JP6211875B2 - Prepreg and manufacturing method thereof - Google Patents

Description

  The present invention relates to a prepreg that has excellent heat resistance and can be molded in a short time.

Although plastic is lighter than metal, its strength and elastic modulus are low, so that its use is often limited as a structural material. Therefore, it is used as a lightweight and high-strength material by combining with a fibrous material having a high elastic modulus such as glass fiber or carbon fiber. In such a composite material, there are two types of fiber mixing methods. There are a method of evenly pulverizing finely cut fibers and a method of impregnating plastics with the fibers having directionality.
The composite material in the latter case is molded from the form of an intermediate substrate generally called a prepreg to obtain a final form. In this case, as the matrix resin constituting the prepreg, a thermosetting resin having appropriate tackiness and flexibility necessary for laminating the prepreg is used.

What is used for the prepreg is a thermosetting resin typified by an epoxy resin, and has characteristics such as excellent heat resistance, solvent resistance, and mechanical properties. However, in order to develop sufficient performance, it is necessary to react and cure by heating. For this purpose, it is necessary to heat while applying pressure for several tens of minutes, and there is a problem that a molding cycle becomes long even in a molded body having a relatively simple shape.
In addition, as a method for producing a prepreg, a method in which a matrix resin is impregnated in a state in which a fiber of a reinforcing material has directionality is mainly used. The composite material obtained by this method has anisotropy in strength and is strong in pulling in the fiber direction, but weak in pulling in a direction perpendicular to the fiber. Therefore, a plurality of prepregs are overlaid so that the fiber directions are different. In such a simple lamination, a lack of adhesive strength between layers often becomes a problem (delamination or delamination).

As a countermeasure, Patent Document 1 proposes a prepreg having a structure in which fine particles of thermoplastic resin are dispersed on the surface of a prepreg composed of an epoxy resin composition and reinforcing fibers.
Alternatively, Patent Documents 2 and 3 propose a technique for improving interlayer strength by disposing a thermoplastic resin film on the surface of a fiber reinforced prepreg and laminating.
However, although these methods improve the interlayer strength, the problem of taking a long time for molding cannot be solved because the thermosetting resin is reacted.

JP-A 63-170428

JP 51-58484 A

JP-A-60-231738

  An object of the present invention is to provide a prepreg in which a reinforcing fiber cloth is impregnated or coated with a polyarylate resin, which has excellent heat resistance and can be molded in a short time.

The inventor of the present invention has reached the present invention as a result of intensive studies to solve such problems.
That is, the gist of the present invention is as follows.
(1) The reinforcing fiber cloth includes a structure represented by the following general formulas (I) and (II), and the molar ratio thereof is 0.10 ≦ {(I) / [(I) + (II)]} ≦ 0 A prepreg obtained by impregnating or coating a polyarylate resin in the range of 90. The glass transition temperature of the polyarylate resin is 200 ° C or higher and lower than 320 ° C.
[In general formula (I), W is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a halo-substituted alkylene group, a carbonyl group, a sulfonyl group, a carboxyl alkylene group, a carboxyl alkylidene group, an alkoxycarbonylalkylene group, Selected from the group consisting of alkoxycarbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, carbon number 3 Selected from the group consisting of ˜7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a C 1-20 aliphatic hydrocarbon group, a carbon number 1-20 alicyclic hydrocarbon groups, C1-C20 aromatic hydrocarbon groups, B group, selected from the group consisting of halogenated alkyl groups. ]
[In the general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms; R ¹¹ , R ¹² , R ¹³ , And R ¹⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon having 1 to 20 carbon atoms. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic group having 1 to 20 carbon atoms. It is chosen from the group which consists of a hydrocarbon group, a C1-C20 aromatic hydrocarbon group, and a halogenated alkyl group, and k is an integer of 2-12. ]
(2) The prepreg according to (1), wherein the reinforcing fibers constituting the reinforcing fiber cloth are glass fibers or carbon fibers.
(3) A plate-like molded body obtained by laminating the prepreg of (1) or (2).
(4) At least one selected from halogenated hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds and aromatic hydrocarbons not containing a halogen group as a solvent, and a solid content concentration of 10 mass at room temperature The method for producing a prepreg according to (1) or (2), wherein the polyarylate resin is dissolved so as to be at least% to obtain a varnish, and the varnish is impregnated or applied to a reinforcing fiber varnish and then dried.

