WO2019065432A1 - 繊維強化複合材料用熱硬化性樹脂組成物、プリフォーム、繊維強化複合材料及び繊維強化複合材料の製造方法 - Google Patents
繊維強化複合材料用熱硬化性樹脂組成物、プリフォーム、繊維強化複合材料及び繊維強化複合材料の製造方法 Download PDFInfo
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Definitions
- the present invention relates to a thermosetting resin composition used for a fiber-reinforced composite material, a preform, a fiber-reinforced composite material using the same, and a method for producing a fiber-reinforced composite material.
- Fiber-reinforced composite materials consisting of reinforcing fibers and matrix resin can be used in material design taking advantage of reinforcing fibers and matrix resin, and their applications are expanded in the aerospace field, sports field, general industrial field, etc. .
- thermosetting resin epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, bismaleimide resin, cyanate resin and the like are used.
- fiber reinforced composite materials such as carbon fiber reinforced composite materials have recently been in increasing demand, particularly for aircraft and automotive applications.
- fiber reinforced composite materials in order to apply a fiber reinforced composite material more generally, a material with low cost and low environmental impact is required.
- the matrix resin used in the conventional method for producing a fiber-reinforced composite material as described above is a liquid or semi-solid resin at normal temperature in order to sufficiently impregnate the reinforcing fiber base.
- a resin tends to remain in a resin preparation facility or a resin injection facility at the time of use, and a large amount of loss tends to occur.
- a prepreg method after a resin film of a matrix resin is produced, a step of impregnating the resin into a reinforcing fiber is performed.
- auxiliary materials such as a film having releasability are often required, and the cost tends to be high.
- thermosetting resin when a liquid or semi-solid thermosetting resin is used as a one-component resin composition in which a main agent, a curing agent, and a catalyst component are compatible in advance, balance between high-speed curing and storage stability of the resin is required. It is difficult to take.
- a two-component resin composition may be used in which a main agent component and a curing agent / catalyst component are separately prepared from a resin system excellent in high-speed curability and mixed immediately before use. Operations and facilities at the manufacturing site become complicated.
- Patent Document 1 discloses a powdery epoxy resin composition obtained by pulverizing a solid crystalline epoxy resin and a solid curing agent at 30 ° C., pressing the same, and then pulverizing it again.
- Patent Document 2 discloses a resin composition comprising a crystalline epoxy resin for use in fiber reinforced composite materials, a crystalline curing agent, and a curing accelerator.
- Patent Document 1 The material described in Patent Document 1 is a solid resin composition in which composition unevenness of a cured resin is unlikely to occur.
- this material is used to make a fiber-reinforced composite material, surface pits and internal voids are generated, and the strength characteristics are greatly reduced. there were.
- Patent Document 2 The material described in Patent Document 2 is a resin composition in which a crystalline epoxy resin, a crystalline curing agent, and a catalyst are compatible. However, the said resin composition was not excellent in the balance of high-speed curability and storage stability of resin.
- the object of the present invention is a fiber-reinforced composite that ameliorates the disadvantages of the above-mentioned prior art, is excellent in the balance between high-speed curing and storage stability, and is easy to handle at room temperature and impregnating to reinforcing fiber base It is an object of the present invention to provide a thermosetting resin composition for material, and a preform for fiber reinforced composite material, and a fiber reinforced composite material using the same.
- the present invention for solving the above problems is as follows.
- thermosetting resin composition for a fiber-reinforced composite material having a specific gravity of 0.90 to 1.30 and a complex viscosity ** of 1 ⁇ 10 7 Pa ⁇ s or more in dynamic viscoelasticity measurement at 25 ° C.
- thermosetting resin composition for a fiber-reinforced composite material which has a porosity of 0.1 to 25% and a complex viscosity ** of 1 ⁇ 10 7 Pa ⁇ s or more in dynamic viscoelasticity measurement at 25 ° C.
- thermosetting resin composition for a fiber reinforced composite material which comprises the thermosetting resin composition for a fiber reinforced composite material according to (1) or (2) and a dry reinforcing fiber base.
