JP2016216565A - Continuous fiber-reinforced polycarbonate resin prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a continuous fiber-reinforced polycarbonate prepreg having excellent heat melting impregnability and bending properties.SOLUTION: The problem is solved by melting (A) a polycarbonate resin having a melt viscosity at 250°C of higher than 100 Pa s and 1000 Pa s or less and impregnating a continuous fiber-reinforced material (B) with it.SELECTED DRAWING: None

Description

  The present invention relates to a prepreg made of continuous fiber reinforced polycarbonate resin containing a specific polycarbonate and a continuous fiber reinforcement. More specifically, the present invention relates to a prepreg made of continuous fiber reinforced polycarbonate resin having high resin impregnation property and excellent toughness by selecting a polycarbonate resin having a specific melt viscosity.

  A fiber-reinforced composite material (hereinafter sometimes referred to as “FRTP”) using a thermoplastic resin as a matrix is already widely known. Such FRTP is usually a single strand, a unidirectional sheet (UD sheet), a woven fabric, or a non-woven fabric as well as a composite material (hereinafter sometimes referred to simply as “thermosetting resin composite”) having a thermosetting resin as a matrix. Is used for manufacturing a prepreg obtained by impregnating a resin in a reinforcing fiber of the form, and the prepreg is subjected to press molding or filament winding molding (FW molding) to manufacture products such as structural members and various parts.

  Since FRTP has the following advantages over thermosetting resin composites, it has recently attracted attention as a high-strength, high-rigidity, and lightweight material. Thermosetting resin composites require time for complete curing from the prepreg and may have problems with productivity. In addition, since the composite cannot be bent after the prepreg is cured, it is likely to be subjected to processing method and shape restrictions. On the other hand, FRTP is excellent in productivity and can be bent to some extent by softening the matrix resin again, and the processing can be repeated. Furthermore, thermosetting resin composites are not preferable in terms of environmental load and cost because it is difficult to effectively use them in recycling scraps and scraps. On the other hand, FRTP plasticizes cutting scraps and end materials again, and makes it possible to freely create other molded products. In general, there is a great expectation for FRTP, but more specifically, for example, a plate material made of a carbon fiber reinforced composite material that can be bent is required.

  As an example of the use of FRTP, there is a prepreg prepared by using a continuous fiber such as glass fiber or carbon fiber to prepare a unidirectionally aligned fiber sheet or woven or knitted fabric and a thermoplastic resin. These prepregs have the advantage that the volume content of the fiber can be increased, and have excellent elastic modulus and strength in the fiber orientation direction.

  In the production of prepregs using FRTP, the impregnation property of the matrix resin into the continuous fibers is important, which greatly affects the mechanical properties such as strength and the appearance. As a method for producing an FRTP prepreg, a solution method, a hot melt method, a slurry method, a fluidized bed method and the like are generally known. Among them, a hot press method in which a resin component is melted and impregnated into continuous fibers is simple, but a good product cannot be obtained with a polycarbonate having low resin melt flowability.

  Patent Document 1 relates to a chopped strand prepreg using a thermoplastic resin in which the thermoplastic resin has a melt viscosity in the range of 1,000 to 15,000 poise, and uses a FRTP plate cut into strips. Therefore, there is a problem that sufficient rigidity cannot be obtained when molding a large molded product.

  Patent Document 2 describes a composite material composed of a thermoplastic resin and carbon fibers. However, since the thermoplastic resin used has a high viscosity and poor impregnation with carbon fibers, the pellets were freeze-ground. It is described that it is preferable to spray a powdery resin. Moreover, the prepreg manufactured from the composite material using the two-dimensional randomly oriented carbon fiber described in Patent Document 2 may be inferior in elastic modulus and strength.

  Patent Document 3 describes a prepreg made of carbon fiber reinforced polycarbonate in which carbon fibers using polycarbonate having a melt viscosity at 250 ° C. of 1 to 100 Pa · s are aligned in one direction. However, in the prepreg described in Patent Document 3, since the polycarbonate has a low viscosity, there is a problem that mold fouling due to a low molecular component is likely to occur at the time of heat forming, and the strength when bent is insufficient.

