite sheet is obtained, for example, by the following method: after selecting natural flake graphite, the resulting product is expanded by acid treatment with a mixed acid solution of concentrated sulfuric acid and an acidulant by rapid heating at a high temperature, and is formed by rolling. Formed in sheet form; but not limited to this method.

In the above description, with regard to the heating and pressurization of the fiber-reinforced resin base material precursor, the method using a roll was mainly shown, but it is not limited to this. The heating and pressurization of the fiber-reinforced resin substrate precursor can also be performed by press molding. In this case, a fiber-reinforced resin base material precursor is formed by overlapping a resin film cut with a specific size on the fiber in advance, and the fiber-reinforced resin base material precursor is punched to impregnate the fiber with the resin (S). The first step), and secondly, the fiber-reinforced resin substrate can be obtained by cooling (the second step).

In the above description, the sizing agent may or may not be attached to the surface of the fiber (T). When using the fiber (T) to which the sizing agent is attached, the type of the sizing agent can be appropriately selected according to the type of the fiber (T) and the resin (S), and is not particularly limited. Fibers (T) treated with epoxy-based sizing agents, urethane-based sizing agents, polyamide-based sizing agents, or fibers (T) that do not contain sizing agents are made into various products. Products, but fibers (T) can be used regardless of the type and presence of sizing agent.

5. Laminate The lamination system of one aspect of the present invention is formed by laminating and integrating two or more fiber-reinforced resin substrates of one aspect of the present invention.

In one embodiment, the fibers derived from the respective fiber-reinforced resin substrates included in the laminate are aligned in the same direction. Thereby, the laminated body is remarkably strengthened with respect to one direction.

In one embodiment, the fibers derived from the respective fiber-reinforced resin substrates included in the laminate are aligned in different directions with each other. Thereby, the laminated body is strengthened irrespective of the direction (with respect to multiple directions).

Two or more fiber-reinforced resin substrates may be integrated by the resin (S) itself contained in the fiber-reinforced resin substrate (by melting of the resin (S)), or it may be separated from the fiber-reinforced resin substrate. Then the layers are integrated. The material of the next layer is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins as described in the description of the resin film.

The thickness of the layered body is not particularly limited, but may be, for example, 0.1 mm or more, 0.5 mm or more, or 1.0 mm or more, and may be 10 mm or less, 5.0 mm or less, or 3.0 mm or less.

6. Manufacturing method of laminated body A method for manufacturing a layered product of an aspect of the present invention includes: Stacking two or more fiber-reinforced resin substrates of one aspect of the present invention to form a laminate precursor; and The above-mentioned layered body precursor is press-molded to obtain a layered body in which two or more of the above-mentioned fiber-reinforced resin base materials are laminated and integrated. This method for producing a layered product can be used to produce a layered product according to an aspect of the present invention.

(Formation of Laminate Precursor) In one embodiment, two or more fiber-reinforced resin substrates are stacked so that the fiber orientation directions of the respective fiber-reinforced resin substrates are mutually aligned in the same direction. Thereby, the obtained laminate is remarkably strengthened in one direction.

In one embodiment, two or more fiber-reinforced resin substrates are stacked so that the fiber orientation directions of the respective fiber-reinforced resin substrates are mutually aligned in different directions. Thereby, the obtained laminated body is strengthened irrespective of the direction (in multiple directions).

In the layered product precursor, two or more fiber-reinforced resin substrates may be directly layered, or may be layered with an adhesive layer interposed therebetween.

The number of fiber-reinforced resin substrates to be stacked in order to form the laminate precursor is not particularly limited, and may be, for example, 2 to 1,000.

(Formation of laminated body) The laminate precursor is press-molded to obtain a laminate in which two or more fiber-reinforced resin base materials are laminated and integrated.

The punching pressure is applied along the layering direction of the fiber-reinforced resin base material, and its magnitude is not particularly limited.

The temperature of press molding may be a temperature higher than the melting point of the resin (S), or may be a temperature lower than the melting point of the fiber.

For the press forming, for example, a vacuum press or the like can be used. In the case of using a vacuum press, the degree of vacuum is not particularly limited, but may be, for example, -0.1 MPa or less.

7. Complex The complex of one aspect of the present invention comprises: The first member, which is the fiber-reinforced resin substrate of one aspect of the present invention or the laminate of one aspect of the present invention; and The second member is an injection-molded body integrated with the first member.