- thermosetting resin composition for a fiber-reinforced composite material according to (1) or (2), wherein the thermosetting resin in the molded article A fiber reinforced composite material, wherein the composition exists as a cured product.
- thermosetting resin composition for fiber reinforced composite materials according to the above (1) or (2) and forming it while impregnating the dry reinforcing fiber base, and the dry reinforcing fiber group
- a method for producing a fiber reinforced composite material comprising a curing step of curing a thermosetting resin composition impregnated in a material and molded.
- thermosetting resin composition for a fiber-reinforced composite material which is excellent in the balance between high-speed curability and storage stability, is easy to handle at normal temperature, and is excellent in impregnating ability to a reinforcing fiber substrate; It is providing the preform for fiber reinforced composite materials using the same, and a fiber reinforced composite material.
- thermosetting resin composition for fiber-reinforced composite materials of the present invention has a domain of each component of [A] main agent, and [B] curing agent and / or [C] catalyst, and specific gravity Is 0.90 to 1.30 and complex viscosity ** in dynamic viscoelasticity measurement at 25 ° C. is 1 ⁇ 10 7 Pa ⁇ s or more.
- thermosetting resin composition for fiber reinforced composite materials may be simply referred to as “the thermosetting resin composition”.
- thermosetting resin composition for fiber reinforced composite materials of the present invention comprises [A] a main ingredient, and domains of each component of [B] curing agent and / or [C] catalyst,
- the thermosetting resin composition for a fiber-reinforced composite material having a modulus of 0.1 to 25% and a complex viscosity ** of 1 ⁇ 10 7 Pa ⁇ s or more in dynamic viscoelasticity measurement at 25 ° C.
- thermosetting resin composition of the present invention has a complex viscosity ** of 1 ⁇ 10 7 Pa ⁇ s or more in dynamic viscoelasticity measurement at normal temperature.
- normal temperature refers to the thing of 25 degreeC.
- the thermosetting resin composition has the above-mentioned complex viscosity ⁇ * , it becomes solid at normal temperature. Therefore, the thermosetting resin composition of the present invention has good handleability at normal temperature, and easily suppresses the cost when producing a fiber-reinforced composite material.
- the upper limit of the complex viscosity ** is not particularly limited, but is usually about 1 ⁇ 10 9 Pa ⁇ s.
- ARES-G2 (manufactured by TA Instruments) is used for measurement of dynamic viscoelasticity. After setting the sample on a parallel plate of 8 mm using this measuring device, add a pulling cycle of 0.5 Hz and measure at a temperature rising rate of 1.5 ° C./min in a temperature range of 0 to 300 ° C. The complex viscosity ⁇ * can be measured.
- thermosetting resin composition of the present invention has various generally used thermosetting resins that can be applied within the range satisfying the requirements of the present invention.
- thermosetting resin for example, epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin, cyanate resin, benzoxazine resin, urethane resin, urea resin and the like can be suitably applied.
- the main agent [A] used in the thermosetting resin composition of the present invention is a component which causes a curing reaction to proceed by heating to form a crosslinked structure.
- the main agent is preferably a monomer component.
- As the main agent for example, a compound having an epoxy group, a compound having a phenol group, a compound having a vinyl group, a compound having a bismaleimide structure, a compound having an isocyanate group, an oxazine compound, a compound having a hydroxyl group, an amino group
- a thermosetting component such as a compound having
- the thermosetting resin preferably contains an epoxy resin from the viewpoint of adhesion to reinforcing fibers and handling. And when an epoxy resin is included as a thermosetting resin, it will be said as a [A] main ingredient containing a compound which has one or more, preferably two or more epoxy groups in one molecule.
- the epoxy resin may be composed of only one type of compound having an epoxy group, or may be a mixture of a plurality of types.
- the [B] curing agent used in the present invention is a component that cures the thermosetting resin by being covalently bonded when it becomes compatible with the main agent.
- the thermosetting resin is an epoxy resin
- a compound having an active group capable of reacting with an epoxy group can be used as a curing agent, and an acid anhydride, a phenolic compound, or the like can be used.
