阅读说明：本技术 纤维增强树脂基材 (Fiber-reinforced resin base material ) 是由 大内山直也 越政之 成濑惠宽 于 2020-03-17 设计创作，主要内容包括：本发明的课题为提供含浸性和热稳定性优异、具有空隙少的表面品质、并且高耐热性的纤维增强树脂基材。本发明的解决手段为一种纤维增强树脂基材,其为使聚苯硫醚树脂组合物含浸于连续的增强纤维中、或者含浸于分散有不连续的纤维的增强纤维基材中而成的纤维增强树脂基材,所述纤维增强树脂基材的由DMA法(弯曲模式)测定的玻璃化转变温度显示为115℃以上。(The present invention addresses the problem of providing a fiber-reinforced resin base material that has excellent impregnation properties and thermal stability, has a surface quality with few voids, and has high heat resistance. The solution of the present invention is a fiber-reinforced resin base material in which a polyphenylene sulfide resin composition is impregnated into continuous reinforcing fibers or into a reinforcing fiber base material in which discontinuous fibers are dispersed, wherein the glass transition temperature of the fiber-reinforced resin base material as measured by a DMA method (bending mode) is 115 ℃ or higher.)

1. A fiber-reinforced resin base material in which a polyphenylene sulfide resin composition is impregnated into continuous reinforcing fibers or into a reinforcing fiber base material in which discontinuous reinforcing fibers are dispersed, wherein the glass transition temperature of the fiber-reinforced resin base material as measured by a DMA method (bending mode) is 115 ℃ or higher.

2. The fiber reinforced resin substrate according to claim 1, wherein the formed sheet has a bending strain (measured at 110 ℃ using an Instron 5565 tensile tester with a thermostatic bath) of 1.1% or more according to ASTM D790.

3. The fiber-reinforced resin substrate according to claim 1 or 2, wherein the polyphenylene sulfide resin composition has a melt viscosity (at an orifice length of 5mm, an orifice diameter of 0.5mm, a temperature of 320 ℃ C., and a shear rate of 9,728 sec)^-1Measured under the conditions of (1) is 120 pas or less.

4. The fiber-reinforced resin substrate according to any one of claims 1 to 3, wherein the polyphenylene sulfide resin composition is a polyphenylene sulfide resin composition comprising (A) a polyphenylene sulfide resin and (B) a thermoplastic resin having a glass transition temperature of 100 ℃ or higher.

5. The fiber-reinforced resin substrate according to claim 4, wherein the polyphenylene sulfide resin (A) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher are contained in an amount of 99 to 60% by weight and 1 to 40% by weight, with the total amount of the polyphenylene sulfide resin (A) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher being 100% by weight, wherein the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher forms an island phase, and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher has a number-average particle diameter of 10 μm or less.

6. The fiber-reinforced resin substrate according to claim 5, wherein the number average particle diameter of the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher, which forms the island phase, is smaller than the distance z between the reinforcing fibers represented by the following formula,

z＝y-2r

z: distance between reinforcing fibers, y: distance between centers of reinforcing fibers, r: the radius of the fiber.

7. The fiber-reinforced resin substrate according to any one of claims 4 to 6, wherein the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher is at least 1 amorphous resin selected from the group consisting of polyetherimide resins, polyethersulfone resins, polyphenylsulfones, polysulfone resins, and polyphenylene ether resins.

8. The fiber-reinforced resin substrate according to any one of claims 4 to 7, wherein the polyphenylene sulfide resin composition further comprises (C) 0.1 to 10 parts by weight of a compound having 1 or more groups selected from epoxy groups, amino groups and isocyanate groups, based on 100 parts by weight of the total of the polyphenylene sulfide resin (A) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher.

Technical Field

The present invention relates to a fiber-reinforced resin base material.

Background

A fiber-reinforced resin base material in which a thermoplastic resin is impregnated into continuous reinforcing fibers or into a reinforcing fiber base material in which discontinuous reinforcing fibers are dispersed is excellent in not only light weight effect but also toughness, welding processability, and recycling property as compared with a fiber-reinforced resin base material using a thermosetting resin, and thus has been widely used in various applications such as transportation equipment for aircrafts, automobiles, and the like, and sports, electric, and electronic components. In recent years, in addition to mechanical strength and weight reduction, which have been added as added values of conventional CFRTP (carbon fiber reinforced thermoplastic resin) intermediate substrates, high added values such as high heat resistance, low water absorption, high toughness, and moldability have been required, and the development of a high-functional CFRTP intermediate substrate has been strongly required mainly for aircraft and automobile applications.

For example, as a structural composite material having excellent mechanical strength, heat resistance, and molding processability, carbon fiber-reinforced thermoplastic resin prepregs described in the following patent documents 1 to 3 are known.

Patent document 1 discloses a carbon fiber-reinforced resin composition in which a carbon fiber is impregnated with a mixture of a copolymer of polyphenylene sulfide (hereinafter, abbreviated to PPS) and polyphenylene sulfide sulfone (hereinafter, abbreviated to PPSs), and at least 1 of PPS and PPSs.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 63-125531

Disclosure of Invention

Problems to be solved by the invention

However, the technique described in patent document 1 has a problem that polyphenylene sulfide sulfone is excellent in heat resistance, but has poor melt retention stability and is a low-toughness polymer, because it has: impregnation failure into the carbon fibers occurs, and the mechanical strength is greatly reduced. Further, there is no description about the glass transition temperature measured by DMA method of the fiber reinforced resin substrate obtained by impregnating the carbon fiber bundles with the PPS resin composition of the present application, which is 115 ℃ or higher, and which can greatly improve the heat resistance and mechanical strength.

Accordingly, an object of the present invention is to provide a fiber-reinforced resin base material having excellent impregnation properties and thermal stability, surface quality with few voids, and high heat resistance.

Means for solving the problems

In order to solve the above problems, the fiber-reinforced resin base material of the present invention is a fiber-reinforced resin base material having a structure comprising,

the fiber-reinforced resin substrate is obtained by impregnating a polyphenylene sulfide resin composition into continuous reinforcing fibers or into a reinforcing fiber substrate in which discontinuous reinforcing fibers are dispersed, and the glass transition temperature of the fiber-reinforced resin substrate measured by a DMA method (bending mode) is 115 ℃ or higher.

The fiber-reinforced resin substrate of the present invention preferably has a flexural strain (measured at 110 ℃ using an Instron 5565 tensile testing machine with a thermostatic bath) of 1.1% or more in a molded sheet according to ASTM D790.

In the fiber-reinforced resin base material of the present invention, it is preferable that the polyphenylene sulfide resin composition has a melt viscosity (orifice diameter) of 5mm, an orifice diameter of 0.5mm, a temperature of 320 ℃ and a shear rate of 9,728sec^-1) Is 120 pas or less.

In the fiber-reinforced resin substrate of the present invention, the polyphenylene sulfide resin composition is preferably a polyphenylene sulfide resin composition containing (a) a polyphenylene sulfide resin and (B) a thermoplastic resin having a glass transition temperature of 100 ℃.

The fiber-reinforced resin base material of the present invention preferably comprises, assuming that the total of the polyphenylene sulfide resin (a) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher is 100% by weight, 99 to 60% by weight of the polyphenylene sulfide resin (a) and 1 to 40% by weight of the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher, wherein the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher forms an island phase, and the number-average particle diameter of the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher is 10 μm or less.

In the fiber-reinforced resin substrate of the present invention, the number average particle diameter of the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher, which forms the island phase, is preferably smaller than the distance z between the reinforcing fibers represented by the following formula.

z＝y-2r

(z: distance between reinforcing fibers, y: distance between centers of reinforcing fibers, r: fiber radius)

In the fiber-reinforced resin substrate of the present invention, the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher is preferably at least 1 amorphous resin selected from the group consisting of polyetherimide resins, polyethersulfone resins, polyphenylsulfones, polysulfone resins, and polyphenylene ether resins.

In the fiber-reinforced resin substrate of the present invention, it is preferable that the polyphenylene sulfide resin composition further contains 0.1 to 10 parts by weight of (C) a compound having 1 or more groups selected from an epoxy group, an amino group and an isocyanate group, based on 100 parts by weight of the total of the polyphenylene sulfide resin (a) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a fiber-reinforced resin base material having excellent impregnation properties, excellent thermal stability, few voids, improved surface quality, and high heat resistance can be obtained.

Drawings

FIG. 1 is a graph showing a dynamic viscoelasticity measurement chart in example 1 and comparative example 5.

FIG. 2 is a graph showing the relationship between the measurement temperature and the bending strain in example 1 and comparative example 5.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The fiber-reinforced resin base material according to the embodiment of the present invention has any of the following 2 forms. The first embodiment is a fiber-reinforced resin base material in which a polyphenylene sulfide resin composition described later is impregnated into continuous reinforcing fibers, and the second embodiment is a fiber-reinforced resin base material in which a polyphenylene sulfide resin composition described later is impregnated into a reinforcing fiber base material in which discontinuous reinforcing fibers are dispersed.

In an embodiment of the present invention, the continuous reinforcing fiber in the first aspect is: the reinforcing fibers are free of interrupted reinforcing fibers in the fiber reinforced resin matrix. Examples of the form and arrangement of the reinforcing fibers in the embodiment of the present invention include reinforcing fibers arranged in a single direction, woven fabrics (cloths), knitted fabrics, braids, tows, and the like. Among these, reinforcing fibers are preferably arranged in a single direction from the viewpoint of efficiently improving mechanical properties in a specific direction.

The reinforcing fiber base material in which the discontinuous reinforcing fibers are dispersed in the second form means: a mat-shaped reinforcing fiber base material obtained by cutting and dispersing the reinforcing fibers in a fiber-reinforced resin base material. The reinforcing fiber base material in the embodiment of the present invention can be obtained by any method such as a wet method of producing a sheet after dispersing reinforcing fibers in a solution, and a dry method using a carding device or an air-laid device. From the viewpoint of productivity, a dry method using a carding device or an air-laid device is preferred.