In one embodiment, the injection-molded body contains resin. The resin is not particularly limited, and examples thereof include the above-mentioned resin (S) and other resins described in the description of the resin film.

The injection-molded body may or may not contain other components other than the resin in addition to the resin. As other components, for example, the above-mentioned fibers (T) and other components described in the description of the resin film, etc. are mentioned.

8. Manufacturing method of composite As for the method for producing the composite of one aspect of the present invention, the fiber-reinforced resin substrate of one aspect of the present invention or the first member of the laminate of one aspect of the present invention is inserted into a mold By injection molding, a composite body including the first member and the second member as an injection-molded body integrated with the first member is obtained. The method for producing the composite can be used to produce the composite of one aspect of the present invention.

In the above description of the composite body, the case where the second member is an injection-molded body containing resin has been mainly shown, but the present invention is not limited to this. The second member may contain any material other than resin, and may be formed by any method other than injection molding. As an example of the material contained in a 2nd member, a metal, a foam, etc. are mentioned, for example. The foam may be, for example, a resin foam or the like. The resin of a resin foam is not specifically limited, For example, polystyrene resin etc. are mentioned. The polystyrene resin may be the above-mentioned resin A (opposite polystyrene resin), and may be a polystyrene resin other than the resin A.

9. Purpose The application of the resin film, fiber-reinforced resin substrate, laminate, and composite (hereinafter, sometimes referred to as "article X" as a general term for these) of one aspect of the present invention described above is not particularly limited, and can be used for Various uses. Various parts for various purposes can be made using Item X, or contain Item X.

1 to 4 , an example of an automobile part composed of the article X will be described. In addition, in an automobile, the position where each automobile part is installed is not necessarily limited to the examples shown in FIGS. 1 to 4 .

As shown in FIG. 1, the article X suitably constitutes, for example, a hood 1, a roof (including a roof frame) 2, a door frame pillar 3, a seat back 4, a headrest bracket 5, an engine part 6, a crash box 7, a front floor Tunnel 8, front floor 9, bottom cover 10, bottom support rod 11, anti-collision beam 12, fender bracket 13, front cover 14, front hood 15, front cross connecting rod 16, transmission central duct 17, radiator Core bracket 18, cab front wall 19, front door inner panel 20, rear trunk rear panel 21, rear trunk side panel 22, rear trunk floor 23, rear trunk shelf 24, etc.

Also, as shown in FIG. 2 , the article X suitably constitutes, for example, a power electronic unit 25 , a plug 26 for rapid charging, an on-board charger 27 , a lithium ion battery 28 , a battery control unit 29 , a power electronic/control unit 30 , and a three-phase synchronous motor. 31. A plug 32 for household charging, etc.

Furthermore, as shown in FIG. 3 , the article X suitably constitutes, for example, a solar twilight sensor 33, an alternator 34, an EDU (electronic injector driver unit) 35, and an electronic throttle valve. 36. Tumble flow control valve 37, throttle valve position sensor 38, radiator fan controller 39, stick coil 40, A/C (air conditioning, air conditioning device) pipe joint 41, diesel engine particles Capture filter 42, headlight reflector 43, charge air duct 44, charge air cooling head 45, intake air temperature sensor 46, gasoline fuel pressure sensor 47, cam/crankshaft position sensor 48, combination Valve 49, oil pressure sensor 50, transmission gear angle sensor 51, continuously variable transmission oil pressure sensor 52, ELCM (Evaporative Leak Check Module) pump 53, water pump impeller 54, Steering rod connector 55, ECU (engine computer unit, engine computer unit) connector 56, ABS (antilock braking system, anti-brake system) reservoir piston 57, actuator cover 58 and the like.

In addition, as shown in FIG. 4 , the article X is also suitably used as a sealing material for sealing a sensor included in the in-vehicle sensor module, for example. Such sensors are not particularly limited, and examples thereof include the atmospheric pressure sensor 59 (for example, for altitude correction), the boost pressure sensor 60 (for example, for fuel injection control), and the atmospheric pressure sensor 61 (for IC) , (for example, for airbags) acceleration sensor 62, (for example for seat adjustment) gauge pressure sensor 63, (for example for fuel tank leak detection) tank pressure sensor 64, (for example for air conditioning control) refrigerant pressure Sensor 65, (for example for ignition coil control) coil drive 66, EGR (exhaust gas recirculation) valve sensor 67, (for example for fuel injection control) air flow sensor 68, (for example for fuel injection control) inlet Tracheal pressure (MAP) sensor 69, etc. These may also be in the form of front-end modules. In addition, the article X suitably constitutes the oil pan 70, the radiator cover 71, the intake manifold 72, and the like.