Patent No. 2507565 JP 2011-178890 A JP 2014-91825 A

  An object of the present invention is to provide a prepreg made of continuous fiber reinforced polycarbonate resin which is excellent in hot melt impregnation property and bending property.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have used a polycarbonate resin having a specific viscosity, thereby impregnating the polycarbonate resin with continuous reinforcing fibers, which has been a problem in the past, and a prepreg made of polycarbonate resin. Has been found to improve the bending properties.

  That is, the present invention relates to the following prepreg made of continuous fiber reinforced polycarbonate resin.

[1] A prepreg made of a fiber reinforced polycarbonate resin obtained by melt-impregnating a continuous fiber reinforcement (B) with a polycarbonate resin (A) having a melt viscosity at 250 ° C. higher than 100 Pa · s and not higher than 1000 Pa · s.

[2] The fiber reinforced polycarbonate resin prepreg according to [1], wherein the continuous fiber reinforcement (B) has a volume content (Vf value) of 30 to 60%.

[3] The fiber reinforced polycarbonate resin prepreg according to [1] or [2], wherein the continuous fiber reinforcement (B) contains glass fibers.

[4] The fiber-reinforced polycarbonate resin prepreg according to [3], wherein the glass fiber contains E glass.

[5] The fiber-reinforced polycarbonate resin prepreg according to any one of [1] to [4], wherein the polycarbonate resin (A) has a melt viscosity at 250 ° C. of 300 to 700 Pa.s.

  In the prepreg made of continuous fiber reinforced polycarbonate resin according to the present invention, the polycarbonate resin has a high resin impregnation property to the fiber and is excellent in the bending property of the prepreg. It can use suitably for a sheet and a film.

  Hereinafter, the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which does not deviate from the summary, it can change arbitrarily and can implement.

[Polycarbonate resin (A)]
The polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as “component (A)”) is obtained by reacting a dihydroxy compound or a small amount thereof with a phosgene or a carbonic acid diester. Or a branched thermoplastic polymer or copolymer. The production method of the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method) can be used. Moreover, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

  Examples of the raw material dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4. -Dihydroxy diphenyl etc. are mentioned, Preferably bisphenol A is mentioned. A compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above-mentioned dihydroxy compound can also be used.

  In order to obtain a branched polycarbonate resin, a part of the above-mentioned dihydroxy compound is mixed with the following branching agents, namely phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3, 1,3,5- Polyhydroxy compounds such as tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), It may be substituted with a compound such as 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Relative Dorokishi compound is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As the polycarbonate resin (A), among those described above, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other dihydroxy compounds Polycarbonate copolymers derived from are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure.

  The polycarbonate resin mentioned above may be used individually by 1 type, and may mix and use 2 or more types.

The polycarbonate resin (A) used in the present invention has a melt viscosity at 250 ° C. higher than 100 Pa · s and 1,000 Pa.s. Polycarbonate that is less than or equal to s is used. The melt viscosity in the present invention refers to a viscosity value measured at a shear rate of 0 sec ⁻¹ or in the vicinity thereof measured by a meltable viscometer such as a capillary rheometer. However, when the viscosity is measured at a shear rate of 0 sec ⁻¹ , the measured value is often unstable. Therefore Specifically measure the melt viscosity of more than three arbitrary points between the shear rate 100~10000sec ^-1, at approximate expression Carreau model, the present invention the value obtained by extrapolating to a shear rate of 0 sec ^-1 It can be used as a viscosity value.

When the above-mentioned melt viscosity is 100 Pa.s or less, the matrix resin becomes brittle, so that sufficient mechanical strength such as bending characteristics cannot be obtained. On the other hand, when the melt viscosity is higher than 1000 Pa.s, Since the fluidity is insufficient, the impregnation property of the fiber reinforced polycarbonate resin prepreg becomes insufficient, and the appearance and mechanical strength may be insufficient. The melt viscosity at 250 ° C. of the polycarbonate resin (A) used in the present invention is preferably 300 to 700 Pa.s, and more preferably 500 to 700 Pa.s.
The polycarbonate resin (A) is preferably an aromatic polycarbonate resin. This is because the aromatic polycarbonate resin is particularly excellent in transparency, impact resistance, heat resistance and the like.

[Continuous fiber reinforcement (B)]
The fiber-reinforced polycarbonate resin prepreg of the present invention may be referred to as a continuous fiber reinforcement (B) (hereinafter referred to as “component (B)”) in order to enhance bending properties such as bending elastic modulus and bending strength of the molded product. ) Is impregnated in the polycarbonate resin (A).