  ADVANTAGE OF THE INVENTION According to this invention, it is a prepreg which impregnated or apply | coated the polyarylate resin to the reinforced fiber cloth, Comprising: The prepreg which is excellent in heat resistance and can be shape | molded in a short time is obtained.

  The polyarylate resin used in the present invention is composed of an aromatic dicarboxylic acid or a derivative thereof and a bisphenol or a derivative thereof, and an aromatic having a structure represented by the following general formulas (I) and (II) as a structural unit. It is a polyester polymer and is produced by methods such as solution polymerization, melt polymerization, and interfacial polymerization.

In general formula (I), W is a single bond, oxygen atom, sulfur atom, alkylene group, alkylidene group, halo-substituted alkylene group, carbonyl group, sulfonyl group, carboxyl alkylene group, carboxyl alkylidene group, alkoxycarbonylalkylene group, alkoxy. Carbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is selected from the group consisting of phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, 3 to 3 carbon atoms Selected from the group consisting of 7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alicyclic hydrocarbon group, C1-C20 aromatic hydrocarbon group, nitro And a group selected from the group consisting of halogenated alkyl groups.

Among these, W is preferably a single bond, a sulfur atom, an alkylene group or an alkylidene group in that it has good solubility and is excellent in the effect of improving heat resistance when used in combination with the following general formula (II). , Ar is preferably a phenylene group, and R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, It is especially preferable that it is 1-4 aliphatic hydrocarbon groups.

  Examples of the bisphenol component for introducing a bisphenol residue into the structure represented by the general formula (I) include 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 9,9-bis (4- Droxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, N-methyl-3,3-bis ( 4-hydroxyphenyl) phthalimidine and the like. These compounds may be used alone or in combination of two or more. Among the above, from the viewpoints of solubility and heat resistance, 2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (4-hydroxy-3-methylphenyl) propane (BPC), 2, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA) can be preferably used.

In general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, Selected from the group consisting of a nitro group and a halogenated alkyl group, and R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of a group, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and k is an integer of 2 to 12.

Among them, when used in combination with the following general formula (I), Ar is preferably a phenylene group from the viewpoint of having good solubility and a high effect of increasing the glass transition temperature. It is particularly preferred to use the acid in equimolar amounts. R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ are each independently preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ are preferably each independently a hydrogen atom or a methyl group, and k is preferably 5.

  Examples of the bisphenol component for introducing a bisphenol residue into the structure represented by the general formula (II) include 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxy-3). , 5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy-3) , 5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Examples thereof include 1-bis (4-hydroxyphenyl) -3,3,5-triethylcyclohexane. These compounds may be used alone or in combination of two or more. Among these, from the viewpoints of solubility and heat resistance, 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane can be preferably used.

  Examples of the aromatic dicarboxylic acid component for introducing an aromatic dicarboxylic acid residue into the structure represented by the general formulas (I) and (II) include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, , 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyl Dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4- Carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid, etc. It is. Among these, terephthalic acid and isophthalic acid are preferable, and it is particularly preferable to use a mixture of both from the viewpoint of solubility in a solvent. In that case, the mixing ratio is arbitrarily in the range of (terephthalic acid / isophthalic acid) = 100/0 to 0/100 (mol%), preferably 80/20 to 10/90 (mol%), more preferably If the range is 60/40 to 25/75 (mol%), the resulting polyarylate resin has excellent solubility.

  Moreover, you may use aliphatic dicarboxylic acids in the range which does not impair the characteristic and effect of this invention. The aliphatic dicarboxylic acids are not particularly limited, and examples thereof include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanedioic acid.

  As the polyarylate resin, aliphatic glycols and dihydroxybenzene may be used as long as the characteristics and effects of the present invention are not impaired. Aliphatic glycols are not particularly limited, but ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts thereof Examples of dihydroxybenzenes such as ethylene oxide adducts of bisphenol S, hydroquinone, resorcinol, and catechol.