In the second embodiment of the present invention, the number average fiber length of the discontinuous reinforcing fibers dispersed in the reinforcing fiber base material is preferably 3 to 100 mm. When the number average fiber length of the discontinuous reinforcing fibers is 3mm or more, the reinforcing effect by the discontinuous reinforcing fibers can be sufficiently exhibited, and the mechanical strength of the obtained fiber-reinforced resin base material can be further improved. Preferably 5mm or more. On the other hand, when the number average fiber length of the discontinuous reinforcing fibers is 100mm or less, the flowability at the time of molding can be further improved. The number average fiber length of the discontinuous reinforcing fibers is more preferably 50mm or less, and still more preferably 30mm or less.

In the second embodiment of the present invention, the number average fiber length of the discontinuous reinforcing fibers can be determined by the following method. First, a sample of 100mm × 100mm was cut out from a fiber-reinforced resin base material, and the cut sample was heated in an electric furnace at 600 ℃ for 1.5 hours to burn out the matrix resin. From the thus-obtained fiber-reinforced resin base material, 400 discontinuous reinforcing fiber bundles were randomly collected. The fiber length of the extracted discontinuous reinforcing fiber bundle was measured by 1mm unit using a vernier caliper, and the number average fiber length (Ln) was calculated by the following equation.

Ln＝ΣLi/400

(Li: measured fiber length (i ═ 1,2, 3,. cndot. 400) (unit: mm)).

The number average fiber length of the discontinuous reinforcing fibers can be adjusted to the above range by cutting the reinforcing fibers to a desired length at the time of manufacturing the reinforcing fiber base material. The orientation of the discontinuous reinforcing fiber mat is not particularly limited, but is preferably isotropically dispersed from the viewpoint of moldability.

The type of the reinforcing fiber in the first and second embodiments is not particularly limited, and carbon fiber, metal fiber, organic fiber, and inorganic fiber can be exemplified. More than 2 of them may be used.

Examples of the carbon fibers include PAN-based carbon fibers using Polyacrylonitrile (PAN) fibers as a raw material, pitch-based carbon fibers using petroleum tar or petroleum pitch as a raw material, cellulose-based carbon fibers using viscose rayon (viscose rayon) or cellulose acetate as a raw material, vapor deposition-based carbon fibers using hydrocarbons or the like as a raw material, and graphitized fibers thereof. Among these carbon fibers, PAN-based carbon fibers are preferably used in view of excellent balance between strength and elastic modulus.

Examples of the metal fibers include fibers made of metal such as iron, gold, silver, copper, aluminum, brass, and stainless steel.

Examples of the organic fiber include fibers made of organic materials such as aromatic polyamide, Polybenzoxazole (PBO), polyphenylene sulfide, polyester, polyamide, and polyethylene. Examples of the aramid fiber include a para-aramid fiber having excellent strength and elastic modulus, and a meta-aramid fiber having excellent flame retardancy and long-term heat resistance. Examples of the para-aramid fiber include polyparaphenylene terephthalamide fiber and copoly-p-phenylene-3, 4' -oxydiphenylene terephthalamide fiber, and examples of the meta-aramid fiber include polyisom-phenylene isophthalamide fiber. The aramid fiber is preferably a para-aramid fiber having a higher elastic modulus than a meta-aramid fiber.

Examples of the inorganic fibers include fibers made of inorganic materials such as glass, basalt, silicon carbide, and silicon nitride. Examples of the glass fibers include E glass fibers (for electric use), C glass fibers (for corrosion resistance), S glass fibers, T glass fibers (high strength, high elastic modulus), and the like. Basalt fibers are obtained by converting mineral basalt into fibers, and are fibers having very high heat resistance. Basalt generally contains FeO or FeO as a compound of iron₂9-25 wt% of TiO or TiO as a titanium compound₂1 to 6% by weight, but the amount of these components may be increased in a molten state to form fibers.

The fiber-reinforced resin base material in the first and second aspects of the present invention is expected to function as a reinforcing material in many cases, and therefore is expected to exhibit high mechanical properties, and in order to exhibit high mechanical properties, it is preferable that the reinforcing fibers contain carbon fibers.

In the fiber-reinforced resin base material according to the first and second aspects of the present invention, the reinforcing fibers are generally formed by arranging 1 or more reinforcing fiber bundles (which are obtained by bundling a plurality of single fibers). The total number of filaments (the number of single fibers) of the reinforcing fibers in the case of arranging 1 or more reinforcing fiber bundles is preferably 1,000 to 2,000,000.

From the viewpoint of productivity, the total number of filaments of the reinforcing fiber is more preferably 1,000 to 1,000,000, still more preferably 1,000 to 600,000, and particularly preferably 1,000 to 300,000. The upper limit of the total number of filaments of the reinforcing fiber is preferably good enough to ensure productivity and dispersibility and workability in consideration of balance with dispersibility and workability.

In the first and second aspects of the present invention, 1 reinforcing fiber bundle is preferably formed by bundling 1,000 to 50,000 single fibers of reinforcing fibers having an average diameter of 5 to 10 μm.

The fiber-reinforced resin base material according to the first aspect of the present invention is characterized in that the thermoplastic resin impregnated into the continuous reinforcing fibers is a polyphenylene sulfide resin composition described later. In the fiber-reinforced resin base material according to the second aspect of the present invention, the thermoplastic resin impregnated into the reinforcing fiber base material in which the reinforcing fibers of the discontinuous fibers are dispersed is a polyphenylene sulfide resin composition described later.

The glass transition temperature of the fiber-reinforced resin substrate of the present invention as measured by DMA method (bending mode) is 115 ℃ or higher, preferably 120 ℃ or higher, and more preferably 125 ℃ or higher. The upper limit of the glass transition temperature of the fiber-reinforced resin substrate measured by the DMA method (bending mode) is preferably 240 ℃, more preferably 230 ℃ or less, and still more preferably 200 ℃ or less. When the glass transition temperature of the fiber-reinforced resin base material measured by DMA method (bending mode) is less than 115 ℃, the mechanical properties of the fiber-reinforced base material at high temperature tend to be lowered, and a fiber-reinforced base material having relatively excellent heat resistance cannot be obtained. When the upper limit of the glass transition temperature of the fiber-reinforced resin substrate measured by the DMA method (bending mode) is within the above-described preferred range, the polyphenylene sulfide resin composition used in the present invention has an appropriate melt viscosity, and therefore, the fiber-reinforced substrate has excellent impregnation properties with the reinforcing fibers, and can be obtained in which the polyphenylene sulfide resin composition is impregnated favorably.

In order to measure the glass transition temperature of the fiber-reinforced resin substrate impregnated with the polyphenylene sulfide resin composition of the present invention, a dynamic viscoelasticity measurement, specifically, a DMA method (bending mode) can be used. In the DMA method (bending mode), a fiber-reinforced resin base material is cut into a prismatic shape having a length of 20mm × a width of 12mm × a thickness of 2mm, and the measurement temperature is 30 to 250 ℃, the temperature rise rate is 2 ℃/min, the measurement frequency is 1Hz (sine wave mode), the strain amplitude is 10 μm, and the measurement is performed in a bending test mode by DMS6100 manufactured by Seiko Instruments inc.

As an example of the glass transition temperature of the fiber-reinforced resin substrate, a dynamic viscoelasticity measurement chart of the fiber-reinforced resin substrate of example 1 (in which a resin composition containing 90 wt% of (A-1) PPS resin, 10 wt% of (B) polyetherimide resin, and 1.0 part by weight of (C-1) isocyanatosilane compound is used and the volume content of carbon fiber is 60%) and a dynamic viscoelasticity measurement chart of the fiber-reinforced resin substrate of comparative example 3 (in which (A-1) PPS resin is 100 wt% and the volume content of carbon fiber is 60%) are shown together in FIG. 1.

As is clear from FIG. 1, the glass transition temperature Tg1 derived from the PPS resin is 125 ℃ in example 1, 110 ℃ in comparative example 5, and 190 ℃ in example 1 for the glass transition temperature Tg2 derived from the polyetherimide resin.

As a device for measuring the melt viscosity of the polyphenylene sulfide resin composition impregnated in the reinforcing fiber bundle of the present invention, a capillary flow meter (Capilograph type 1C manufactured by Toyo Seiki Seisaku-Sho Ltd.) was used, using an orifice having a diameter of 0.5mm and a length of 5mm, and the temperature was 320 ℃ and the shear rate was 9,728sec^-1The melt viscosity was measured under the conditions of (1). The melt viscosity of the polyphenylene sulfide resin composition of the present invention is preferably 120Pa · s or less, more preferably 100Pa · s or less, and further preferably 70Pa · s or less. When the melt viscosity is 120Pa · s or less, the resin impregnation into the reinforcing fiber bundles is excellent, and the decrease in mechanical strength and the decrease in surface quality associated with the increase in porosity can be effectively prevented.

The fiber-reinforced resin substrate of the present invention is a fiber-reinforced substrate having excellent high-temperature bending strain characteristics, and the bending strain of the molded sheet according to ASTM D790 (measured at 110 ℃ using an Instron 5565 tensile tester equipped with a thermostatic bath) is preferably 1.1% or more, more preferably 1.2% or more. When the bending strain is within the above-described preferred range, the fiber-reinforced base material is excellent in heat resistance.

Here, the polyphenylene sulfide resin composition of the present invention is preferably the following polyphenylene sulfide resin composition: the polyphenylene sulfide resin composition comprises 99 to 60 wt% of a polyphenylene sulfide resin (A) and 1 to 40 wt% of a thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher, wherein the polyphenylene sulfide resin composition contains a polyphenylene sulfide resin (A) and a thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher, and the number average particle diameter of the thermoplastic resin component having a glass transition temperature of 100 ℃ or higher is 10 [ mu ] m or less.