  As the continuous fiber reinforcement (B) used in the present invention, glass fiber or carbon fiber can be used. And since it is excellent in the reinforcement effect of a polycarbonate resin composition, as a form of a continuous fiber reinforcement (B), the fiber woven fabrics, such as cloth, or the fiber which opened the fiber bundle and was arranged in one direction is preferable. . The volume content value (Vf value) of the continuous fiber reinforcement is used as an index of the filling amount of the continuous fiber reinforcement, and the volume content value (Vf value) of the continuous fiber reinforcement is preferably 30 to 60%, preferably 35 to 35%. More preferably, it is 50%. This is because if the Vf value is small, the reinforcing reinforcement is not sufficient, and if the Vf value is too large, it is difficult to impregnate the resin with the reinforcing material, resulting in poor appearance and strength.

<Glass fiber>
There is no restriction | limiting in particular in the glass composition of the glass fiber used by this invention, Although what consists of glass compositions, such as A glass, C glass, E glass, etc. can be used, Especially the alkali-free of the following component compositions E glass which is glass is preferable because it does not adversely affect the polycarbonate resin (A).

(E glass composition: mass%)
SiO _2: 52~56
Al ₂ O _3: 12~16
Fe ₂ O ₃ : 0 to 0.4
CaO: 16-25
MgO: 0-6
B ₂ O _3: 5~13
TiO _2: 0~0.5
_{R 2 O (Na 2 O +} K 2 O): 0~0.8

  The glass fiber may be surface-treated with a surface treatment agent to be described later, and by such surface treatment, the adhesiveness between the resin component and the glass is improved, and high mechanical strength can be achieved. It becomes like this.

<Carbon fiber>
There is no restriction | limiting in particular in carbon fiber, Well-known carbon fibers, such as a polyacrylonitrile (PAN) type | system | group and a petroleum and coal pitch type | system | group, can be used.

[Surface treatment agent for reinforcing fibers]
Especially in this invention, in order to improve the adhesiveness of a continuous fiber reinforcement (B) and a resin component, the decomposition | disassembly of polycarbonate resin (A) by contact with glass fiber and polycarbonate resin (A) is suppressed. Therefore, it is preferable to use what processed the surface of the continuous fiber reinforcement (B) with the surface treating agent. Examples of suitable surface treatment agents include silane coupling agents such as aminosilane and epoxysilane, and silicone compounds.

[Other ingredients]
The fiber-reinforced polycarbonate resin prepreg of the present invention may contain other components as necessary in addition to the polycarbonate resin (A) and the continuous fiber reinforcing material (B). Examples of other components that can be contained in the polycarbonate resin composition of the present invention include the following.

<Phosphorus heat stabilizer>
The fiber-reinforced polycarbonate resin prepreg of the present invention can contain a phosphorus heat stabilizer. Phosphorus heat stabilizers are generally effective in improving the residence stability at high temperatures and the heat resistance stability when using resin molded products when melt-kneading resin components.

  Examples of the phosphorus-based heat stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, trivalent phosphorus is included, and it is easy to express a discoloration suppressing effect. Phosphites such as phosphites and phosphonites are preferred.

<Antioxidant>
The polycarbonate resin composition used in the present invention preferably contains an antioxidant such as a hindered phenol-based antioxidant as desired. By containing the antioxidant, it is possible to suppress hue deterioration and deterioration of mechanical properties during heat retention.

<Other additives>
The polycarbonate resin composition used in the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include mold release agents, ultraviolet absorbers, dyes and pigments, antistatic agents, flame retardants, anti-dripping agents, impact strength improvers, and other resins other than the components (A) and (B). Is mentioned.

(Other inorganic components)
When making a continuous fiber reinforced prepreg made of polycarbonate resin of the present invention, by adding glass short fibers or carbon short fibers having a fiber length of 10 mm or less as inorganic components other than the continuous fiber reinforcing material (B) component, further mechanical properties Can be increased. Examples of the short fiber filler include short glass fibers, short carbon fibers, wollastonite, various inorganic whiskers and the like.
Moreover, the anisotropy at the time of shrinkage can also be improved by adding a plate-like or spherical filler. Examples of the plate-like filler include glass flakes, mica and talc, and examples of the spherical filler include glass beads and silica beads.