The automobile parts composed of the article X are not limited to those illustrated with reference to FIGS. 1 to 4 , but are also suitable for use in, for example, high-voltage (wiring harness) connectors, millimeter-wave radomes, IGBTs (Insulated Gate Bipolar Transistors, insulated gate bipolars) Transistor case, battery fuse terminal, radiator grill, instrument cover, inverter cooling water pump, battery monitoring unit, structural parts, high voltage connector, motor control ECU (engine computer unit), inverter, piping parts, Carbon canister purification valve, power unit, busbar, motor reducer, carbon canister, etc. Moreover, the automobile part which consists of the article X may be, for example, a stack frame or the like.

The article X is also suitable for use in motorcycle parts and bicycle parts, and more specifically, motorcycle parts, a motorcycle cowl, and the like are exemplified.

Item X can also meet the requirements of lightweight, water resistance, chemical resistance, weather resistance, etc., so it is also suitable for parts such as aircraft and drones.

In addition, since the article X is excellent in wear resistance, it is also suitable for sliding parts such as gears and bearings.

Item X can also be used in various electrical appliances because of its excellent chemical resistance. For example, it is also preferable to use a part constituting a water heater, specifically, a part of a natural refrigerant heat pump water heater known as a so-called "EcoCute (registered trademark)" or the like. Examples of such parts include sprinkler parts, pump parts, piping parts, and the like, and more specifically, single-ended circulation joints, release valves, mixing valve units, heat-resistant traps, pump housings, composite water valves, and water inlets. Accessories, resin joints, piping parts, resin pressure reducing valves, elbows for water supply hydrants, etc.

Item X is also suitable for home appliances, electronic equipment, and more specifically, microwave ovens, telephones, mobile phones, refrigerators, vacuum cleaners, OA (Office Automation) equipment, power tool parts, electrical parts use, antistatic Application, high frequency electronic parts, high heat dissipation electronic parts, high voltage parts, electromagnetic wave shielding parts, communication equipment, AV (audiovisual, audio-visual) equipment, computers (including notebook computers), registers, electric fans, exhaust fans , sewing machines, ink peripheral parts, ribbon cassettes, air cleaner parts, toilet seat parts for warm water cleaning, toilet seats, toilet lids, electric cooker parts, optical pickup equipment, parts for lighting fixtures, DVD (Digital Versatile Disc, digital Versatile Disc), DVD-RAM (Digital Versatile Disc Random Access Memory, Digital Versatile Disc-Random Access Memory), DVD pickup parts, DVD pickup substrates, hard disk parts, switch parts, sockets, monitors , camcorders, digital cameras, filaments, plugs, high-speed color photocopiers (laser printers), inverters, air conditioners, keyboards, converters, televisions, fax machines, optical connectors, semiconductor chips, LEDs (Light Emitting Diode, light-emitting diode) parts, washing machine/washer dryer parts, dishwasher/dishwasher dryer parts, etc.

The article X is also suitable for building materials, and more specifically, an outer wall panel, a rear panel, a partition wall panel, a signal lamp, an emergency lighting lamp, a wall material, etc. are mentioned.

Item X is also applicable to miscellaneous goods, daily necessities, etc. More specifically, chopsticks, lunch boxes, cutlery containers, food trays, food packaging materials, sinks, boxes, toys, fishing tackle, sporting goods, water skis, doors Covers, door steps, automatic machine (ATM) parts, pachinko table parts, remote control cars, remote control storage boxes, stationery, musical instruments, tumblers, dumbbells, helmet case products, etc.

For each of the various parts described above, some or all of the parts may be made using, or contain, item X. [Example]

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

(Example 1) <Preparation of resin> 100 parts by mass of resin A-1 (opposite polystyrene resin, racemic pentad: 98 mole %; MFR: 13 g/10 min; melting point: 270°C) and resin B-1 (Fuma Acid-modified polyphenylene ether, the modification amount is 1.7% by mass, and the glass transition point is 220° C.) After 18 parts by mass of dry blending, a two-shaft kneader (manufactured by Coperion; ZSK32MC) with a cylinder diameter of 32 mm is used, and the The resin (S) was obtained by melt-kneading at a set temperature of 300°C. The obtained resin (S) was dried at 140°C for 5 hours.