In the polyarylate resin used in the present invention, the molar ratio of the structures represented by the general formulas (I) and (II) needs to satisfy the following formula.
0.10 ≦ {(I) / [(I) + (II)]} ≦ 0.90

  The molar ratio is more preferably 0.15 to 0.85, and further preferably 0.20 to 0.80. When the molar ratio is less than 0.10, the solubility of the polyarylate resin to be used in the organic solvent becomes insufficient, and the heat resistance of the polyarylate resin becomes inferior. When the molar ratio exceeds 0.90, the heat resistance is sufficient, but the solubility in an organic solvent is insufficient.

  The polyarylate resin used in the present invention is a resin solution having a concentration of 1 g / dl dissolved in a 60/40 (mass ratio) mixture of phenol / 1,1,2,2-tetrachloroethane at a temperature of 25 ° C. The inherent viscosity in is preferably 0.40 to 1.20 dl / g, and more preferably 0.45 to 1.00 dl / g. Inherent viscosity is an index of molecular weight, but in the present invention, if the inherent viscosity of the polyarylate resin used is less than 0.40 dl / g, the mechanical properties of the prepreg obtained are inferior. If the inherent viscosity exceeds 1.20 dl / g, the viscosity of the varnish increases when the polyarylate resin to be used is dissolved in an organic solvent, and the impregnation property and coating property are deteriorated.

  In order to keep the inherent viscosity of the polyarylate resin, that is, the molecular weight within a predetermined range, the method of adjusting the molecular weight by controlling the reaction rate by adjusting the polymerization time, the blending of monomer of aromatic dicarboxylic acid component or dihydric phenol component A method of adjusting the molecular weight by polymerizing with a slight excess of any of the components, alcohols or phenols having only one reactive functional group in the molecule, or end-capping agents with carboxylic acids And a method of adjusting the molecular weight by adding together with the monomer. Among these, the method of adding a terminal blocking agent is preferable because the molecular weight can be easily controlled.

  Examples of the end-capping agent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, phenol, cresol and the like. , 2,6-xylenol, 2,4-xylenol, p-tert-butylphenol, cumylphenol and other phenols, benzoic acid, methylbenzoic acid, naphthoic acid, acetic acid, propionic acid, butyric acid, oleic acid, stearic acid And the like, or derivatives thereof.

  The polyarylate resin used in the present invention has a glass transition temperature of 200 ° C. or higher and lower than 320 ° C., preferably 210 ° C. or higher and lower than 310 ° C., more preferably 220 ° C. or higher and lower than 300 ° C., more preferably 230 ° C. or higher. More preferably, it is less than 290 degreeC. By setting the glass transition temperature within a predetermined range, a prepreg having heat resistance and excellent adhesiveness can be obtained. When the glass transition temperature is less than 200 ° C., the obtained prepreg is inferior in heat resistance, and when the glass transition temperature is 320 ° C. or more, the adhesiveness when the prepreg is laminated is inferior.

  To the polyarylate resin used in the present invention, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a thioether-based antioxidant, a phosphorus-based antioxidant, or the like may be added as long as the characteristics are not impaired. .

  The polyarylate resin used in the present invention can be used as a varnish by dissolving in an organic solvent. The solid content concentration at the time of dissolution can be arbitrarily determined.

  In the present invention, the polyarylate resin used has a molar ratio of the structures represented by the general formulas (I) and (II) of 0.10 ≦ {(I) / [(I) + (II)]} ≦ 0. By polymerizing to 90 to obtain a polyarylate resin, the solubility in an organic solvent is particularly excellent. Such polyarylate resins can be suitably dissolved in organic solvents such as halogenated hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds and aromatic hydrocarbons, and the resulting varnish This also improves the stability.