- the [C] catalyst used in the present invention is a component that rapidly facilitates the curing reaction due to the sole curing reaction of the main ingredient and / or the bond formation between the main ingredient and the curing agent.
- the thermosetting resin is an epoxy resin, imidazoles, organic phosphorus compounds and the like can be used as the catalyst.
- thermosetting resin composition of the present invention is a thermosetting resin composition having domains of each component of [A] main agent, [B] curing agent, and / or [C] catalyst.
- “having the domain of each component” means that the components in the resin composition are not compatibilized uniformly at the molecular level, and each component is dispersed in the state of having the domain diameter of the micrometer order. It is Usually, each domain has a form in contact at the interface.
- micrometer order refers to a range of 0.1 ⁇ m to 10000 ⁇ m.
- thermosetting resin composition having domains of the respective components can be produced, for example, by mixing powdery raw materials of the respective components and pressing them with a press or the like as described later.
- the present invention is not limited to this method. For example, after heat melting, compatibilizing each component, cooling, and precipitation and solidifying each component for each domain, heat having the domain of each component A curable resin composition can also be obtained.
- the distribution form of the domain of each component can be identified using various two-dimensional mapping methods.
- mapping analysis using active energy rays such as ultraviolet light, visible light, infrared light, electron beams, and X-rays is effective, and those capable of identifying chemical compositions are more preferable.
- the domain diameter of each component is subjected to chemical composition mapping by infrared spectroscopy, 100 domain widths in the range where the absorbance of each component is equal to or higher than the threshold are measured, and the average value is defined as the domain diameter. If it is difficult to determine the component only by infrared spectroscopy, the component may be determined by combining elemental analysis. Alternatively, 100 domain widths of each component observed by a microscope using a staining agent may be measured, and the average value thereof may be used as the domain diameter.
- thermosetting resin composition When the thermosetting resin composition is not compatibilized uniformly at the molecular level, and the thermosetting resin composition has domains of each component, the proportion at which the main agent, the curing agent and / or the catalyst contact each other is Since there are few, it can be set as the thermosetting resin composition which has the outstanding storage stability. In addition, by applying a thermosetting resin system excellent in high-speed curing property, a thermosetting resin composition excellent in the balance between high-speed curing property and storage stability can be obtained.
- the domain diameter of each component in the thermosetting resin composition is preferably 0.5 to 500 ⁇ m, more preferably 1 to 300 ⁇ m, and still more preferably 10 to 200 ⁇ m.
- the domain diameter of each component is 0.5 to 500 ⁇ m, storage stability is sufficiently ensured, and when the thermosetting resin is melted and then cured, it tends to be a cured product with less unevenness.
- thermosetting resin composition of the present invention the product of the curing time x (minutes) at 150 ° C. and the curing reaction progress rate y (%) when stored for 1 week in an environment of 40 ° C. Is preferable, and it is more preferable to satisfy (formula 2).
- the curing time x (minutes) at 150 ° C. is obtained as the curing time when the value of the cure index calculated from the value of the ionic viscosity measured using a dielectric measurement device described later exceeds 90%.
- the curing reaction progress rate y (%) is measured by differential scanning calorimetry (DSC), the calorific value due to the curing reaction of the resin composition immediately after preparation, and the resin composition after storage for 1 week in an environment of 40.degree.
- the calorific value due to the curing reaction is measured, and is calculated from the ratio thereof by using (Equation 5) described later.
- thermosetting resin composition is an index showing the balance between high-speed curing and storage stability of the thermosetting resin composition.
- high-speed curing property and storage stability of the thermosetting resin are in a trade-off relationship, but as described above, the thermosetting resin composition of the present invention is excellent in the balance between high-speed curing property and storage stability.
- the resin composition can be obtained.
- the thermosetting resin composition of the present invention has a [C] catalyst, and relative to 100% by mass of the thermosetting resin composition for fiber reinforced composite materials
- the content is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 2 to 15% by mass.
- the range of the content of the catalyst may be a combination of any of the upper limit and the lower limit of the range of the above content.