<Manufacture of resin film> FIG. 5 is a schematic diagram illustrating an example of a method for producing a resin film according to an aspect of the present invention. As shown in Fig. 5, the resin (S) obtained in the above-mentioned "Preparation of Resin" was supplied to a film forming machine (manufactured by Chuangyan Co., Ltd., spiral shape: full thread; spiral diameter: 30 mm) equipped with a uniaxial kneader. mm; L/D (long/diameter, aspect ratio): 38; extrusion temperature: 320°C) 101, extrude onto the roller 102 set at 100°C, in the order of rollers 103 and 104 set at 90°C Roll conveyance is performed, and then, by slitting using a razor blade 105, both ends in the width direction of the resin film precursor 106 being conveyed are continuously removed to obtain an unstretched resin film 107. The obtained resin film 107 is wound up to obtain a roll 108 . In the above-mentioned slitting process, the portion up to 2.0 cm from both ends in the width direction of the resin film precursor 106 was removed as an end portion, and the length in the width direction of the resin film precursor 106 was 25 cm. At this time, the width (2.0 cm) of the removed edge corresponds to 8% when the length (25 cm) in the width direction of the resin film precursor 106 is set to 100%. As a result of this slitting process, the length in the width direction of the obtained resin film 107 became 21 cm.

<Evaluation of resin film> (1) Slitting workability The presence or absence of film breakage accompanying the slitting process in the above-mentioned "manufacturing of resin film" was visually observed, and slitting processability was evaluated according to the following evaluation criteria. [Evaluation Criteria] ○: No film breakage (rupture) occurred, and a resin film was continuously obtained ×: Film breakage (crack) occurred, and a resin film was not continuously obtained

(2) Thickness of central part and end part The elongated resin film (the resin film precursor before slitting and the resin film after slitting) obtained in the above-mentioned "manufacturing of resin film" was measured by a micrometer-type thickness gauge ( Mitutoyo Co., Ltd.) measured the thickness of the center part of the width direction, the thickness of the edge part of the width direction, and the difference of these thicknesses. In addition, the average thickness of the resin film after slit processing was also measured by the said micrometer type thickness meter. The results are shown in Table 1. Here, the so-called "thickness of the central part in the width direction" (abbreviated as "the thickness of the central part" in Table 1) means that 25 cm is cut along the length direction at the stage when the resin film can be stably produced, and then the width of the cut resin film is The central part of the direction was cut parallel to the longitudinal direction to obtain a slice, and the average value was obtained by measuring the thickness of the slice at 5 cm intervals in the longitudinal direction. In Example 1, the film for measurement was cut out after 20 minutes of production at 3 m/min. In addition, the so-called "thickness at the end in the width direction" (abbreviated as "the thickness at the end" in Table 1) is the same as the film for measurement of the "thickness at the center in the width direction" described above, at the stage where the resin film can be stably produced 25 cm were cut in the longitudinal direction, and the average value was obtained by measuring the thickness of 5 locations in the width direction from the end of the cut resin film in the width direction at 5 cm intervals along the longitudinal direction. In Example 1, the measurement was performed using the film for measurement used for the measurement of "the thickness of the central part in the width direction". In addition, when the said average value differs in the both ends of the width direction of the resin film cut out, the average value of the end with the larger difference with respect to the said "thickness of the width direction center part" is used. The difference in thickness (the difference between the thickness at the end in the width direction and the thickness at the center in the width direction) is calculated by the difference in thickness [%]=((the thickness at the end in the width direction - the thickness at the center in the width direction)/the center in the width direction part thickness) × 100 formula. Furthermore, the "average thickness of the resin film" after the slitting process refers to the average thickness of a total of 30 thicknesses obtained by dividing the resin film into 6 regions equally in the width direction and measuring the thickness of 5 regions in each region. . In addition, in the description of the above-mentioned thickness, the "resin film precursor" before slitting is also abbreviated as "resin film".