  The judgment of the superiority or inferiority of the solubility of the polyarylate resin used as the varnish in the organic solvent can be confirmed, for example, by whether or not it is completely dissolved at a solid content concentration of 10% by mass or more at room temperature. In general, depending on the structural unit, the polyarylate resin can be dissolved only in a specific organic solvent, has low solubility in the solvent, or dissolves, but dissolves in a few days, sometimes in several hours after the dissolution. There is a problem that the nature is bad. In the present invention, even when any of the organic solvents listed above is used, it is determined that a solvent that dissolves only at a solid content concentration lower than 10% by mass or gels during dissolution does not have solubility. do. In addition, when such a polyarylate resin is used, it is difficult to use it as a varnish because the impregnation property and coating property of the reinforcing fiber cloth are reduced.

  In the present invention, the method for producing the varnish is not particularly limited, but in a state where the varnish is maintained at a constant temperature, a predetermined amount of an organic solvent and a polyarylate resin are placed in a container to form a mixed solution, and the mixed solution is stirred with a stirrer, or For example, the container may be sealed and shaken. The time required from the start of dissolution until the entire amount is dissolved is affected not only by the solubility of the polyarylate resin but also by the dissolution method, but preferably the conditions allow the entire amount to be dissolved within 24 hours, more preferably within 5 hours. Is preferable from the viewpoint of workability. During the dissolution, the state of the mixed solution is observed in a timely manner, and if any insoluble matter (precipitation), turbidity, and gelation are not observed, it can be confirmed that the solution is completely dissolved. At this time, depending on the size and fine structure of the polyarylate resin particles, it may take time to dissolve. In such a case, after pulverizing the polyarylate resin particles to a size of 100 μm or less, It is possible to improve workability by dissolving.

  The organic solvent used for the dissolution is at least one organic solvent selected from halogenated hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds, and aromatic hydrocarbons. The organic solvent to be used is not particularly limited as long as the polyarylate resin can be dissolved into a varnish, and is preferably selected according to the process suitability for using the varnish.

  Specific examples of the halogenated hydrocarbon include, for example, dichloromethane, chloroform, chloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, dibromomethane, tribromomethane, Examples include bromoethane, 1,2-dibromoethane, 1-bromopropane and the like.

  Specific examples of the halogenated aromatic hydrocarbon include chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and the like.

  Specific examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

  Specific examples of the ether compound include 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like.

  Specific examples of the ketone compound include cyclopentanone and cyclohexanone.

  Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.

The polyarylate resin used in the present invention can be made into a varnish by dissolving in the organic solvent. In addition, when setting it as a varnish, in order to provide desired performance, you may melt | dissolve resin other than polyarylate resin within the range of the performance required by this invention. Examples of other resins include polycarbonate, polystyrene, polyester, acrylic resin, polyphenylene ether, polysulfone, polyethersulfone, and polyetherimide. Various additives such as an antioxidant, a flame retardant, an ultraviolet absorber, a fluidity modifier, and a fine particle inorganic filler may be mixed and used.

  The solid content concentration of the varnish obtained in the present invention is preferably 1 to 40% by mass, and more preferably 5 to 35% by mass. When the solid content concentration is less than 1% by mass, voids are generated between the reinforcing fibers of the obtained prepreg when impregnating or applying the varnish to the reinforcing fiber cloth and drying, not only deteriorating the appearance as a prepreg but also laminating. Adhesiveness at the time is greatly reduced, and the performance as a prepreg is greatly reduced. When the solid content exceeds 40% by mass, when the varnish is impregnated into the reinforcing fiber cloth, the varnish does not penetrate into the gaps between the fibers of the reinforcing fiber, and the impregnation becomes insufficient, or a portion that is not covered after the application occurs. Then it becomes a problem. The application means a state in which one side or both sides of the reinforcing fiber cloth are completely covered with a coating film made of varnish even if the impregnation is not completed.

  In the present invention, a prepreg is obtained by impregnating or applying a varnish to a reinforcing fiber cloth and then drying. In the prepreg obtained by this method, the solid content impregnated or applied is preferably 20 to 90% by mass, and more preferably 30 to 80% by mass. When the solid content is less than 20% by mass, it is difficult to obtain a prepreg with few pores. When the solid content exceeds 90% by weight, when laminating, the outflow of the solid content increases between the deformed or laminated prepregs, which makes it difficult to handle.