- the content of the catalyst of 1 to 30% by mass makes it possible for the thermosetting resin composition to have good high-speed curability and maintain excellent storage stability.
- the ratio of the number of moles of the active group of the [B] curing agent to the number of moles of the active group in the [A] main agent is in the range of 0.5 to 2.0. Preferably, the range is 0.8 to 1.6.
- [A] The mechanical properties and heat resistance of a fiber-reinforced composite material by setting the ratio of the number of moles of the active group of the [B] curing agent to the number of moles of the active group in the main agent to 0.5 to 2.0. It is easy to be excellent.
- the first aspect of the thermosetting resin composition of the present invention has a specific gravity of 0.90 to 1.30, preferably 0.95 to 1.25, and 1.00 to 1.20. Is more preferred.
- the specific gravity range may be a combination of any of the upper limit and the lower limit of the specific gravity range.
- the specific gravity is less than 0.90, a large number of voids exist in the thermosetting resin composition, the resin becomes brittle, and the handleability is deteriorated, and when it is formed into a fiber-reinforced composite material, it contains a large amount of voids inside. It is easy to become a body.
- specific gravity exceeds 1.30 the density of a thermosetting resin composition may be too high, and it may become difficult to melt.
- the porosity is 0.1 to 25%, preferably 0.1 to 20%, and 0.1 to 16%. More preferable.
- the porosity is calculated by the following (Equation 3) from the specific gravity of the thermosetting resin composition and the value of the specific gravity of the thermosetting resin composition substantially without voids.
- the specific gravity of the thermosetting resin composition having substantially no voids is calculated by adding the specific gravity of the component contained in the thermosetting composition by the volume fraction of the compounding ratio.
- Porosity (%) 100 ⁇ (specific gravity of thermosetting resin composition) / (specific gravity of thermosetting resin composition without voids) ⁇ 100 (Equation 3)
- the porosity is 0.1 to 25%, while having sufficient handleability at normal temperature, the impregnating property to the reinforcing fiber base is also excellent.
- thermosetting resin composition of the present invention as described above is, for example, after sufficiently mixing the powdery materials of the respective components of the [A] main agent and the [B] curing agent and / or the [C] catalyst. It can be manufactured by pressurizing and pressing each component.
- the pressure applied at this time is preferably 5 to 100 MPa, and more preferably 10 to 50 MPa.
- the pressure range may be a combination of any of the upper limit and the lower limit of the pressure range. By setting the pressure in the range of 5 to 100 MPa, each component can be easily pressure-bonded and the handleability of the resin composition can be easily improved.
- thermosetting resin composition of this invention is not specifically limited, A thing of various forms, such as a lump, rod shape, plate shape, a film, a fiber, a granule, can be used. In particular, from the viewpoint of the impregnating ability to the reinforcing fiber and the handleability, it is preferable to be in the form of block, plate or granules.
- the major axis of the thermosetting resin composition of the present invention is preferably 1.5 mm or more, more preferably 3 mm or more, and still more preferably 10 mm or more. If the major diameter is less than 1.5 mm, the resin composition is heated and melted, air is easily contained when impregnated into the fiber-reinforced substrate, and when the resin is cured, the amount of voids inside the molded body increases, and the strength is increased. Characteristics tend to deteriorate.
- a major axis refers to the length of the longest part in the thermosetting resin composition. The upper limit of the major axis is not particularly limited, but is usually about 1 m (1000 mm).
- the content of all the crystalline components is preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less in 100% by mass of the thermosetting resin composition. It is more preferable that it is mass% or less, and it is further more preferable that it is 90 mass% or more and 100 mass% or less.
- the content of all the crystalline components includes a plurality of different crystalline components, it means the total content of them.
- the total content of the crystalline components is 70% by mass or more, it becomes easy to simultaneously achieve the handleability at room temperature of the thermosetting resin composition and the impregnating property to reinforcing fibers when heated to a high temperature.
- the crystalline component is a component which is solid at normal temperature and has a melting point at a temperature above normal temperature.