<Manufacture of fiber-reinforced resin base material> FIG. 6 is a schematic diagram illustrating an example of a method for producing a fiber-reinforced resin substrate according to an aspect of the present invention. As shown in FIG. 6 , the double-sided overlapping of the resin film 107 obtained in the above-mentioned “manufacturing of the resin film” is formed by roving carbon fiber (“TRH50-30M” manufactured by Mitsubishi Chemical Corporation) 109 opened by air flow. A fiber-reinforced resin base material precursor, and a release sheet (polytetrafluoroethylene sheet) 110 is overlapped on both sides of the fiber-reinforced resin base material precursor. For the thus formed (roll conveyed), the heating roller 111 is heated and pressurized by setting one of 270° C., so that the resin (S) of the resin film 107 is continuously impregnated in the carbon fibers, and secondly, by setting the The cooling roll 112 was cooled at 100° C., and then the release sheet 110 on both sides was peeled off to obtain a fiber-reinforced resin base material 113 . Further, the fiber-reinforced resin base material 113 was wound up at a speed of 10 m/min to obtain a roll 114 . One of the series of steps of the above "fabrication of fiber-reinforced resin base material" is carried out continuously, and the above-mentioned winding speed is equal to the roller conveying speed. The obtained fiber-reinforced resin base material contains carbon fibers oriented in one direction (roll conveyance direction), and resin (S) impregnated in the carbon fibers, the volume content (Vf) of the carbon fibers is 50%, and the thickness is 100%. μm. Here, the fiber-reinforced resin base material contains the above-mentioned carbon fibers as continuous fibers.

<Evaluation of Fiber Reinforced Resin Base Materials> (1) Impregnation With respect to the fiber-reinforced resin base material obtained in the above-mentioned "Manufacture of fiber-reinforced resin base material", the impregnation property was evaluated by the water immersion method. Specifically, the fiber-reinforced resin substrate was cut into a 5 cm square, immersed in 200 ml of water (ion-exchanged water), and left to stand for 24 hours, and then the fiber-reinforced resin substrate was taken out. The water after taking out the fiber-reinforced resin substrate was visually observed, and the impregnation property was evaluated according to the following evaluation criteria. [Evaluation Criteria] 〇: Carbon fiber does not exist in water ×: Carbon fibers are present in water

<Manufacture of laminated body> The fiber-reinforced resin base material obtained in the above-mentioned "manufacturing of fiber-reinforced resin base material" was cut out to 10 cm×10 cm, and 20 sheets were superimposed along one direction to form a laminate precursor. With a vacuum press, under the conditions of vacuum degree below -0.1 MPa and 330°C, the pressing pressure is 0 MPa for 20 minutes, 5 MPa for 10 minutes, 15 MPa for 28 minutes, and 60 The layered body precursor was press-molded stepwise along the layering direction under the condition of 2 minutes at MPa, then returned to atmospheric pressure, and cooled to 20° C. to obtain a layered body. The thickness of the obtained laminate was 2.0 mm.

<Evaluation of Laminates (Bending Properties)> Using a diamond cutter, the laminated body obtained in the above-mentioned "manufacturing of laminated body" was cut so that the length in the fiber direction was 10 cm and the width was 1 cm, followed by annealing (drying at 120°C for 12 hours), and A test piece was prepared. For this test piece, the bending properties were measured in accordance with ISO 178:2010. Specifically, the test piece was placed on a pair of support beams arranged at intervals along the fiber alignment direction in the test piece, and a force was applied from the upper to the lower side of the central portion of the test piece by the indenter. Under the conditions that the temperature is 23°C, the radius of the indenter is 5 mm, the distance between the fulcrums (support beams) is 6 cm, and the test speed is 3 mm/min, the bending strength (MPa) and the elastic modulus (GPa) are measured as the bending strength. characteristic. The results are shown in Table 1.

＜Manufacture of complexes＞ FIG. 7 is a schematic diagram for explaining an example of a method for producing a composite of one aspect of the present invention. As shown in FIG. 7( a ), the fiber-reinforced resin substrate 113 obtained in the above-mentioned “Manufacture of Fiber-Reinforced Resin Substrate” (preliminarily in such a way that the length along the fiber orientation direction α is 6 cm and the width is 1 cm) Cut out; thickness 100 μm) and inserted into a mold (internal dimensions: length 6 cm, width 1 cm, thickness 1 mm) 115 set at 160°C. Next, as shown in FIG. 7( b ), the resin (S) obtained in the above-mentioned “preparation of resin” is heated and melted at 320° C., and injected into the mold 115 with an injection pressure of 50 MPa. Next, as shown in FIG. 7( c ), the pressure of the mold 115 is kept at 50 MPa for 15 seconds, and the injection molded body (resin (S)) 116 is cured. Next, the mold 115 is removed, and as shown in FIG. 7( d ), a composite body 117 is obtained. The composite 117 includes a first member (thickness: 100 μm) as the fiber-reinforced resin base material 113 , and a second member (thickness: 900 μm) as an injection-molded body 116 integrated with the fiber-reinforced resin base material 113 .