  Examples of the reinforcing fiber constituting the reinforcing fiber cloth include glass fiber, carbon fiber, organic fiber, ceramic fiber, and the like. Any form such as a woven fabric and a non-woven fabric can be used. Moreover, you may use the synthetic paper which mixed paper-made these fibers in the state of the short fiber using fibrid. Among these, glass fiber and carbon fiber are particularly preferable in terms of excellent workability and adhesiveness as a prepreg to be obtained. The thickness of the reinforcing fiber cloth is preferably 5 to 50 μm, more preferably 10 to 45 μm, and still more preferably 15 to 40 μm.

  The method for impregnating the reinforcing fiber cloth with varnish is not particularly limited, and a known method can be used. As the impregnation method, for example, a method using a commercially available or self-made continuous impregnation apparatus, a method of immersing reinforcing fibers in a varnish made of polyarylate resin, a reinforcing paper is spread on a plate such as a release paper, a glass plate, a stainless plate, Examples thereof include a method of coating a varnish composed of a polyarylate resin, and it is obtained by evaporating and drying an organic solvent from an impregnated varnish. By adopting such a method, it is possible to perform molding processing in a shorter time than when a conventional thermosetting resin such as epoxy is used, and the obtained prepreg has excellent heat resistance. It will be a thing.

  The method for applying the varnish to the reinforcing fiber cloth is not particularly limited, and a known method can be used. As the coating method, for example, coating can be performed using a commercially available coating machine. When performing double-sided coating, after single-sided coating, once dried and then coated again on the opposite side, after single-sided coating and then coated on the opposite side without drying, both sides simultaneously The method of coating is mentioned. These coating methods can be appropriately selected in consideration of workability and performance of the obtained prepreg. The prepreg can be obtained by evaporating and drying an organic solvent from the coated varnish after the coating.

  The thickness of the prepreg varies depending on the thickness of the reinforcing fiber cloth used, but is preferably 10 to 150 μm, more preferably 20 to 140 μm, and further preferably 30 to 130 μm. The prepreg can be obtained by impregnating or coating the reinforcing fiber cloth with varnish, and then drying. However, although it depends on the amount of solids contained in the prepreg, the thickness of the reinforcing fiber cloth used is approximately three times the thickness. Further, by obtaining a prepreg, a prepreg having excellent heat resistance, mechanical properties, adhesiveness and appearance can be obtained.

  The prepreg obtained as described above can be used as it is without being subjected to heat treatment for curing. In addition, since the polyarylate resin contained in the prepreg melts and exhibits fluidity when heated above its glass transition temperature, the prepreg can be laminated as it is or by laminating the prepreg as it is and forming a laminate. it can. Since the laminate is excellent in adhesion between prepregs, the mechanical strength is sufficiently improved and the heat resistance is also excellent. Moreover, such a laminated body can be used as a high-strength plate-like molded body. Furthermore, this plate-shaped molded body can be molded into a desired shape. The moldability varies depending on the material of the reinforcing fiber cloth to be used and the amount of the solid content containing the prepreg, but can be formed according to a predetermined mold. Punching or the like may be performed as long as the mechanical properties are not significantly impaired. Since the prepreg of the present invention does not use a thermosetting resin, it is particularly excellent in workability such as adhesion, moldability, and punchability. The forming and punching can be performed by cold working, but can be performed under heating as necessary.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

1. Evaluation method (1) Inherent viscosity (ηinh)
Relative viscosity (ηrel) was measured under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C. using a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 60/40 as a solvent. From the obtained relative viscosity, the inherent viscosity was calculated from the following formula.
ηinh (dl / g) = Ln (ηrel) / c (c: concentration)

(2) Glass transition temperature Using a differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer), the glass was heated from 30 ° C. to 400 ° C. at a heating rate of 10 ° C./min. The onset temperature of the discontinuous change derived from the transition temperature was defined as the glass transition temperature.