The polyphenylene sulfide resin composition of the present invention has a glass transition temperature as measured by the DMA method (stretching mode) of 110 ℃ or lower, but when combined with the fiber-reinforced base material of the embodiment of the present invention, the glass transition temperature of the fiber-reinforced resin base material as measured by the DMA method (bending mode) is 115 ℃ or higher, and high heat resistance can be exhibited. Therefore, a fiber-reinforced resin base material having greatly improved heat resistance can be provided without impairing the basic properties (chemical resistance, flame retardancy, and insulation) of a polyphenylene sulfide resin (hereinafter abbreviated to PPS in some cases). The reason, though not clear at present, is considered as follows: the PPS resin composition is impregnated in a fixed inter-fiber distance of the reinforcing fiber bundle, a dense sea-island structure in which the sea phase is (A) the PPS resin and the island phase is (B) the thermoplastic resin having a glass transition temperature of 100 ℃ or higher is present between the fibers, and the interface adhesion between the resin and the fibers is greatly improved, thereby dramatically improving the heat resistance as a continuous fiber reinforced resin base material.

The PPS resin (a) in the embodiment of the present invention is a polymer having a repeating unit represented by the following structural formula (I), and is preferably a polymer containing a repeating unit represented by the following structural formula (I) in an amount of 70 mol% or more, more preferably 90 mol% or more, from the viewpoint of heat resistance.

[ chemical formula 1]

The PPS resin (a) may have less than about 30 mol% of its repeating units, for example, a repeating unit having the following structure.

[ chemical formula 2]

The PPS copolymer having the above structure in a part thereof has a low melting point, and therefore, such a resin composition is advantageous in moldability.

The melt viscosity of the PPS resin (a) used in the present invention is not particularly limited, and is preferably higher in order to obtain more excellent toughness. For example, it is preferably more than 80 pas (310 ℃ C., shear rate 1,000 sec)^-1) The range of (b) is more preferably 100 pas or more, and still more preferably 150 pas or more. The upper limit is preferably 600Pa · s or less in view of maintaining melt fluidity.

In the present invention, the melt viscosity of the PPS resin (A) is at 310 ℃ and the shear rate is 1,000sec^-1The value of (2) was measured using Capilograph manufactured by Toyo Seiki Seisaku-Sho Ltd.

An example of a method for producing the PPS resin (a) used in the present invention will be described below, but the method is not limited to the following method as long as the PPS resin (a) having the above-described structure can be obtained.

First, the contents of the polyhalogenated aromatic compound, the vulcanizing agent, the polymerization solvent, the molecular weight modifier, the polymerization assistant and the polymerization stabilizer used in the production method will be described.

[ polyhalogenated aromatic Compound ]

The polyhalogenated aromatic compound is a compound having 2 or more halogen atoms in 1 molecule. Specific examples thereof include polyhalogenated aromatic compounds such as p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3, 5-trichlorobenzene, 1,2,4, 5-tetrachlorobenzene, hexachlorobenzene, 2, 5-dichlorotoluene, 2, 5-dichlorop-xylene, 1, 4-dibromobenzene, 1, 4-diiodobenzene and 1-methoxy-2, 5-dichlorobenzene, and preferably p-dichlorobenzene is used. Further, a copolymer can be prepared by combining 2 or more different polyhalogenated aromatic compounds, but it is preferable to use a para-dihalogenated aromatic compound as a main component.

The amount of the polyhalogenated aromatic compound to be used is, for example, in the range of 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, and more preferably 1.005 to 1.2 mol per 1 mol of the vulcanizing agent, from the viewpoint of obtaining the PPS resin (a) having a viscosity suitable for processing.

[ vulcanizing agent ]

Examples of the vulcanizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of 2 or more of them, and among them, sodium sulfide is preferably used. These alkali metal sulfides may be used in the form of a hydrate or an aqueous mixture, or in the form of an anhydride.

Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of 2 or more of them, and among them, sodium hydrosulfide is preferably used. These alkali metal hydrosulfides can be used in the form of a hydrate or an aqueous mixture, or in the form of an anhydride.

In addition, an alkali metal sulfide prepared in situ (in situ) in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide may also be used. Alternatively, an alkali metal sulfide may be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and transferred to a polymerization vessel for use.

Alternatively, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide may be used. Further, an alkali metal sulfide can be used by preparing an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide and transferring the alkali metal sulfide into a polymerization vessel.

The amount of the vulcanizing agent charged means a residual amount obtained by subtracting a loss of the vulcanizing agent from an actual charged amount when the loss of the vulcanizing agent occurs partially before the start of the polymerization reaction due to a dehydration operation or the like.

The alkali metal hydroxide and/or alkaline earth metal hydroxide may be used together with the vulcanizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of 2 or more of them, as preferred examples, and specific examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide, and the like, and among them, sodium hydroxide is preferably used.

In the case of using an alkali metal hydrosulfide as the vulcanizing agent, it is particularly preferable to use an alkali metal hydroxide together, and the amount thereof used may be exemplified in the range of 0.95 to 1.20 mol, preferably 1.00 to 1.15 mol, and more preferably 1.005 to 1.100 mol, relative to 1 mol of the alkali metal hydrosulfide.

[ polymerization solvent ]

As the polymerization solvent, an organic polar solvent is preferably used. Specific examples thereof include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-epsilon-caprolactam, aprotic organic solvents typified by 1, 3-dimethyl-2-imidazolidinone, N-dimethylacetamide, N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone and tetramethylene sulfoxide, and mixtures thereof, and these are preferably used because they have high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, sometimes abbreviated as NMP) is particularly preferably used.

As for the amount of the organic polar solvent to be used, a range of 2.0 to 10 moles, preferably 2.25 to 6.0 moles, more preferably 2.5 to 5.5 moles per 1 mole of the sulfiding agent can be selected.

[ molecular weight modifier ]

The polyhalogenated aromatic compound may be used in combination with a monohalogen compound (which may not necessarily be an aromatic compound) in order to form a terminal of the PPS resin to be produced (a), to adjust the polymerization reaction and the molecular weight, and the like.

[ polymerization auxiliary agent ]

In order to obtain the PPS resin (A) having a high polymerization degree in a shorter time, the use of a polymerization assistant is also one of preferable modes. The polymerization assistant is a substance having an action of increasing the viscosity of the obtained PPS resin (A). Specific examples of such a polymerization assistant include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates, alkaline earth metal phosphates, and the like. These may be used alone, or 2 or more kinds may be used simultaneously. Among them, organic carboxylates, water, and alkali metal chlorides are preferable, and further, as the organic carboxylates, alkali metal carboxylates are preferable, and as the alkali metal chlorides, lithium chloride is preferable.

The alkali metal carboxylate is a compound represented by the general formula R (COOM) n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms, M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is 1.). The alkali metal carboxylate may also be used in the form of a hydrate, an anhydride or an aqueous solution. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, potassium p-toluate, and a mixture thereof.

The alkali metal carboxylate can be formed by adding an approximately equivalent stoichiometric amount of an organic acid and one or more compounds selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal hydrogencarbonate, respectively, and reacting them. Among the alkali metal carboxylates, it is considered that the lithium salt is expensive although it has high solubility in the reaction system and high effect of an auxiliary, and the solubility of potassium, rubidium and cesium salts in the reaction system is insufficient, and therefore, it is most preferable to use sodium acetate which is inexpensive and has appropriate solubility in the polymerization system.

The amount of the alkali metal carboxylate used as the polymerization assistant is usually in the range of 0.01 to 2 moles, preferably in the range of 0.1 to 0.6 moles, more preferably in the range of 0.2 to 0.5 moles, based on 1 mole of the charged alkali metal sulfide, from the viewpoint of obtaining a higher degree of polymerization.

The amount of water added when water is used as a polymerization assistant is usually in the range of 0.3 to 15 moles, preferably in the range of 0.6 to 10 moles, more preferably in the range of 1 to 5 moles, based on 1 mole of the charged alkali metal sulfide, from the viewpoint of obtaining a higher degree of polymerization.

These polymerization assistants may be used in combination of 2 or more, and when, for example, alkali metal carboxylate and water are used in combination, the respective smaller amounts can achieve high molecular weights.

The timing of adding these polymerization aids is not particularly limited, and they may be added at any time point during the pretreatment step, the start of polymerization, or during the polymerization, which will be described later, or may be added in a plurality of times. In addition, when water is used as the polymerization assistant, it is effective to add the polyhalogenated aromatic compound after charging the compound and during the polymerization reaction.

[ polymerization stabilizer ]

The polymerization stabilizer may be used for stabilizing the polymerization reaction system and preventing side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses an undesired side reaction. One of the criteria for the side reaction is the generation of thiophenol, which can be suppressed by adding a polymerization stabilizer. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. The alkali metal carboxylate also functions as a polymerization stabilizer, and therefore, is one of the polymerization stabilizers. In addition, it is described above that, in the case of using an alkali metal hydrosulfide as a vulcanizing agent, it is particularly preferable to use an alkali metal hydroxide together, and here, an excess amount of the alkali metal hydroxide relative to the vulcanizing agent can also be used as a polymerization stabilizer.

These polymerization stabilizers may be used either individually or in combination of 2 or more. The polymerization stabilizer is preferably used in a proportion of usually 0.02 to 0.2 mol, more preferably 0.03 to 0.1 mol, and still more preferably 0.04 to 0.09 mol, based on 1 mol of the charged alkali metal sulfide. When the amount is in the above preferred range, the effect of stabilization is sufficient and the yield of the polymer is not lowered.

The timing of adding the polymerization stabilizer is not particularly limited, and may be added at any time point during the pretreatment step, the start of polymerization, or during the polymerization, which will be described later, or may be added in a plurality of times.

Next, the method for producing the PPS resin (a) used in the present invention will be specifically described in the order of the pretreatment step, the polymerization reaction step, the recovery step, and the post-treatment step.

[ pretreatment Process ]

(A) In the method for producing the PPS resin, the vulcanizing agent is usually used in the form of a hydrate, but it is preferable to remove an excessive amount of water from the system by heating a mixture containing the organic polar solvent and the vulcanizing agent before adding the polyhalogenated aromatic compound.

Further, as described above, as the vulcanizing agent, a vulcanizing agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, in situ in the reaction system or in a tank different from the polymerization tank may also be used. The method is not particularly limited, but the following methods are preferably mentioned: adding an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ℃, preferably from room temperature to 100 ℃, heating to at least 150 ℃ or higher, preferably from 180 to 260 ℃, and distilling off water under normal pressure or reduced pressure. The polymerization assistant may also be added at this stage. In addition, toluene or the like may be added to promote the removal of water by distillation.