<Method for producing prepreg made of continuous fiber reinforced polycarbonate resin>
The method for producing a prepreg made of continuous fiber reinforced polycarbonate resin is a method in which a molten resin is poured from a T-die of an extruder, joined with an unrolled continuous fiber sheet and impregnated, and a method in which a powder resin is dispersed and heated and melted on continuous fibers There is a method of heat laminating a resin film. Since the polycarbonate used in the prepreg made of continuous fiber reinforced polycarbonate resin of the present invention is excellent in fluidity, a method of discharging and impregnating a molten resin from an extruder, and a method of thermally laminating a resin into a film are particularly preferably used.

  The step of impregnating a specific polycarbonate into a continuous fiber by a melting method uses a method of solidifying a prepreg after melt penetration by a combination of a heating press and a cooling press, in addition to the method using the extruder, a double belt press. There is a method of providing a heating zone and a cooling zone.

<Shape and characteristics of prepreg>
The thickness of the fiber-reinforced polycarbonate resin prepreg of the present invention is usually 50 to 500 μm, preferably 150 to 350 μm per sheet. For example, it is 170-305 micrometers. If the thickness of one prepreg is less than 50 μm, the resin component cannot be sufficiently impregnated, so that the obtained prepreg may be opened and difficult to handle. On the other hand, if the thickness of one prepreg exceeds 500 μm, there is a possibility that sufficient physical properties cannot be obtained because the content of reinforcing fibers is reduced.
The continuous fiber reinforced polycarbonate resin prepreg of the present invention has a high impregnation property with respect to the continuous fiber of the polycarbonate resin at the time of manufacture, and the manufactured prepreg has excellent bending characteristics. For this reason, it is possible to manufacture the molded article excellent in the bending characteristic by laminating | stacking and heat-molding the prepreg made from the continuous fiber reinforced polycarbonate resin of this invention, for example.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

<Measurement of melt viscosity>
For measuring the melt viscosity of the polycarbonate resin (A) component, Capillograph 1D PMD-C manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The value obtained by extrapolating from the Carreau model approximation was used as the viscosity value at a shear rate of 0 sec ⁻¹ .

<Evaluation of continuous fiber impregnation>
The impregnation property of the continuous fibers of polycarbonate was evaluated by observing the fracture surface in the thickness direction of the continuous fiber resin sheet having a width of 20 mm of the prepreg with a microscope (× 50 times). Good if there is almost no air bubbles between the resin and the fiber and has good adhesion, good if there are few air bubbles between the resin and the fiber, and good adhesion, acceptable if there are many air bubbles and low adhesion did.

<Bending elastic modulus>
The flexural modulus was measured with Autograph AG-5000B manufactured by Shimadzu Corporation in accordance with JIS K7074. In addition, what destroyed the resin part at the time of sample cutting was made into the defect.

<Measurement of fiber volume content (Vf value)>
As the fiber volume content value of the prepreg made of continuous fiber reinforced polycarbonate resin, the density of the test piece for bending test was calculated by a method according to JIS K7112. Subsequently, in accordance with JIS K7075, the thermoplastic resin was burned off using a burner, and the fiber mass content was calculated. Finally, the Vf value of the test piece was calculated from the obtained density and fiber mass content and the density of carbon fiber and glass fiber.

[Materials used]
<Bisphenol A type polycarbonate resin (A)>
(A-1) “Iupilon (registered trademark) H-4000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., 250 ° C. melt viscosity 700 Pa · s
(A-2) “Iupilon (registered trademark) HL-7001” manufactured by Mitsubishi Engineering Plastics Co., Ltd., 250 ° C. melt viscosity 500 Pa · s
(A-3) “Iupilon (registered trademark) HL-8000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., 250 ° C. melt viscosity 300 Pa · s
(A-4) “Iupilon (registered trademark) H-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., 250 ° C. melt viscosity 1800 Pa · s
(A-5) Polycarbonate having a melt viscosity of 90 Pa · s at 250 ° C. produced by an interfacial polymerization method <continuous fiber reinforcement (B)>
(B-1) Glass fiber: manufactured by Nitto Boseki Co., Ltd. RS 240QR-483AS (2400 tex)
(B-2) Carbon fiber: PAN-based carbon fiber Pyrofil TRH50 60M RJ (60k) manufactured by Mitsubishi Rayon Co., Ltd.
(B-3) Glass fiber cloth: 258 manufactured by Asahi Glass Co., Ltd. (thickness 0.093 mm, 106.5 g / m 2, twill)
(B-4) Carbon fiber cloth: CFP3110 (30k, 160g / m2, plain weave) manufactured by Arisawa Manufacturing Co., Ltd.