- the melting point can be determined by differential scanning calorimetry (DSC) according to JIS K 7121: 2012 as described later.
- the component which is solid at normal temperature also includes a glassy solid component, but since the viscosity of the glassy solid component is unlikely to decrease even when heated to high temperatures, the impregnation property to reinforcing fibers when heated to high temperatures is poor.
- a glassy solid component is a component which does not have melting
- the glass transition temperature refers to one determined by differential scanning calorimetry (DSC) according to JIS K 7121: 1987. A sample for measurement of glass transition temperature is collected in an aluminum sample pan, and measurement is performed at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere. The midpoint of the displacement of the region where the baseline shifts to the heat absorption side in the DSC curve thus obtained is adopted as the glass transition temperature.
- thermosetting resin composition of the present invention a plurality of crystalline components having a content of 10% by mass or more are present in 100% by mass of the thermosetting resin composition, and among the crystalline components, the melting point is
- the difference between the melting point of the crystalline component having the highest melting point and the melting point of the crystalline component having the lowest melting point is preferably 60 ° C. or less, more preferably 50 ° C. or less, and further preferably 40 ° C. or less preferable.
- thermosetting resin composition of this invention may contain the other component within the range which does not impair the effect of this invention.
- various organic and inorganic fibers such as glass fibers, aramid fibers, carbon fibers and boron fibers are used as dry reinforcing fibers.
- carbon fibers are suitably used because they are lightweight, and fiber-reinforced composite materials excellent in mechanical properties such as strength and elastic modulus can be obtained.
- the dry reinforcing fiber refers to a reinforcing fiber in a state in which the reinforcing resin is not impregnated with the matrix resin. Therefore, the preform for fiber reinforced composite materials of the present invention is different from a prepreg in which a matrix resin is impregnated with reinforcing fibers.
- the dry reinforcing fiber in the present invention may be impregnated with a small amount of binder.
- a binder is a component which binds the interlayer of the reinforced fiber base material laminated
- a dry reinforcement fiber since it is in the state by which the resin composition is impregnated, it does not call it a dry reinforcement fiber.
- the reinforcing fibers may be either staple fibers or continuous fibers, and both may be used in combination.
- continuous fibers are preferably used.
- dry reinforcing fibers are sometimes used in the form of strands, but dry reinforcing fiber substrates obtained by processing reinforcing fibers into mats, woven fabrics, knits, braids, unidirectional sheets and the like are preferably used.
- a woven fabric which is easy to obtain a high Vf fiber-reinforced composite material and is excellent in handleability is preferably used.
- the fiber volume content Vf of the reinforcing fiber is preferably 30 to 85%, more preferably 35 to 70%. It is inside.
- the range of the fiber volume fraction Vf may be a range combining any of the upper limit and the lower limit of the range of the above-mentioned fiber volume fraction Vf.
- the fiber volume fraction Vf of the fiber-reinforced composite material mentioned here is a value defined and measured in accordance with ASTM D3171 (1999). That is, it is a value measured in a state after the reinforcing fiber is impregnated with the thermosetting resin composition and the composition is cured. Therefore, the measurement of the fiber volume content Vf of a fiber reinforced composite material can be represented using the following (Formula 4) from thickness h of a fiber reinforced composite material.
- a specific method of measuring the thickness h of the fiber-reinforced composite material is a method capable of correctly measuring the thickness of the fiber-reinforced composite material, as described in JIS K 7072 (1991), JIS B 7502 (1994) Measure with a micrometer specified in or equivalent or better than this. If the fiber-reinforced composite material has a complicated shape and can not be measured, cut out a sample (a sample having a certain shape and size for measurement) from the fiber-reinforced composite material and measure it be able to.
- the preform for a fiber-reinforced composite material of the present invention comprises the thermosetting resin composition of the present invention and a dry reinforcing fiber base.
- the preform for fiber reinforced composite materials is in the form in which the thermosetting resin composition is in direct or indirect contact with the surface of the dry reinforcing fiber substrate.
- the thermosetting resin composition may be on the dry reinforcing fiber substrate, or the dry reinforcing fiber substrate may be on the thermosetting resin composition. Alternatively, any of these may be stacked.