The amount of water in the polymerization system during the polymerization reaction is preferably 0.3 to 10.0 mol per 1 mol of the sulfidizing agent charged. The water content in the polymerization system is obtained by subtracting the water content removed from the polymerization system from the water content charged into the polymerization system. The charged water may be in any form of water, an aqueous solution, crystal water, or the like.

[ polymerization reaction Process ]

The PPS resin (A) is produced by reacting a vulcanizing agent with a polyhalogenated aromatic compound in an organic polar solvent at a temperature of 200 ℃ or higher and lower than 290 ℃.

At the start of the polymerization reaction step, the organic polar solvent, the vulcanizing agent and the polyhalogenated aromatic compound are preferably mixed in an inert gas atmosphere at a temperature preferably ranging from room temperature to 240 ℃, more preferably from 100 to 230 ℃. The polymerization assistant may also be added at this stage. The order of charging these raw materials may be different or simultaneous.

The mixture is generally warmed to a temperature in the range of 200 ℃ to 290 ℃. The rate of temperature rise is not particularly limited, and may be usually selected from a rate of 0.01 to 5 ℃/min, and more preferably from 0.1 to 3 ℃/min.

The temperature is usually raised to 250 to 290 ℃ at the end, and the reaction is usually carried out at this temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

From the viewpoint of obtaining a higher polymerization degree, the following method is effective: at the stage before the final temperature is reached, the temperature is increased to 270-290 ℃ after the reaction is carried out for a certain time at 200-260 ℃. In this case, the reaction time at 200 ℃ to 260 ℃ may be selected from the range of usually 0.25 hour to 20 hours, preferably 0.25 hour to 10 hours.

In order to obtain a polymer having a higher degree of polymerization, it is sometimes effective to perform polymerization in a plurality of stages. When the polymerization is carried out in a plurality of stages, it is effective at a time point at which the conversion of the polyhalogenated aromatic compound in the system at 245 ℃ becomes 40 mol% or more, preferably 60 mol%.

The conversion rate of polyhalogenated aromatic compounds (hereinafter abbreviated as PHA) is calculated by the following formula. The residual amount of PHA can be generally determined by gas chromatography.

(a) The polyhalogenated aromatic compound is added in excess in terms of molar ratio to the alkali metal sulfide

Conversion rate [ PHA charge amount (mol) — PHA residual amount (mol) ]/[ PHA charge amount (mol) — PHA excess amount (mol) ]

(b) Cases other than the above (a)

Conversion rate [ PHA charge amount (mol) -PHA residual amount (mol)/[ PHA charge amount (mol) ]

[ recovering step ]

(A) In the method for producing a PPS resin, after completion of polymerization, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. For (A) the PPS resin, any known recovery method can be employed.

For example, a method of recovering a particulate polymer by slow cooling after completion of the polymerization reaction can be used. The slow cooling rate in this case is not particularly limited, but is usually about 0.1 ℃/min to 3 ℃/min. It is also not necessary to perform slow cooling at the same speed throughout the entire process of the slow cooling step, and a method of performing slow cooling at 0.1 to 1 ℃/min and then at a speed of 1 ℃/min or more until the polymer particles are crystallized and precipitated may be employed.

Further, it is also one of preferable methods to carry out the above-mentioned recovery under a quenching condition, and one preferable method of the recovery method is a flash (flush) method. The flash evaporation method is a method comprising: the polymerization reaction is carried out from high temperature and high pressure (generally more than 250 ℃)、8kg/cm²The above) is subjected to flash evaporation in an atmosphere of normal pressure or reduced pressure, and the polymer is recovered as a powder while recovering the solvent; the term "flash evaporation" as used herein means that the polymerization reaction product is ejected from a nozzle. The atmosphere in which the flash vaporization is carried out may specifically be, for example, nitrogen or water vapor under normal pressure, and the temperature thereof may be selected from the range of 150 ℃ to 250 ℃.

[ post-treatment Process ]

(A) The PPS resin may be produced through the polymerization and recovery steps, and then subjected to acid treatment, hot water treatment, or washing with an organic solvent.

Preferable conditions for the acid treatment are as follows. (A) The acid used in the acid treatment of the PPS resin is not particularly limited as long as it does not have an effect of decomposing the PPS resin (a), and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, propionic acid, and the like, and among them, acetic acid and hydrochloric acid are more preferably used. Nitric acid, which degrades the PPS resin (A) by decomposition, should be avoided.

The acid treatment method includes a method of immersing the PPS resin (a) in an acid or an aqueous acid solution, and may be appropriately stirred or heated as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing PPS resin powder in an aqueous solution having a PH of 4 heated to 80 to 200 ℃ and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, about 4 to 8. The acid-treated PPS resin (a) is preferably washed several times with water or warm water in order to remove the residual acid, salt, and the like. The water used for washing is preferably distilled water or deionized water, in order not to impair the desired effect of chemical modification of the PPS resin (a) by acid treatment.

Preferable conditions for the hot water treatment are as follows. When the PPS resin (a) is subjected to hot water treatment, the temperature of the hot water is preferably set to 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 150 ℃ or higher, and particularly preferably 170 ℃ or higher. When the above-mentioned preferable hot water temperature is set, a sufficient effect of the ideal chemical modification of the PPS resin (A) can be obtained.

In order to exhibit the desired effect of chemical modification of the PPS resin (a) by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is not particularly limited, and the hot water treatment may be carried out by a method of charging a predetermined amount of the PPS resin (a) into a predetermined amount of water, heating and stirring the mixture in a pressure vessel, a method of continuously performing the hot water treatment, or the like. The ratio of the PPS resin (a) to water is preferably higher than water, but a bath ratio of the PPS resin (a) to 1 liter of water of 200g or less may be selected.

In addition, the atmosphere for the treatment is preferably an inert atmosphere in order to avoid decomposition of the terminal group. In the PPS resin (A) after the hot water treatment, it is preferable to wash the PPS resin (A) with warm water several times in order to remove the residual components.

Preferable conditions for washing with an organic solvent are as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin (a), and examples thereof include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1, 3-dimethylimidazolidinone, hexamethylphosphoric triamide, piperazinones, sulfoxide/sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, and tetrahydrofuran, halogen solvents such as chloroform, dichloromethane, trichloroethylene, ethylene dichloride, tetrachloroethylene, monochloroethane, dichloroethane, tetrachloroethane, hexachloroethane, and chlorobenzene, halogen solvents such as methanol, ethanol, propanol, butanol, pentanol, and the like, Alcohol and phenol solvents such as ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform, and the like are particularly preferably used. These organic solvents may be used in a mixture of 1 or 2 or more.

The method of washing with an organic solvent includes a method of immersing the PPS resin (a) in an organic solvent, and may be appropriately stirred or heated as necessary. The washing temperature for washing the PPS resin (a) with the organic solvent is not particularly limited, and any temperature of about room temperature to 300 ℃ may be selected. The cleaning efficiency tends to be higher as the cleaning temperature is higher, but the cleaning effect is generally sufficient at a cleaning temperature of from room temperature to 150 ℃. The cleaning may be carried out in a pressure vessel under pressurized conditions at a temperature not lower than the boiling point of the organic solvent. The cleaning time is also not particularly limited. Although depending on the washing conditions, in the case of batch washing, a sufficient effect can be obtained by washing for 5 minutes or more. In addition, continuous cleaning may be performed.

The PPS resin (a) may be used after completion of polymerization by thermal oxidation crosslinking treatment based on heating under an oxygen atmosphere and heating with a crosslinking agent such as peroxide added thereto to increase the molecular weight.

When the dry heat treatment is performed for the purpose of high molecular weight by thermal oxidative crosslinking, the temperature is preferably 160 to 260 ℃, and more preferably 170 to 250 ℃. The oxygen concentration is preferably set to 5 vol% or more, and more preferably 8 vol% or more. The upper limit of the oxygen concentration is not particularly limited, but is about 50 vol%. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heating apparatus may be a conventional hot air dryer, or may be a rotary or stirring blade heating apparatus, but in the case of efficient and more uniform treatment, a rotary or stirring blade heating apparatus is more preferably used.

In addition, dry heat treatment may be performed for the purpose of suppressing thermal oxidative crosslinking and removing volatile components. The temperature is preferably 130 to 250 ℃, and more preferably 160 to 250 ℃. In this case, the oxygen concentration is preferably set to less than 5 vol%, more preferably less than 2 vol%. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heating apparatus may be a conventional hot air dryer, or may be a rotary or stirring blade heating apparatus, but in the case of efficient and more uniform treatment, a rotary or stirring blade heating apparatus is more preferably used.

However, in order to achieve the aim of toughness, the PPS resin (a) is preferably not subjected to a high molecular weight by thermal oxidation crosslinking treatment, that is, is preferably substantially linear PPS.

The thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher in the embodiment of the present invention is not particularly limited in kind, but preferably used is polyimide, polyarylketone, polysulfone, polyarylate, polyphenylene ether, polycarbonate, polyetherimide, polyethersulfone, polyphenylsulfone, polysulfone, polyamideimide, or a liquid crystal polymer, more preferably used is an amorphous resin such as polyetherimide, polyethersulfone, polyphenylsulfone, polysulfone, or polyphenylene ether, and particularly preferably used is polyetherimide or polyethersulfone.

In the present invention, the glass transition temperature of the components (A) and (B) can be determined by a melting temperature simulation isothermal method. In the melting temperature simulated isothermal method, the glass transition temperature was calculated by the following formula in accordance with JIS K7121 using a temperature modulation DSC (manufactured by TA Instruments, inc.).

Glass transition temperature (extrapolated glass transition onset temperature + extrapolated glass transition end temperature)

[ polyetherimide resin and polyether sulfone resin ]

The polyetherimide resin used in the present invention is a resin having an imide bond and an ether bond in a repeating skeleton. As a representative structure, the following structure can be exemplified.

[ chemical formula 3]

Generally marketed by General Electric Company under the trademark "ULTEM" (registered trademark).

The polyethersulfone resin used in the present invention is a resin having a sulfone bond and an ether bond in a repeating skeleton. As a representative structure, the following structure can be exemplified.