<Evaluation of Composites (Bending Properties)> The flexural properties of the composite obtained in the above-mentioned "Production of the composite" were measured in accordance with ISO 178:2010. Specifically, as shown in FIG. 8 which is a schematic diagram for explaining the test method of the bending characteristics of the composite body, in the state where the fiber-reinforced resin base material 113 side in the composite body 117 faces downward, the The composite body 117 is placed on one pair of support beams 118 arranged at intervals along the fiber orientation direction α of the fiber-reinforced resin base material 113, and is applied from the upper to the downward direction of the central portion of the composite body 117 by an indenter (not shown). Force (the direction of the force is indicated by a white arrow). Under the conditions that the temperature is 23°C, the radius of the indenter is 5 mm, the distance between the fulcrums (support beam 118) is 3 cm, and the test speed is 2 mm/min, the bending strength (MPa), elastic modulus (GPa) and Strain (%) as bending characteristic. The flexural properties of the composite and the rate of improvement of the flexural properties with respect to the individual resins (in which the fiber-reinforced resin base material is omitted in the composite) (relative values when the flexural properties of the individual resins are set to 100%) are shown. in Table 1.

(Example 2) Except using resin A-2 (para-row polystyrene resin, racemic pentad: 98 mole %; MFR: 9 g/10 min; melting point: 270°C) instead of resin A-1 in Example 1 , and the test and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1) The test and evaluation were carried out in the same manner as in Example 1, except that the preparation of the resin B-1 in Example 1 was omitted. In addition, in the comparative example 1, since the resin film was not obtained by cracking with the slitting process, the test and evaluation of the fiber-reinforced resin base material, the laminate, and the composite were omitted. The results are shown in Table 1.

(Comparative Example 2) The test and evaluation were carried out in the same manner as in Example 1, except that the preparation of the resin B-1 in Example 2 was omitted. In addition, in the comparative example 2, since the resin film was not obtained by cracking with the slitting process, the test and evaluation of the fiber-reinforced resin base material, the laminate, and the composite were omitted. The results are shown in Table 1.

(Comparative Example 3) Except using resin A-3 (para-row polystyrene resin, racemic pentad: 98 mole %; MFR: 4 g/10 min; melting point: 270°C) instead of resin A-1 in Example 1, The test and evaluation were carried out in the same manner as in Example 1, except that the preparation of the resin B-1 in Example 1 was omitted. The results are shown in Table 1.

(Example 3) Tests and evaluations were carried out in the same manner as in Example 1, except that roving glass fibers (“RS24QR” manufactured by Nittobo Industries, Ltd.) were used in place of the roving carbon fibers in Example 1 so that the fiber content shown in Table 1 was obtained. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 3 resin A-1 [mass part] 100 - 100 - - 100 A-2 [mass parts] - 100 - 100 - - A-3 [mass part] - - - - 100 - B-1 [mass part] 18 18 - - - 18 Evaluation of resin films Thickness before slitting (resin film precursor) Central part [μm] 50 50 50 50 50 50 end [μm] 189 193 186 188 206 193 Thickness difference [%] 278 286 272 276 312 286 Slitting workability 〇 〇 × × 〇 〇 Thickness after slitting Central part [μm] 50 50 - - 50 50 end [μm] 51 51 - - 53 51 Thickness difference [%] 2.0 2.0 - - 6.0 2.0 Average thickness [μm] 50 50 - - 50 50 Fiber Reinforced Resin Base fiber type CF CF - - CF GF Fiber content [vol%] 50 50 - - 50 51 Evaluation of Fiber Reinforced Resin Substrates Impregnation 〇 〇 - - × 〇 Evaluation of Laminates (Bending Properties) Strength [MPa] 100 100 - - 80 40 Elastic modulus [GPa] 1760 1770 - - 780 1070 Evaluation of composites (flexural properties) Strength [MPa] (Increase rate [%]) 10.4 (270) 10.5 (273) - - 4.2 (110) 7.9 (210) Elasticity rate [GPa] (increase rate [%]) 200 (250) 200 (250) - - 95 (119) 170 (210) Strain [%] (Increase rate [%]) 3.5 (160) 3.6 (165) - - 2.2 (100) 3.9 (180)