(3) Solubility Seal a total of 30 g of resin and organic solvent weighed to a prescribed concentration in a glass screw cap bottle with an internal volume of 50 ml, and use a mix rotor at a room temperature of 23 ° C. and a screw cap bottle at 70 rpm. Rotated. Rotation was stopped 24 hours after the start of rotation. Thereafter, the resin solution in the screw cap bottle was visually observed, and the solubility was evaluated according to the following criteria. As organic solvents, chloroform, chlorobenzene, N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 1,3-dioxolane, cyclohexanone and toluene are used so as to have respective concentrations of 10, 20, and 30% by mass. A resin solution was prepared.
◯: Completely dissolved and transparent.
Δ: Cloudy.
X: There was insoluble matter.

(4) Solution stability For each resin solution whose solubility was evaluated in (3), the screw cap bottle whose rotation was stopped was allowed to stand at room temperature of 23 ° C. for 48 hours. Thereafter, the resin solution in the screw cap bottle was visually observed, and the solution stability was evaluated according to the following criteria.
○: Transparency was maintained and the viscosity was not increased. Δ: Cloudy and slightly thickened. However, it had fluidity.
X: Gelled. There was no fluidity.

(5) Fibrous reinforcement content rate It measured based on JISK7052 or JISK7075.

(6) Interlayer adhesion The prepreg was laminated by hot pressing under the conditions of temperature, pressure and time. The obtained plate-shaped molded body was broken by applying a bending stress, and the fracture surface was observed. If delamination was observed on the fracture surface, it was judged as “x”, and if not, it was judged as “◯”.

Example 1
In a reaction vessel having an internal volume of 100 L equipped with a water cooling jacket and a stirrer, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA) 3 0.000 mol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter BPTMC) 3.00 mol and p-tertbutylphenol (hereinafter PTBP) 0.30 mol were dissolved. In a separate container, 3.08 mol of terephthalic acid dichloride (hereinafter TPC) and 3.08 mol of isophthalic acid dichloride (hereinafter IPC) were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped.
After standing separation, the aqueous phase was extracted, and 20 g of acetic acid was added to the remaining dichloromethane phase. Thereafter, 30 L of ion-exchanged water was added, stirred for 20 minutes, and allowed to stand again to extract the aqueous phase. This washing operation was repeated until the aqueous phase became neutral, and then the dichloromethane phase was poured into 50 ° C. warm water in a container equipped with a homomixer to evaporate the methylene chloride to obtain a powdered polyarylate. .

  The powdery polyarylate was dehydrated and then dried at 130 ° C. under reduced pressure for 24 hours using a vacuum dryer to obtain a polyarylate resin. The inherent viscosity of this resin was 0.52 dl / g, no crystallization and melting peak was observed by DSC measurement, and the glass transition temperature was 225 ° C.

  Each resin solution in which the obtained polyarylate resin was dissolved was evaluated for solubility and solution stability. As a result, all the resin solutions had good solubility and solution stability.

On the other hand, the obtained polyarylate resin was dissolved in chloroform to prepare a varnish having a resin concentration of 20% by mass. The obtained varnish was impregnated into a plain weave E glass woven fabric having a thickness of 24 μm and a basis weight of 27 g / m ² (E03E-SK manufactured by Unitika Glass Fiber Co., Ltd.), dried at 150 ° C., and a glass fiber content of 52 mass%. Prepreg was obtained.

  Ten prepregs obtained were overlapped, sandwiched between aluminum plates coated with a release agent on the surface, and pressed at 340 ° C. and a pressure of 10 MPa for 3 minutes. It was taken out in a state of being overlapped with the aluminum plate, pressed with a water-cooled press, and cooled for 1 minute. After cooling sufficiently, the aluminum plate was peeled off to obtain a single plate-like molded body. When the cross-section of the obtained plate-like molded body, which was broken by applying a bending stress, was observed, no release surface derived from delamination was observed. The evaluation results are shown in Table 1.

Examples 2-5, 6-7
A polyarylate resin was synthesized and evaluated in the same manner as in Example 1 except that the blending ratios of BPA, BPTMC, PTBP, TPC, and IPC were changed to those shown in Tables 2 and 3. The evaluation results are shown in Tables 1 and 2.