[ chemical formula 4]

Commercially available under the trade marks of "VICTREX" (registered trade mark) PES "SUMIKAEXCEL" (registered trade mark).

When comparing a polyetherimide resin and a polyethersulfone resin, the polyetherimide resin can exhibit high toughness in a smaller amount and is therefore preferable.

The compounding ratio of the PPS resin (a) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher in the present invention is preferably in the range of 99 to 60 wt%/1 to 40 wt%, more preferably in the range of 97 to 70 wt%/3 to 30 wt%, and still more preferably in the range of 95 to 80 wt%/5 to 20 wt%. (A) When the amount of the metal compound represented by the formula (i) is within the above-described preferred range, the toughness-improving effect is excellent, and the melt flowability is also excellent.

The PPS resin composition used in the present invention has (a) excellent heat resistance, chemical resistance, barrier properties, and toughness inherent in PPS resins. In order to exhibit the above characteristics, (A) the PPS resin forms a sea phase (continuous phase or matrix) and (B) the thermoplastic resin having a glass transition temperature of 100 ℃ or higher forms an island phase (dispersed phase). The number-average dispersed particle diameter of the thermoplastic resin component (B) having a glass transition temperature of 100 ℃ or higher is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 500nm or less. The lower limit of the number-average dispersed particle diameter of the thermoplastic resin component (B) having a glass transition temperature of 100 ℃ or higher is preferably 1nm or higher from the viewpoint of productivity. (B) When the number-average dispersed particle diameter of the thermoplastic resin component having a glass transition temperature of 100 ℃ or higher is in the range of more than 10 μm, the toughness-improving effect is remarkably impaired, which is not preferable. By forming the continuous phase of the PPS resin (a), the properties of the PPS resin (a) excellent in chemical resistance and flame retardancy can be greatly reflected in the properties of the obtained composition.

Here, the average dispersed particle size means: a test piece of ASTM4 was molded at a molding temperature of (A) melting peak temperature of PPS resin +20 ℃, a sheet of 0.1 μm or less was cut from the center thereof at-20 ℃ in the cross-sectional area direction of the dumbbell sheet, and the maximum and minimum diameters of 100 arbitrary dispersed portions of the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or more when observed at a resolution (particle image) of 0.38nm and a magnification of 50 to 60 ten thousand times) were measured first using a Hitachi-Tech transmission electron microscope (H-7100 type transmission electron microscope (resolution (particle image)) manufactured by Hitachi Ltd. and the average value thereof was determined as the dispersed particle diameter, and the average dispersed particle diameter was determined by determining the average value thereof.

(C) Compound having one or more groups selected from epoxy group, amino group and isocyanate group

In the present invention, it is preferable to add (C) a compound having at least one group selected from an epoxy group, an amino group, and an isocyanate group as a compatibilizer for the purpose of further improving the interfacial adhesiveness between the resin and the reinforcing fiber.

Examples of the epoxy group-containing compound include glycidyl ethers of bisphenols such as bisphenol A, resorcinol, hydroquinone, catechol, bisphenol F, salicin, 1,3, 5-trihydroxybenzene, bisphenol S, trihydroxydiphenyldimethylmethane, 4' -dihydroxybiphenyl, 1, 5-dihydroxynaphthalene, cardanol, and 2,2,5,5, -tetrakis (4-hydroxyphenyl) hexane, glycidyl ether-based epoxy compounds such as glycidyl ether obtained by halogenating bisphenol instead of bisphenol, diglycidyl ether of butanediol, glycidyl ester-based compounds such as glycidyl phthalate, glycidyl amine-based compounds such as N-glycidylaniline, linear epoxy compounds such as epoxidized polyolefin, and epoxidized soybean oil, glycidyl epoxy resins, and the like, Cyclic non-glycidyl epoxy resins such as vinylcyclohexene dioxide and dicyclopentadiene dioxide.

Further, Novolac type epoxy resins can be exemplified. The Novolac epoxy resin has 2 or more epoxy groups and is usually obtained by reacting a Novolac phenol resin with epichlorohydrin. In addition, the Novolac type phenol resin can be obtained by condensation reaction of phenols and formaldehyde. The phenols as the raw material are not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, bisphenol a, resorcinol, p-tert-butylphenol, bisphenol F, bisphenol S, and condensates thereof.

Examples of the compound having an amino group include alkoxysilanes having an amino group. Specific examples of such compounds include amino group-containing alkoxysilane compounds such as γ - (2-aminoethyl) aminopropylmethyldimethoxysilane, γ - (2-aminoethyl) aminopropyltrimethoxysilane and γ -aminopropyltrimethoxysilane.

Examples of the compound containing 1 or more isocyanate groups include isocyanate compounds such as 2, 4-tolylene diisocyanate, 2, 5-tolylene diisocyanate, diphenylmethane-4, 4' -diisocyanate and polymethylenepolyphenyl polyisocyanate, and alkoxysilane compounds containing an isocyanate group such as γ -isocyanatopropyltriethoxysilane, γ -isocyanatopropyltrimethoxysilane, γ -isocyanatopropylmethyldimethoxysilane, γ -isocyanatopropylmethyldiethoxysilane, γ -isocyanatopropylethyldimethoxysilane, γ -isocyanatopropylethyldiethoxysilane and γ -isocyanatopropyltrichlorosilane.

Among these, in order to dramatically improve the interfacial adhesiveness between the resin and the reinforcing fiber, at least 1 compound selected from a compound containing 1 or more isocyanate groups or a compound containing 2 or more epoxy groups is preferable, and a compound containing 1 or more isocyanate groups is more preferable.

The amount of the component (C) is in the range of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the PPS resin (A) and the thermoplastic resin (B) having a glass transition temperature of 100 ℃ or higher.

In the fiber-reinforced resin base material of the present invention, the number-average dispersed particle diameter of the thermoplastic resin component having a glass transition temperature of 100 ℃ or higher (B) which forms the island phase in the polyphenylene sulfide resin composition forming the sea-island structure is made smaller than the distance between the reinforcing fibers represented by the following formula, whereby the heat resistance of the fiber-reinforced resin base material of the present invention can be dramatically improved.

z＝y-2r

(z: distance between reinforcing fibers, y: distance between centers of reinforcing fibers, r: fiber radius)

In the present invention, the polyphenylene sulfide resin composition impregnated in the reinforcing fiber bundles is usually obtained by melt kneading. As a representative example, the following methods can be mentioned: the resin composition is fed to a commonly known melt-kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a roll-type kneader as a melt-kneading machine, and kneaded at a temperature of the melting peak temperature of the resin composition plus a processing temperature of 5 to 100 ℃. In this case, the order of mixing the raw materials is not particularly limited, and any of the following methods may be used: a method of mixing all the raw materials and then melt-kneading them by the above-mentioned method; a method of mixing a part of the raw materials, then melt-kneading the mixture by the above-mentioned method, and further mixing the remaining raw materials and melt-kneading the mixture; or a method of mixing a part of the raw materials and then mixing the remaining raw materials using a side feeder in the melt-kneading process using a single-screw extruder or a twin-screw extruder; and so on. It is needless to say that the small amount of the additive component may be formed by kneading and granulating the other components by the above-mentioned method or the like, and then adding the resulting mixture before forming.

For the purpose of modification, the following compounds may be added. A plasticizer such as a polyalkylene oxide oligomer-based compound, a thioether-based compound, an ester-based compound or an organophosphorus compound, a nucleating agent such as polyether ether ketone, montanic acid wax-based compounds, a metal soap such as lithium stearate or aluminum stearate, a mold release agent such as a polycondensate of ethylenediamine, stearic acid and sebacic acid, a color preventive such as hypophosphite, a phenol-based antioxidant such as (3, 9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane), (a phosphorus-based antioxidant such as (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite), water, a plasticizer such as an organic phosphorus-based compound, a nucleating agent such as a polyether ether ketone, a montanic acid wax, a metal soap such as lithium stearate or aluminum stearate, a mold release agent such as an ethylenediamine, stearic acid and a sebacic acid polymer, a silicone-based compound, a phenol-based antioxidant such as (3, 2,4,8, 10-tetraoxaspiro [5,5] undecane), and the like, may be blended, A lubricant, an ultraviolet screening agent, a colorant, a foaming agent, and the like. When the amount of any of the above-mentioned compounds is more than 20% by weight of the total composition, the inherent properties of the resin are impaired, and it is not preferable to add the compound in an amount of 10% by weight or less, and more preferably 1% by weight or less.

The fiber-reinforced resin base material according to the embodiment of the present invention can be obtained by impregnating continuous reinforcing fibers with a thermoplastic resin (first embodiment). Alternatively, the thermoplastic resin may be impregnated into a reinforcing fiber base material in which reinforcing fibers of discontinuous fibers are dispersed (second embodiment).

As a method of impregnating the continuous reinforcing fibers with the thermoplastic resin in the first embodiment, for example, there can be mentioned: a film method in which a sheet-like thermoplastic resin is melted and pressurized to impregnate a reinforcing fiber bundle with the thermoplastic resin; a blending (kneading) method in which a fibrous thermoplastic resin is blended with reinforcing fiber bundles, and then the fibrous thermoplastic resin is melted and pressurized to impregnate the reinforcing fiber bundles with the thermoplastic resin; a powder method in which a powdery thermoplastic resin is dispersed in gaps between fibers in a reinforcing fiber bundle, and then the powdery thermoplastic resin is melted and pressurized to impregnate the reinforcing fiber bundle with the thermoplastic resin; in the drawing method, the reinforcing fiber bundles are impregnated with the molten thermoplastic resin, and the thermoplastic resin is impregnated into the reinforcing fiber bundles by applying pressure. The drawing method is preferable in that a wide variety of fiber-reinforced resin substrates having various thicknesses and fiber volume contents can be produced.

The thickness of the fiber-reinforced resin base material in the first embodiment of the present invention is preferably 0.1 to 10 mm. When the thickness is 0.1mm or more, the strength of the molded article obtained using the fiber-reinforced resin base material can be improved. More preferably 0.2mm or more. On the other hand, when the thickness is 1.5mm or less, the reinforcing fibers are more easily impregnated with the thermoplastic resin. More preferably 1mm or less, still more preferably 0.7mm or less, and still more preferably 0.6mm or less.