- the thermosetting resin composition and the dry reinforcing fiber substrate may be in a form in which they are indirectly in contact with each other via a film, a non-woven fabric, or the like.
- the fiber-reinforced composite material of the present invention is a molded article obtained by impregnating the thermosetting resin composition of the present invention with a reinforcing fiber base, and the thermosetting resin composition is present as a cured product in the molded article. It is a thing.
- the fiber reinforced composite material of the present invention can be obtained by impregnating the thermosetting resin composition of the present invention into a dry reinforcing fiber substrate, molding it, and curing the composition.
- the method for producing a fiber-reinforced composite material of the present invention comprises the steps of melting the thermosetting resin composition of the present invention and forming it while impregnating the dry reinforcing fiber base, and impregnating the dry reinforcing fiber base And a curing step of curing the formed thermosetting resin composition.
- the press forming method is particularly preferably used from the viewpoints of productivity and shape freedom of the formed body.
- a preform composed of a thermosetting resin composition and a reinforcing fiber is disposed between a rigid open mold and a flexible film, and the inside is vacuum suctioned while applying atmospheric pressure. It can be thermoformed, or can be thermoformed while being pressurized with a gas or liquid.
- the method for producing the fiber-reinforced composite material of the present invention will be described using an example of the press-forming method.
- the fiber-reinforced composite material of the present invention is prepared, for example, by placing a preform for fiber-reinforced composite material having the thermosetting resin composition of the present invention and dry reinforcing fibers in a mold heated to a specific temperature and pressing it. By pressurizing and heating, the resin composition is melted, impregnated into the reinforcing fiber base, and then cured as it is.
- the temperature of the mold during press molding should be a temperature above the temperature at which the complex viscosity ** of the resin composition used falls to 1 ⁇ 10 1 Pa ⁇ s, from the point of impregnation of the reinforcing fiber substrate. Is preferred.
- thermosetting resin composition of each example, the following resin raw materials were used.
- the unit of the content ratio of the resin composition in Tables 1 to 3 means “parts by mass” unless otherwise specified.
- Thermosetting Resin Composition was obtained by injecting
- thermosetting resin composition The weight of the thermosetting resin composition prepared as described above in air and water at normal temperature was measured, and the specific gravity was calculated by the Archimedes method. The sample to be measured was about 3 g in air weight regardless of the size of the sample. The average of five measurements was taken as the specific gravity of the sample.
- ⁇ Void ratio of thermosetting resin composition The specific gravity of each component contained in the thermosetting resin composition prepared as described above was calculated by the Archimedes method. The specific gravity of the thermosetting resin composition having substantially no voids was calculated by adding the calculated specific gravities of the respective components by the volume fraction of the compounding ratio contained in the thermosetting resin composition.
- thermosetting resin composition was calculated using the above-mentioned (Formula 3) formula.
- a two-dimensional chemical composition mapping was obtained from the infrared absorption peak intensity specific to each component by infrared spectroscopy (total reflection measurement method) of the sample surface .
- a range in which the infrared absorption peak intensity of each component is continuously 1/3 or more of the maximum value is regarded as the domain of the component, and any X axis drawn in the mapping chart The width of the domain on a straight line of direction was measured.
- thermosetting resin composition One hundred domain widths were measured, and the average value was adopted as the domain diameter.
- ⁇ Viscosity measurement of thermosetting resin composition The thermosetting resin composition prepared as described above was used as a sample and measured by dynamic viscoelasticity measurement. ARES-G2 (manufactured by TA Instruments) was used as a measurement device. The sample was set on a parallel plate of 8 mm, a pulling cycle of 0.5 Hz was added, and the complex viscosity ** at 25 ° C. was measured. ⁇ Measurement of 150 ° C. Curing Time x of Thermosetting Resin Composition> In order to confirm the high-speed curability of the thermosetting resin composition prepared as described above, the curing time at the time of heating at 150 ° C.