Example 8
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 3.00 mol of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter BPC), BPTMC 3.00 mol and PTBP 0.30 mol were dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1. The obtained resin was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 9
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion-exchanged water, then 3.00 mol of BPA, 3.00 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ), And PTBP 0.30 mol was melt | dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1. The obtained resin was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 10
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 3.00 mol of BPA, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter referred to as DMBPC). 3.00 mol and PTBP 0.30 mol were dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1. The obtained resin was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 11
The polyarylate resin obtained in Example 1 was dissolved in chloroform to prepare a varnish having a resin concentration of 20% by mass. The obtained varnish was impregnated into a plain woven carbon fiber woven fabric (TR1120M manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 150 μm and a basis weight of 120 g / m ² , dried at 150 ° C., and a prepreg having a carbon fiber content of 37% by mass was obtained. Obtained.
Three of the obtained prepregs were overlapped, sandwiched between aluminum plates coated with a release agent on the surface, and pressed at 340 ° C. and a pressure of 10 MPa for 3 minutes. It took out in the state which overlapped with the aluminum plate, and it pressed with the water-cooled press, and cooled for 1 minute. After cooling sufficiently, the aluminum plate was peeled off to obtain a single plate-like molded body. When the cross-section of the obtained plate-like molded body, which was broken by applying a bending stress, was observed, no release surface derived from delamination was observed. The evaluation results are shown in Table 2.

Comparative Examples 1-4
A polyarylate resin was synthesized in the same manner as in Example 1 except that the blending ratio of BPA, BPC, BPTMC, BPZ, PTBP, TPC, and IPC was changed to that shown in Table 3, and the inherent viscosity and glass transition temperature. Was measured. In addition, the solubility and solution stability were evaluated in the same manner as in Example 1. These were less soluble in organic solvents than the examples. The evaluation results are shown in Table 3.

Comparative Example 5
A polyarylate resin was synthesized and evaluated in the same manner as in Example 1 except that the blending ratio of BPC, BPZ, PTBP, TPC, and IPC was changed to that shown in Table 3. The obtained polyarylate resin had good solubility and interlayer adhesion at the time of lamination, but the glass transition temperature was low, and the obtained molded product had low heat resistance. The evaluation results are shown in Table 3.

Comparative Example 6
In place of the polyarylate resin, the inherent viscosity and glass transition temperature of the polycarbonate resin (Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics) were measured, and the solubility and solution stability were evaluated in the same manner as in Example 1. . The polycarbonate resin was inferior in solubility to the polyarylate resin obtained in the examples.
A polycarbonate resin was dissolved in chloroform to prepare a varnish having a resin concentration of 10% by mass. The obtained varnish was impregnated into a plain weave E glass woven fabric (E03E-SK manufactured by Unitika Glass Fiber Co., Ltd.) having a thickness of 24 μm and a basis weight of 27 g / m ² and dried at 120 ° C. to obtain a prepreg.
In the obtained prepreg, many pores not partially filled with the matrix were observed. Ten prepregs obtained were overlapped and pressed at 340 ° C. and 10 MPa for 3 minutes. When the section obtained by applying a bending stress to the obtained plate-like compact and rupturing it was observed, a part of the delamination surface was observed. The evaluation results are shown in Table 4.

Comparative Example 7
Bisphenol A diglycidyl ether (Mitsubishi Chemical Co., Ltd. jER828) 2000 g, 4,4′-diaminodiphenylmethane (Tokyo Kasei Co., Ltd., reagent) 525 g, toluene 316 g, 2-butanone 316 g were put in an autoclave equipped with a stirrer, under a nitrogen atmosphere. B stage epoxy resin mixture was obtained by mixing at 80 ° C. for 30 minutes. The resulting epoxy resin mixture was discharged from the autoclave, impregnated into a plain weave E glass woven fabric having a thickness of 24 μm and a basis weight of 27 g / m ² (E03E-SK manufactured by Unitika Glass Fiber Co., Ltd.), then gradually warmed from room temperature, A B-stage prepreg having a glass fiber content of 50% by mass was obtained by drying at 80 ° C. for 2 hours and reacting while distilling off toluene and 2-butanone.
10 sheets of the obtained prepregs were overlapped and pressed under conditions of 150 ° C. and 10 MPa, and the state was maintained for 3 hours to obtain one sheet-like molded body. When the cross-section of the obtained plate-like molded body, which was broken by applying a bending stress, was observed, no release surface derived from delamination was observed.