In the first aspect of the present invention, the volume content of the fiber-reinforced resin base material is preferably 20 to 70 vol%. In other words, the reinforcing fibers are preferably contained in an amount of 20 to 70 vol% (20 vol% or more and 70 vol% or less) based on the entire fiber-reinforced resin base material (100 vol%). By containing 20 vol% or more of the reinforcing fiber, the strength of a molded article obtained using the fiber-reinforced resin base material can be further improved. More preferably 30% by volume or more, and still more preferably 40% by volume or more. On the other hand, by containing 70 vol% or less of the reinforcing fibers, the reinforcing fibers are more easily impregnated with the thermoplastic resin. More preferably 60% by volume or less, and still more preferably 55% by volume or less. The volume content can be adjusted to a desired range by adjusting the amounts of the reinforcing fibers and the thermoplastic resin to be charged.

The volume content (Vf) of the reinforcing fibers in the fiber-reinforced resin base material can be measured by measuring the mass W of the fiber-reinforced resin base material₀Thereafter, the fiber-reinforced resin substrate was heated at 50 ℃ for 240 minutes in the air to burn out the thermoplastic resin component, and the mass W of the remaining reinforcing fibers was measured₁And calculated by the following formula (i).

Vf (% by volume) to (W)₁/ρf)/{W₁/ρf+(W₀-W₁)/ρr}×100 (i)

ρ f: density (g/cm) of reinforcing fibers³)

ρ r: density (g/cm) of thermoplastic resin³)

The fiber-reinforced resin base material according to the embodiment of the present invention may have a desired impregnation property selected according to its usage and purpose. Examples thereof include prepregs with further improved impregnation properties, semi-impregnated semi-pregs (semi-pregs), and woven fabrics (fabrics) with low impregnation properties. In general, a molding material having a higher impregnation property is more preferable because a molded product having excellent mechanical properties can be obtained by molding in a short time.

In the second aspect of the present invention, examples of the method for impregnating the reinforcing fiber base material in which the discontinuous fibers are dispersed with the thermoplastic resin include: a method of supplying a thermoplastic resin by an extruder and impregnating the thermoplastic resin into a reinforcing fiber base material; a method of dispersing and melting thermoplastic resin powder in the fiber layer of the reinforcing fiber base material; a method of making a thermoplastic resin into a film and laminating the film with a reinforcing fiber base material; a method in which a thermoplastic resin is dissolved in a solvent, the reinforcing fiber base material is impregnated with the solution, and the solvent is evaporated; a method of forming a thermoplastic resin into fibers and forming mixed filaments with discontinuous fibers; a method in which a reinforcing fiber base material is impregnated with a precursor of a thermoplastic resin and then polymerized to form a thermoplastic resin; a method of using a melt-blown nonwoven fabric and performing lamination; and so on. Any method can be used, but a method of supplying a thermoplastic resin by an extruder and impregnating the thermoplastic resin into a reinforcing fiber base material has an advantage that the thermoplastic resin does not need to be processed 2 times, a method of dispersing a thermoplastic resin powder in a fiber layer of a reinforcing fiber base material and melting the same has an advantage that impregnation is easily performed, and a method of forming a film of a thermoplastic resin and laminating the film with a reinforcing fiber base material has an advantage that a product with good quality can be obtained.

The thickness of the fiber-reinforced resin base material in the second embodiment of the present invention is preferably 0.1 to 10 mm. When the thickness is 0.1mm or more, the strength of the molded article obtained using the fiber-reinforced resin base material can be improved. More preferably 1mm or more. On the other hand, when the thickness is 10mm or less, the reinforcing fibers are more easily impregnated with the thermoplastic resin. More preferably 7mm or less, and still more preferably 5mm or less.

In the second aspect of the present invention, the fiber-reinforced resin base material preferably has a volume content of 20 to 70 vol%. In other words, the discontinuous fibers are preferably contained in an amount of 20 to 70 vol% in the entire fiber-reinforced resin substrate (100 vol%). By containing 20 vol% or more of the discontinuous fibers, the strength of a molded article obtained by using the fiber-reinforced resin base material can be further improved. More preferably 30% by volume or more. On the other hand, when the content of the discontinuous fibers is 70 vol% or less, the discontinuous fibers are more easily impregnated with the thermoplastic resin. More preferably 60% by volume or less, and still more preferably 50% by volume or less. The volume content (Vf) can be calculated by the above equation (i).

In the second aspect of the present invention, the fiber-reinforced resin base material may have a desired impregnation property selected according to the use and purpose thereof. In general, a molding material having a higher impregnation property is more preferable because a molded product having excellent mechanical properties can be obtained by molding in a short time.

In the production of the fiber-reinforced resin base material according to the second aspect of the present invention, a method of adjusting the thickness and the volume content of the fiber-reinforced resin base material to a desired thickness and volume content includes a method of heating and pressing the fiber-reinforced resin base material using a press machine. The press machine is not particularly limited as long as it can achieve the temperature and pressure necessary for impregnation of the thermoplastic resin, and a normal press machine having upper and lower planar platens or a so-called double-belt press machine having a mechanism for 1 pair of endless steel belts to travel can be used.

The fiber-reinforced resin base materials in the first and second embodiments of the present invention are laminated in an arbitrary configuration by 1 or more, and then molded while applying heat and/or pressure as necessary, thereby obtaining a molded article.

Examples of the method of applying heat and/or pressure include: a press molding method in which a fiber-reinforced resin base material obtained by laminating a plurality of fiber-reinforced resin base materials having an arbitrary composition is placed in a mold or on a pressing plate, and then the mold or the pressing plate is closed and pressed; an autoclave molding method in which a molding material obtained by laminating a plurality of molding materials having an arbitrary composition is put into an autoclave and pressurized and heated; a bag molding method in which a fiber-reinforced resin base material obtained by laminating a film or the like in an arbitrary configuration is enclosed in a film or the like, the inside is brought into a reduced pressure state, and the inside is heated in an oven while being pressurized at atmospheric pressure; a tape winding (wrapping tape) method in which a tape is wound while tension is applied to a fiber-reinforced resin base material laminated in an arbitrary configuration, and the resultant is heated in an oven; an internal pressure molding method in which a fiber-reinforced terminal-modified polyamide resin obtained by laminating a plurality of layers of any desired structures is placed in a mold, and a gas, a liquid, or the like is injected into a core placed in the mold, and the core is pressurized; and so on. In particular, from the viewpoint of obtaining a molded article having few voids in the obtained molded article and excellent appearance quality, it is preferable to adopt a molding method in which pressurization is performed using a mold.

As the press molding method, there can be adopted: a hot press method in which a fiber-reinforced resin base material is placed in a mold in advance, and pressurization and heating are performed while the mold is closed, and then the fiber-reinforced resin base material is cooled by cooling the mold in a state where the mold is closed, thereby obtaining a molded product; press molding is a method in which a fiber-reinforced resin base material is heated to a temperature equal to or higher than the melting temperature of a thermoplastic resin by a heating device such as a far infrared heater, a hot plate, a high-temperature oven, or dielectric heating in advance, and the fiber-reinforced resin base material is placed on a mold to be the lower surface of the molding mold in a state where the thermoplastic resin is melted and softened, and then the mold is closed and clamped, followed by pressure cooling. The press molding method is not particularly limited, but press molding is preferable from the viewpoint of increasing the molding cycle and improving productivity.

The fiber-reinforced resin base material and the molded article according to the first and second aspects of the present invention can be subjected to integration molding such as insert molding (insert molding) and over-mold (outert molding), an adhesion process with excellent productivity such as heat-based correction treatment, thermal welding, vibration welding, and ultrasonic welding, and integration using an adhesive, thereby obtaining a composite.

The fiber-reinforced resin base material in the first and second aspects of the present invention is preferably a composite molded article obtained by joining a molded article containing a thermoplastic resin at least partially.

The molded article (molding substrate and molded article) comprising a thermoplastic resin, which is integrated with the fiber-reinforced resin substrate in the first and second embodiments of the present invention, is not particularly limited, and examples thereof include resin materials and molded articles, metal materials and molded articles, inorganic materials and molded articles, and the like. Among them, the resin material and the molded article are preferable in view of the adhesive strength with the fiber-reinforced thermoplastic resin in the present invention.

The matrix resin of the molding material and the molded article integrated with the fiber-reinforced resin base material in the first and second embodiments of the present invention may be the same resin as the fiber-reinforced resin base material and the molded article thereof, or may be a different resin. In order to further improve the adhesive strength, the same kind of resin is preferable. In the case of different kinds of resins, it is more preferable to provide a resin layer at the interface.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the description of these examples. The physical properties of each of the examples and comparative examples were evaluated by the following methods.

[ volume fraction (Vf) ]

The mass W of the fiber-reinforced resin base material obtained in each of examples and comparative examples was measured₀Thereafter, the fiber-reinforced resin base material was heated at 550 ℃ for 240 minutes in the air to burn out the resin component, and the mass W of the remaining reinforcing fibers was measured₁The volume content (Vf) of the fiber-reinforced resin base material was calculated by the following formula (i).

Vf (% by volume) to (W)₁/ρf)/{W₁/ρf+(W₀-W₁)/ρr}×100(i)

ρ f: density (g/cm) of reinforcing fibers³)

ρ r: density (g/cm) of resin composition³)

[ measurement of molecular weight of Polymer ]

The molecular weight of the PPS resin (a) used in the present invention is calculated in terms of polystyrene by Gel Permeation Chromatography (GPC), which is one of Size Exclusion Chromatography (SEC). The measurement conditions of GPC are as follows.