Several embodiments and/or examples of the present invention have been described in detail above, but it is easy for the artisan to describe such illustrative embodiments and/or examples without materially departing from the novel teachings and effects of the present invention. The examples are subject to various modifications. Therefore, these various modifications are also included within the scope of the present invention. The entire contents of the documents described in this specification and the application on which priority under the Paris Convention of the present application is based are cited.

1: Hood 2: roof 3: door frame pillars 4: Seat back 5: Headrest bracket 6: Engine parts 7: Crash box 8: Front floor access 9: Front Floor 10: Bottom cover 11: Bottom support rod 12: Anti-collision beam 13: Fender bracket 14: Front cover 15: Front hood 16: Front transverse connecting rod 17: Transmission central pipe 18: Radiator core bracket 19: The front wall of the cab 20: Front door inner panel 21: Rear trunk rear panel 22: Rear trunk side panel 23: Rear trunk floor 24: Rear trunk shelf 25: Power Electronics Unit 26: Plug for fast charging 27: Car Charger 28: Lithium-ion battery 29: Battery Control Unit 30: Power Electronics/Control Unit 31: Three-phase synchronous motor 32: Plug for home charging 33: Solar Twilight Sensor 34: Alternator 35: EDU 36: Electronic throttle valve 37: Tumble flow control valve 38: Throttle valve position sensor 39: Radiator fan controller 40: Rod coil 41: A/C pipe joint 42: Diesel Particulate Capture Filter 43: Headlight reflector 44: Charge air duct 45: Charge air cooling head 46: Intake air temperature sensor 47: Gasoline fuel pressure sensor 48: Cam/Crankshaft Position Sensor 49: Combination valve 50: Oil pressure sensor 51: Gearbox gear angle sensor 52: CVT oil pressure sensor 53: ELCM Pump 54: Water pump impeller 55: Steering rod connector 56: ECU connector 57: ABS reservoir piston 58: Actuator Cover 59: Atmospheric pressure sensor 60: Boost pressure sensor 61: Atmospheric pressure sensor 62: Accelerometer 63: Gauge pressure sensor 64: In-box pressure sensor 65: Refrigerant pressure sensor 66: Coil Drive 67: EGR valve sensor 68: Air flow sensor 69: Intake pipe pressure sensor 70: Oil pan 71: Radiator cover 72: Intake manifold 101: Film forming machine 102: Roller 103: Roller 104: Roller 105: Razor Blade 106: Resin film precursor 107: Resin film 108: Reel 109: Roving carbon fiber 110: Release sheet 111: Heating roller 112: cooling roll 113: Fiber-reinforced resin substrate 114: Reel 115: Mold 116: Injection molding 117: Complex 118: Support beam X:Item α: fiber orientation direction

FIG. 1 is a schematic diagram illustrating an automobile part. FIG. 2 is a schematic diagram illustrating an automobile part. FIG. 3 is a schematic diagram illustrating an automobile part. FIG. 4 is a schematic diagram illustrating an automobile part. FIG. 5 is a schematic diagram illustrating an example of a method for producing a resin film according to an aspect of the present invention. FIG. 6 is a schematic diagram illustrating an example of a method for producing a fiber-reinforced resin substrate according to an aspect of the present invention. FIGS. 7( a ) to ( d ) are schematic views for explaining an example of a method for producing a composite of one aspect of the present invention. Fig. 8 is a schematic diagram for explaining the test method of the bending properties of the composite body.