Comparative Example 8
The B-stage prepreg obtained in Comparative Example 7 was overlapped with 10 sheets and pressed at 150 ° C. and 10 MPa for 3 minutes to obtain one sheet-like molded body. The obtained plate-like molded body was an integrated laminate, but since it was not completely cured, only a flexible and sticky surface was obtained.

Comparative Example 9
The B-stage prepreg obtained in Comparative Example 7 was overlapped with 10 sheets and pressed at 340 ° C. and 10 MPa for 3 minutes to obtain one sheet-like molded body. Although the obtained plate-like molded body was an integrated laminate, only a flexible one was obtained.

  The polyarylate resins obtained in Examples 1 to 11 had a glass transition temperature of 200 ° C. or higher and excellent heat resistance. Moreover, the solubility with respect to various organic solvents and the solution stability were excellent. A prepreg using a varnish in which such a polyarylate resin is dissolved in an organic solvent can be laminated even in a short time, and can be made into a plate-like molded article having improved interlayer adhesion.

  In Comparative Examples 1 to 4, since the polyarylate resin having a predetermined structure was not used, the polyarylate resin was dissolved in a specific organic solvent only at a relatively low concentration, and the solution stability was inferior. Therefore, no prepreg was produced.

  In Comparative Example 5, since the predetermined polyarylate resin was not used, the glass transition temperature was less than 200 ° C., and the heat resistance as a prepreg was insufficient.

  In Comparative Example 6, since a polycarbonate resin was used instead of the polyarylate resin, it was dissolved in a specific organic solvent only at a relatively low concentration, and the solution stability was poor. Even when a varnish obtained by dissolving the polyarylate resin in an organic solvent was used, only a prepreg having poor interlayer adhesion was obtained because the resin concentration was low.

  In Comparative Examples 7 to 9, since the epoxy resin, which is a thermosetting resin, was used instead of the polyarylate resin, the molding time required for the laminating process using the prepreg was increased, and the obtained plate-shaped molded body was flexible. And inferior in rigidity.

Claims (4)

The reinforcing fiber cloth includes a structure represented by the following general formulas (I) and (II), and the molar ratio is 0.10 ≦ {(I) / [(I) + (II)]} ≦ 0.90 A prepreg obtained by impregnating or coating a polyarylate resin in a range , wherein the glass transition temperature of the polyarylate resin is 200 ° C. or higher and lower than 320 ° C.
[In general formula (I), W is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a halo-substituted alkylene group, a carbonyl group, a sulfonyl group, a carboxyl alkylene group, a carboxyl alkylidene group, an alkoxycarbonylalkylene group, Selected from the group consisting of alkoxycarbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, carbon number 3 Selected from the group consisting of ˜7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a C 1-20 aliphatic hydrocarbon group, a carbon number 1-20 alicyclic hydrocarbon groups, C1-C20 aromatic hydrocarbon groups, B group, selected from the group consisting of halogenated alkyl groups. ]
[In the general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms; R ¹¹ , R ¹² , R ¹³ , And R ¹⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon having 1 to 20 carbon atoms. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic group having 1 to 20 carbon atoms. It is chosen from the group which consists of a hydrocarbon group, a C1-C20 aromatic hydrocarbon group, and a halogenated alkyl group, and k is an integer of 2-12. ] The prepreg according to claim 1, wherein the reinforcing fibers constituting the reinforcing fiber cloth are glass fibers or carbon fibers. A plate-like molded body obtained by laminating the prepreg according to claim 1 or 2. Using at least one selected from halogenated hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds, and aromatic hydrocarbons not containing a halogen group as a solvent, a solid content concentration of 10% by mass or more at room temperature The method for producing a prepreg according to claim 1 or 2, wherein the polyarylate resin is dissolved to obtain a varnish, the varnish is impregnated or coated on a reinforcing fiber varnish, and then dried.