An apparatus: senshu Scientific Co., Ltd. ultra-high temperature GPC device SSC-7100

Column name: senshu Scientific Co, Ltd. column GPC3506

Eluent: 1-chloronaphthalene

The detector: differential refractive index detector

Column temperature: 210 deg.C

Pre-oven temperature: 250 deg.C

Pump thermostat temperature: 50 deg.C

Detector temperature: 210 deg.C

Flow rate: 1.0mL/min

Sample injection amount: 300 μ L (sample concentration: about 0.2 wt%)

[ Polymer flowability (melt viscosity) ]

The polyphenylene sulfide resin compositions obtained in the examples and comparative examples were dried in a vacuum dryer at 100 ℃ for 12 hours or more. As a melt viscosity measuring device, a capillary flowmeter (Capilograph 1C, manufactured by Toyo Seiki Seisaku-Sho Ltd.) was used, using an orifice having a diameter of 0.5mm and a length of 5mm, and having a shear rate of 9,728sec at 320 ℃ C^-1The melt viscosity (melt viscosity before residence) was measured under the conditions of (1). However, the resin composition was left for 5 minutes and then measured to melt. The smaller the value of the melt viscosity, the higher the fluidity.

[ Polymer Heat resistance: DMA method (stretching mode) ]

The resin composition pellets obtained in each example and comparative example were processed at a processing temperature of melting point +60 ℃ to prepare a pressurized film sample having a width of 8mm × a length of 40mm × a thickness of 0.1mm, and the storage elastic modulus and the loss elastic modulus were measured under the following measurement conditions using a dynamic viscoelasticity measuring apparatus (DMS6100) manufactured by Seiko Instruments inc. Next, a graph of each measurement temperature and loss tangent was prepared, and the temperature shown as a peak in this graph was taken as the glass transition temperature. The higher the glass transition temperature, the more excellent the heat resistance of the polymer.

Measurement mode: stretching mode

Temperature conditions: 1, maintaining at 50 deg.C for 2 min, and 2, heating from 30 deg.C to 250 deg.C

Temperature increase rate: 2 ℃/min

Measurement frequency: 1Hz

Minimum tension: 200mN

Strain amplitude: 10 μm

Tension gain: 1.5

Initial value of force amplitude: 2,000mN

[ Heat resistance of composite article: DMA method (bending mode) ]

The fiber-reinforced resin substrates (width 50mm × thickness 0.08mm, unidirectional substrate) obtained in each of examples and comparative examples were laminated and press-molded in the 0 ° direction so that the thickness became 2mm, thereby obtaining a fiber-reinforced resin molded article. From the molded article, a prism shape having a width of 12mm × a length of 20mm × a thickness of 2mm was cut to prepare a sample, and the storage elastic modulus and the loss elastic modulus were measured under the following measurement conditions using a dynamic viscoelasticity measuring apparatus (DMS6100) manufactured by Seiko Instruments inc. Next, a graph of each measurement temperature and loss tangent was prepared, and the temperature shown as a peak in this graph was taken as the glass transition temperature. The higher the glass transition temperature, the more excellent the heat resistance of the composite product.

Measurement mode: bending mode

Temperature conditions: 1, maintaining at 50 deg.C for 2 min, and 2, heating from 30 deg.C to 250 deg.C

Temperature increase rate: 2 ℃/min

Measurement frequency: 1Hz

Minimum tension: 200mN

Strain amplitude: 10 μm

Tension/compression gain: 1.5

Initial value of force amplitude: 2,000mN

[ mechanical Properties (tensile test) of composite article ]

The fiber-reinforced resin substrates (width 50mm × thickness 0.08mm, unidirectional substrate) obtained in each of examples and comparative examples were laminated and press-molded in the 0 ° direction so as to have a thickness of 1.0mm × width 100mm × length 250mm, to obtain a fiber-reinforced resin molded article. From this molded article, a rectangular shape having a width of 15mm × a length of 125mm × a thickness of 1.0mm was cut out for use in the measurement of the tensile test, and the tensile test was performed according to ASTM D3039 (each n is 5). The larger the numerical values of the tensile strength and the tensile elongation, the more excellent the mechanical properties of the composite material.

[ mechanical Properties (bending test) of composite article ]

The fiber-reinforced resin substrates (width 50mm × thickness 0.08mm, unidirectional substrate) obtained in each of examples and comparative examples were laminated and press-molded in the 0 ° direction so as to have a thickness of 2.0mm × width 100mm × length 250mm, to obtain a fiber-reinforced resin molded article. From this molded article, a rectangular shape having a width of 15mm × a length of 125mm × a thickness of 2.0mm was cut for bending test measurement, and a bending test was performed according to ASTM D790 (each n is 5). The larger the numerical values of the flexural strength and the flexural modulus, the more excellent the mechanical properties of the composite material.

[ Heat resistance of composite article (high temperature bending test) ]

The fiber-reinforced resin substrates (width 50mm × thickness 0.08mm, unidirectional substrate) obtained in each of examples and comparative examples were laminated and press-molded in the 0 ° direction so as to have a thickness of 2.0mm × width 100mm × length 250mm, to obtain a fiber-reinforced resin molded article. From this molded article, a rectangular shape having a width of 15mm × a length of 125mm × a thickness of 2.0mm was cut for bending test measurement, and bending tests at 23 ℃,90 ℃, 110 ℃ and 120 ℃ were performed according to ASTM D790 using an Instron 5565 equipped with a thermostatic bath (each n is 5). The greater the value of the flexural modulus, the more excellent the rigidity of the composite material at high temperatures.

[ impregnation Property and thermal stability ]

The thickness direction cross section of the fiber reinforced resin base material obtained in each of examples and comparative examples was observed as follows. A sample in which a fiber-reinforced resin base material is embedded with an epoxy resin is prepared, and the sample is polished until a cross section in the thickness direction of the fiber-reinforced resin base material can be observed well. The polished sample was imaged at 400-fold magnification using an ultra-deep color 3D shape measuring microscope VHX-9500 (controller section)/VHZ-100R (measurement section) (manufactured by Keyence corporation). The imaging range was set to a range of 500 μm in thickness × width of the fiber-reinforced resin base material. In the captured image, the area of the portion occupied by the resin and the area of the portion that becomes the void (void) are obtained, and the impregnation rate is calculated by the following equation.

Impregnation rate (%) < 100 × (total area of sites occupied by resin)/{ (total area of sites occupied by resin) + (total area of sites forming voids) }

Since voids are reduced when impregnation property and thermal stability are high and voids are increased when at least one of impregnation property and thermal stability is low, the impregnation property and thermal stability of the fiber-reinforced resin substrate are evaluated on the following 2 levels using the impregnation rate as a criterion, and the product is regarded as good. The fiber-reinforced resin base material in the first embodiment is produced at a processing temperature of melting point +60 ℃ and 100 ℃. The fiber-reinforced resin base material in the second embodiment is produced at a processing temperature of melting point +60 ℃ and 100 ℃.

Good: the impregnation rate is 98% or more.

Poor: the impregnation rate is less than 98 percent.

[ surface quality ]

The surface quality of the fiber-reinforced resin base materials obtained in the examples and comparative examples was visually observed. The surface quality was evaluated on the following 2 grades, and good results were regarded as passed.

Good: no cracks on the surface, discoloration of the matrix resin, and exposure of the reinforcing fibers were observed

Poor: cracks on the surface, discoloration of the matrix resin, and exposure of the reinforcing fibers were observed

The fiber-reinforced resin base material in the first embodiment is produced at a processing temperature of melting point +60 ℃ and 100 ℃. The fiber-reinforced resin base material in the second embodiment is produced at a processing temperature of melting point +60 ℃ and 100 ℃.

[ raw materials ]

In examples and comparative examples, the following materials were used as raw materials.

< reference example 1 > (A) polyphenylene sulfide resin

< production of polyphenylene sulfide (A-1) >

A70-liter autoclave equipped with a stirrer was charged with 8,267.37g (70.00 mol) of 47.5% sodium hydrosulfide, 2,957.21g (70.97 mol) of 96% sodium hydroxide, 11,434.50g (115.50 mol) of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 2,583.00g (31.50 mol) of sodium acetate, and 10,500g of ion-exchanged water, and the mixture was gradually heated to 245 ℃ over about 3 hours under normal pressure while passing nitrogen therethrough, and after 14,780.1g and 280g of NMP were distilled off, the reaction vessel was cooled to 160 ℃. The amount of residual moisture in the system per 1 mole of charged alkali metal sulfide including the moisture consumed in the hydrolysis of NMP was 1.06 moles. The amount of hydrogen sulfide scattered was 0.02 mol per 1 mol of the charged alkali metal sulfide.

Next, 10,235.46g (69.63 moles) of p-dichlorobenzene and 9,009.00g (91.00 moles) of NMP were added, the reaction vessel was sealed under nitrogen, and the temperature was raised to 238 ℃ at a rate of 0.6 ℃/min while stirring at 240 rpm. After the reaction was carried out at 238 ℃ for 95 minutes, the temperature was raised at a rate of 0.8 ℃ per minute to 270 ℃. After 100 minutes reaction at 270 ℃, 1260g (70 moles) of water was cooled to 250 ℃ at a rate of 1.3 ℃/minute while being pressed in over 15 minutes. Thereafter, the mixture was cooled to 200 ℃ at a rate of 1.0 ℃/min and then quenched to a temperature close to room temperature.

The contents were taken out, diluted with 26,300g of NMP, and the solid was separated by filtration using a sieve (80 mesh), and the resulting particles were washed with 31,900g of NMP and separated by filtration. This was washed several times with 56,000g of ion-exchanged water, and after filtration and separation, 70,000g of a 0.05 wt% aqueous acetic acid solution was washed with the water and separation was carried out by filtration. The obtained water-containing PPS particles were washed with 70,000g of ion-exchanged water, separated by filtration, dried with hot air at 80 ℃ and dried under reduced pressure at 120 ℃. GPC measurement of the obtained PPS was carried out, and the weight average molecular weight was 73,000, and the degree of dispersion was 2.80.

< production of polyphenylene sulfide (A-2) >

A70-liter autoclave equipped with a stirrer and a bottom plug valve was charged with 8.27kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94kg (70.63 mol) of 96% sodium hydroxide, 11.45kg (115.50 mol) of NMP, 1.89kg (23.1 mol) of sodium acetate, and 5.50kg of ion-exchanged water, and the mixture was gradually heated to 245 ℃ over about 3 hours under normal pressure while passing nitrogen therethrough, and after distilling off 9.77kg of water and 0.28kg of NMP, the reaction vessel was cooled to 200 ℃. The amount of residual moisture in the system per 1 mole of charged alkali metal sulfide including the moisture consumed in the hydrolysis of NMP was 1.06 moles. The amount of hydrogen sulfide scattered was 0.02 mol per 1 mol of the charged alkali metal sulfide.