[Examples 1 to 12, Comparative Examples 1 to 4]
-Preparation of resin film The films of the resin compositions described in Tables 1 and 2 were produced as follows. First, using a film extruder with a screw diameter of 26 mm, barrel temperature 250 ° C., die (D) temperature 250 ° C., pressure roll (R 1) temperature 40 ° C., first cooling roll (R 2) temperature 150 ° C., second cooling roll ( R3) Under the condition of a temperature of 130 ° C., a film having a thickness of 100 μm was obtained from each material resin.

<Preparation of prepreg made of continuous fiber reinforced polycarbonate resin>
Centering on a cloth made of continuous fibers and a reinforcing fiber layer aligned in one direction opened in advance, the resin film and release paper were stacked in this order on the upper and lower surfaces, and set in a heating press. As a setting condition of the heating type press apparatus, a heating temperature of 240 ° C., 1 MPa, and 3 minutes were heated, and then a prepreg having a thickness of 100 to 370 μm was obtained by cooling with a cooling plate set to 20 ° C. for 5 minutes.

<Creation of composite sheet for physical property evaluation>
The continuous fiber reinforced polycarbonate resin prepreg was cut to 70 × 70 mm, and the number of sheets to be stacked was adjusted so that the thickness after pressing was 1 mm. The superposed prepreg was heated and pressed at a heating temperature of 210 ° C. and 1 MPa for 3 minutes, and then cooled by a cooling plate set at 20 ° C. for 5 minutes. In the case of a unidirectional fiber, 0 ° and 90 ° were alternately stacked.
The obtained composite plate after pressing was cut into a width of 15 mm and a length of 60 mm (fiber direction), and these were used as test pieces for bending tests.

The composition of the prepregs of the above Examples and Comparative Examples, and the properties of the prepreg and composite sheet test pieces are summarized in the following table.

In each of the above Examples, the results of the prepreg impregnation property and the flexural modulus of the composite sheet were all good. On the other hand, in Comparative Examples 1 and 3 in which the melt viscosity at 250 ° C. of the used polycarbonate resin is lower than 100 Pa · s, the flexural modulus of the composite sheet is inferior, and in Comparative Examples 2 and 4 higher than 1000 Pa · s. Since the composite sheet was poor in impregnation property, the composite sheet could not be easily opened, the bending characteristics were lowered, and the bending elastic modulus could not be measured. In Examples 7 and 11 in which the Vf value (volume content value) of the prepreg is lower than 30%, the flexural modulus of the composite sheet is slightly inferior to the other examples, and the Vf value is higher than 60%. In Examples 8 and 12, since the impregnation properties were slightly inferior to those of other examples, the flexural modulus was not measurable. However, also in these examples, prepregs that can be used without any particular problem were obtained.
From the above, it was confirmed that when the melt viscosity of the polycarbonate resin (A) is adjusted to a range higher than 100 Pa · s and 1000 Pa · s or less, the bending elastic modulus and impregnation property of the prepreg are improved. Moreover, it was confirmed that the favorable bending elastic modulus and impregnation property of a prepreg were realizable also by adjusting Vf value (volume content value).

Claims (5)

  A fiber reinforced polycarbonate resin prepreg obtained by melt-impregnating a continuous fiber reinforcement (B) with a polycarbonate resin (A) having a melt viscosity at 250 ° C. higher than 100 Pa · s and not higher than 1000 Pa · s.   The fiber-reinforced polycarbonate resin prepreg according to claim 1, wherein the continuous fiber reinforcement (B) has a volume content (Vf value) of 30 to 60%.   The fiber reinforced polycarbonate resin prepreg according to claim 1 or 2, wherein the continuous fiber reinforcement (B) contains glass fibers.   The fiber-reinforced polycarbonate resin prepreg according to claim 3, wherein the glass fiber contains E glass. The fiber reinforced polycarbonate resin prepreg according to any one of claims 1 to 4, wherein the polycarbonate resin (A) has a melt viscosity at 250 ° C of 300 to 700 Pa.s.