Claims (25)

A resin film used to manufacture a fiber-reinforced resin substrate, The above-mentioned resin film is a non-stretched film and contains a resin (S), and the resin (S) contains a para-polystyrene resin (A) and a functional group-modified polyarylene ether resin (B). The resin film of claim 1 has an average thickness of 10 μm or more and less than 100 μm. The resin film of claim 1, wherein the MFR of the above-mentioned opposite-row polystyrene resin (A) is 5-30 g/10 min. The resin film according to claim 1, comprising 1 to 30 parts by mass of the above-mentioned functional group-modified polyarylene ether resin (B) relative to 100 parts by mass of the above-mentioned opposite-row polystyrene resin (A). The resin film of claim 1 is in the shape of a long strip, and the difference between the thickness of the end portion in the width direction and the thickness of the central portion in the width direction is in the range of -10% to 10%. A method for producing a resin film, which is used to produce the resin film as claimed in any one of claims 1 to 5, comprising: The above-mentioned resin film is obtained by removing the end portion of the non-extended resin film precursor comprising the resin (S), which comprises the opposite row polystyrene resin (A), and the functional group-modified resin film is obtained by slitting. Properties of poly(arylene ether) resin (B). The manufacturing method of the resin film of Claim 6 which removes the both ends of the width direction of the said resin film precursor of elongate shape by slitting. The manufacturing method of the resin film of Claim 6 which rolls the said resin film precursor of elongate shape, and removes the both ends of the width direction of this resin film precursor continuously by slit processing. A fiber-reinforced resin substrate comprising fibers and resin (S) impregnated in the fibers; The above-mentioned resin (S) includes a para-row polystyrene resin (A) and a functional group-modified polyarylene ether resin (B). The fiber-reinforced resin substrate according to claim 9, wherein the fibers are at least one selected from the group consisting of carbon fibers and glass fibers. The fiber-reinforced resin substrate according to claim 9, wherein the fibers are woven, non-woven, or oriented in one direction. The fiber-reinforced resin substrate according to claim 9, wherein the fibers are continuous fibers. A method for manufacturing a fiber-reinforced resin base material, which is used to manufacture the fiber-reinforced resin base material as claimed in any one of claims 9 to 12, comprising: The first step is to heat a fiber-reinforced resin base material precursor, the fiber-reinforced resin base material precursor comprising the resin film according to any one of Claims 1 to 5, and fibers overlapping the resin film; and In the second step, the above-mentioned fiber-reinforced resin base material is obtained by cooling the above-mentioned fiber-reinforced resin base material precursor. The method for producing a fiber-reinforced resin substrate according to claim 13, wherein in the first step, the fiber-reinforced resin substrate precursor is heated at a temperature equal to or higher than the melting point of the resin film. The method for producing a fiber-reinforced resin base material according to claim 13, wherein in the first step, the fiber-reinforced resin base material precursor is heated using a roll. The method for producing a fiber-reinforced resin base material according to claim 13, wherein in the first step, the fiber-reinforced resin base material precursor is pressurized with a roll. The method for producing a fiber-reinforced resin base material according to claim 13, wherein in the first step, the heating and pressurization of the fiber-reinforced resin base material precursor are simultaneously performed. The method for producing a fiber-reinforced resin base material according to claim 13, wherein in the second step, the fiber-reinforced resin base material precursor is cooled at a temperature below 200°C. The method for producing a fiber-reinforced resin base material according to claim 13, wherein in the second step, the fiber-reinforced resin base material precursor is cooled using a roll. The method for producing a fiber-reinforced resin substrate according to claim 13, comprising: a third step of winding up the fiber-reinforced resin substrate at a speed of 1 to 30 m/min after the second step. The method for producing a fiber-reinforced resin substrate according to claim 20, wherein in one or more steps selected from the group consisting of the first step, the second step, and the third step, the fiber-reinforced resin is A release sheet is overlapped on one or both sides of the substrate precursor. A layered product obtained by layering and integrating two or more fiber-reinforced resin substrates according to any one of claims 9 to 12. A method for manufacturing a laminate, comprising: Stacking two or more fiber-reinforced resin substrates as claimed in any one of claims 9 to 12 to form a laminate precursor; and The above-mentioned layered body precursor is press-molded to obtain a layered body in which two or more of the above-mentioned fiber-reinforced resin base materials are laminated and integrated. A complex comprising: The first member, which is the fiber-reinforced resin base material according to any one of claims 9 to 12 or the laminate according to claim 22; and The second member is an injection-molded body integrated with the first member. A method of manufacturing a composite, comprising: injection molding in a state where a first member serving as the fiber-reinforced resin substrate according to any one of claims 9 to 12 or the laminate according to claim 22 is inserted into a mold , to obtain a composite including the first member and the second member as an injection-molded body integrated with the first member.

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