Thereafter, the mixture was cooled to 200 ℃ and 10.42kg (70.86 mol) of p-dichlorobenzene and 9.37kg (94.50 mol) of NMP were added thereto, the reaction vessel was sealed under nitrogen, and the temperature was raised from 200 ℃ to 270 ℃ at a rate of 0.6 ℃/min while stirring at 240rpm, and the reaction was carried out at 270 ℃ for 140 minutes. Thereafter, 2.40kg (133 moles) of water was pressed in while cooling from 270 ℃ to 250 ℃ over 15 minutes. Then, the mixture was gradually cooled from 250 ℃ to 220 ℃ over 75 minutes, and then quenched to near room temperature, and the contents were taken out.

The contents were diluted with about 35 liters of NMP to prepare a slurry, which was stirred at 85 ℃ for 30 minutes and then separated by filtration using an 80-mesh metal net (mesh size: 0.175mm) to obtain a solid. The resulting solid was similarly washed with about 35 liters of NMP and separated by filtration. The following operations were repeated a total of 3 times: the obtained solid was diluted with 70 liters of ion-exchanged water, stirred at 70 ℃ for 30 minutes, filtered with an 80-mesh wire gauze, and the solid was recovered. The obtained solid and 32g of acetic acid were diluted with 70 liters of ion-exchanged water, stirred at 70 ℃ for 30 minutes, and then filtered through an 80-mesh metal net, and the obtained solid was further diluted with 70 liters of ion-exchanged water, stirred at 70 ℃ for 30 minutes, and then filtered through an 80-mesh metal net to recover the solid. The solid obtained as described above was dried at 120 ℃ under a nitrogen stream, thereby obtaining dried PPS. The obtained dried PPS resin in 210 degrees C in 1-chloronaphthalene completely dissolved, GPC measurement, weight average molecular weight 48,600, dispersity is 2.66.

< reference example 2 > (B) thermoplastic resin having glass transition temperature of 100 ℃ or higher

Polyetherimide (hereinafter PEI): ULTEM (registered trade Mark) 1000, manufactured by GE corporation, having a glass transition temperature of 220 DEG C

Polyethersulfone (PES): SUMIKAEXCEL (registered trademark) 3600G manufactured by Sumitomo chemical Co., Ltd., glass transition temperature of 225 deg.C

Modified polyphenylene ether (m-PPE): "Iupiace" (registered trademark) YPX100L, manufactured by Mitsubishi Chemical Corporation, glass transition temperature of 211. degC

< reference example 3 > (C) Compound having 1 or more groups selected from epoxy group, amino group and isocyanate group

(C-1) 3-isocyanatopropyltriethoxysilane: KBE9007, manufactured by shin-Etsu chemical industries Ltd

(C-2)2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane: KBM303, manufactured by shin-Etsu chemical industries Ltd

(C-3) 3-aminopropyltriethoxysilane: KBE-903, manufactured by shin-Etsu chemical industries, Ltd

< reference example 4 > carbon fiber bundle

(CF-1): carbon fiber bundle (Toray Industries, Inc. manufactured under the brand name T700S-12K)

Examples 1 to 7 and comparative examples 1 to 6 (methods for producing pellets of resin compositions)

The raw materials except for the carbon fiber bundles shown in table 1 were dry-blended at the ratios shown in table 1, and then melt-kneaded using a TEX30 α type twin-screw extruder (screw diameter 30mm, L/D45, kneading part 5, co-rotating full-mesh type screw) manufactured by japan steel manufacturing provided with a vacuum vent at a barrel temperature set so that the resin temperature at the die exit became 300 ℃ under conditions of a screw rotation speed of 300rpm and a discharge amount of 20Kg/hr, pelletized by a strand cutter, and subjected to the above evaluation. The evaluation results are shown in table 1.

Examples 1 to 7 and comparative examples 4 to 6 (methods for producing fiber-reinforced resin base material) ]

16 bobbins (bobbins) around which carbon fiber bundles are wound are prepared, and the carbon fiber bundles are continuously fed out from the bobbins by thread guides (thread guides). The resin composition obtained by the above method, which is quantitatively supplied from a filled feeder, is impregnated into the continuously fed carbon fiber bundles in an impregnation die. The carbon fiber impregnated with the resin composition in the impregnation die was continuously drawn from the nozzle of the impregnation die at a drawing speed of 1m/min using a drawing roll. The temperature at which the carbon fiber is drawn is referred to as a processing temperature. The drawn carbon fiber bundle is passed through a cooling roll to cool and solidify the resin composition, and is wound up as a continuous fiber-reinforced resin base material by a winder. The obtained fiber-reinforced resin base material had a thickness of 0.08mm and a width of 50mm, and a fiber-reinforced resin base material in which reinforcing fibers were aligned in one direction and had a volume content of 60% was obtained. The obtained fiber-reinforced resin base material was subjected to the above evaluation. The evaluation results are shown in table 1.

[ Table 1]

The results of examples 1 to 7 and comparative examples 1 to 6 are compared.

In example 1, the heat resistance of the polymer was equivalent to that of comparative example 1 containing no (CF-1), and the glass transition temperature Tg1 was 110 ℃, but in the composite product, the heat resistance was significantly improved by increasing the temperature to Tg1 — 125 ℃. In addition, according to FIGS. 1 and 2, in comparative example 5 in which PEI containing no component (B) was used, Tg1 of the composite was lowered from 125 ℃ to 110 ℃ and bending strain at 110 ℃ was lowered from 1.1% to 0.7%, with the result that heat resistance was impaired. In comparative example 6, which contained no component (C-1) as compared with example 1, it was found that the improvement effect could not be sufficiently exhibited if component (B) or component (C) was not contained in the fiber-reinforced resin substrate impregnated with the PPS resin composition of the present invention, because the Tg1 of the composite product was lowered from 125 ℃ to 110 ℃ as compared with example 1, and the impregnation was poor, and the surface quality was lowered.

Further, it is found that examples 3 and 4 in which the component (B) was changed to a component other than PEI and examples 5 and 6 in which the component (C) was changed to a component other than (C-1) were each a composite material having excellent heat resistance and mechanical strength as in example 1.

Industrial applicability

The fiber-reinforced resin base material and the molded article thereof according to the first and second aspects of the present invention exhibit excellent characteristics, and can be used for various applications such as aircraft parts, automobile parts, electric and electronic parts, building members, various containers, daily necessities, miscellaneous goods for daily use, and sanitary goods. The fiber-reinforced resin base material and the molded article thereof according to the embodiment of the present invention are particularly preferably used for applications to aircraft engine peripheral parts, aircraft part external decorative parts, automobile body parts and vehicle frames, automobile engine peripheral parts, automobile hood internal parts, automobile gear parts, automobile interior decorative parts, automobile external decorative parts, intake and exhaust system parts, engine cooling water system parts, automobile electrical parts, and electrical and electronic parts, which require impregnation property, heat aging resistance, and surface appearance, among others. Specifically, the fiber-reinforced resin and the molded article thereof according to the embodiment of the invention are preferably used for aircraft engine peripheral parts such as fan blades, aircraft-related parts such as landing gear cases, winglets, spoilers, edge portions, rudders, elevators, dampers, ribs (rib), automobile body parts such as various sheets, front portions of the bodies, underbody portions, various pillars, various members, various frames, various beams, various brackets, various rails, and various hinge portions, automobile engine peripheral parts such as engine covers, intake pipes, timing belt covers, intake manifolds, pipe covers, throttle bodies, and radiator fans, top and bottom portions of radiator tanks, cylinder covers, oil pans, brake pipes, pipes for fuel piping, and exhaust system parts, and automobile engine covers such as gears, actuators, bearing supports, bearing covers, chain guides, chain guide plates, and the like, Automobile gear parts such as chain tighteners, gear lever brackets, steering wheel lock brackets, lock cylinders, door handles in automobiles, door handle cases, rearview mirror frames, air conditioner switches, instrument panels, console boxes, storage cases, automobile interior parts such as steering wheels and interior trims, automobile exterior parts such as front covers, rear fenders, filler caps, doors, head covers, rearview mirrors, tailgate plates, license plate trims, roof side rails, engine seat brackets, rear trims, rear spoilers, trunk lids, rocker panels, molding lines, lamp covers, air outlet grilles, fenders and side sills, intake manifolds, intercooler intake pipes, turbo chargers, exhaust pipe covers, inner wall covers, bearing supports, engine mounts, engine top covers, mufflers, and throttle bodies, intake and exhaust system parts such as chain covers, thermostat cases, outlet pipes, radiator tanks, alternators, alternator, engine room temperature control systems, and the like, And engine cooling water system components such as ducts, connectors, wire harness connectors, motor components, lamp holders, vehicle-mounted sensor switches, automobile electrical components such as combination switches, electric/electronic components such as generators, motors, transformers, converters, voltage regulators, rectifiers, resistors, inverters, relays, power contacts, switchgears, interrupters, switches, knife switches, multipole rods, motor housings, television housings, notebook computer housings and internal components, CRT display housings and internal components, printer housings and internal components, cellular phones, mobile computers, portable terminal housings and internal components such as handheld mobile devices, housings and housings for ICs or LEDs, condenser flaps, fuse holders, various gears, various housings, electrical components such as industrial cabinets, connectors for SMT, electrical components such as power distribution systems, and the like, Card connectors, sockets, coils, bobbins, sensors, LED lamps, sockets, resistors, relays, relay housings, reflectors, small switches, power supply components, bobbins, capacitors, variable capacitor housings, optical pickup chassis, resonators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, earphones, small motors, head bases, power modules, Si power modules, SiC power modules, semiconductors, liquid crystals, FDD brackets, FDD chassis, motor brush holders, transformer components, parabolic antennas, computer-related components, and the like.