- dielectric measurement As a dielectric measurement apparatus, an MDE-10 cure monitor manufactured by Holometrix-Micromet was used. A Viton O-ring with an inner diameter of 32 mm and a thickness of 3 mm is installed on the lower surface of the programmable mini-press MP2000 with TMS-1 inch type sensor embedded in the lower surface, temperature of press is set to 150 ° C, resin composition inside O-ring The set was set, the press was closed, and the time change of the ionic viscosity of the resin composition was followed. Dielectric measurements were performed at frequencies of 1, 10, 100, 1000 and 10000 Hz, and the accompanying software was used to obtain a log ( ⁇ ) of frequency-independent ionic viscosity log.
- Cure index ⁇ log ( ⁇ t) -log ( ⁇ min) ⁇ / ⁇ log ( ⁇ max) -log ( ⁇ min) ⁇ ⁇ 100 (Equation 5) Cure index: (unit:%) ⁇ t: Ion viscosity at time t (unit: ⁇ ⁇ cm) ⁇ min: Minimum value of ionic viscosity (unit: ⁇ ⁇ cm) ⁇ max: Maximum value of ionic viscosity (unit: ⁇ ⁇ cm). ⁇ Measurement of reaction progress rate y at 40 ° C. for 1 week storage of thermosetting resin composition> In order to confirm the storage stability of the thermosetting resin composition prepared as described above, the curing reaction progress rate after storage for 1 week in a 40 ° C. environment was measured.
- DSC Differential scanning calorimetry
- thermosetting resin composition at room temperature The handleability at room temperature of the thermosetting resin composition prepared as described above was compared and evaluated in the following three steps. When the thermosetting resin composition is lifted by hand, those without fracture or deformation are “A”, those with partial chipping or slight deformation “B”, easily cracked or deformed when lifted "C” is something that would be done.
- the fiber reinforced composite material was manufactured by the following press molding method.
- Carbon fiber woven fabric CO6343 carbon fiber: T300-3K, structure: plain weave, fabric weight
- a predetermined temperature melting temperature
- About 290 g of the thermosetting resin composition prepared as described above was set on a substrate obtained by laminating 9 sheets of 198 g / m 2 (manufactured by Toray Industries, Inc.). Thereafter, the mold was clamped with a press.
- the inside of the mold was depressurized to atmospheric pressure-0.1 MPa by a vacuum pump and then pressed at a maximum pressure of 4 MPa.
- the mold temperature was set at a temperature 10 ° C. higher than the melting point of the component having the highest melting point among the crystalline components contained in the thermosetting resin composition used.
- the mold was opened and demolded to obtain a fiber-reinforced composite material.
- the amount of voids in the fiber-reinforced composite material is less than 1% and the void is not substantially present, “A”, the appearance of the resin-impregnated portion is not recognized in the appearance of the fiber-reinforced composite material, When the void content is 1% or more and less than 3% and the resin-impregnated portion is not found in the appearance of the fiber reinforced composite material, “B”, the void amount in the fiber reinforced composite material is 3% or more, or the resin is not impregnated in the appearance "C” is given if the part is recognized.
- the amount of voids in the fiber-reinforced composite material can be determined by observing the cross-section of the fiber-reinforced composite material, which has been smoothly polished, with a cross-section that has been selected smoothly, by means of a falling optical microscope. Calculated from area ratio.
- composition unevenness of fiber reinforced composite materials About the composition nonuniformity of the fiber reinforced composite material obtained as mentioned above, it compared and evaluated by the following three steps.
- Tg glass transition temperature
- Example 1 As shown in Table 1, 100 parts by mass of crystalline biphenyl type epoxy resin "jER” (registered trademark) YX4000, 1,2,3,6-tetrahydrophthalic anhydride "" RIKACID "(registered trademark) TH” The powdery raw materials of 83 parts by mass and 5 parts by mass of triphenylphosphine “TPP” are sufficiently mixed, and an appropriate amount is charged into a circular die with a diameter of 100 mm, and then pressed at a pressure of 5 MPa A thermosetting resin composition was prepared.
- thermosetting resin composition had a complex viscosity ** of 2.3 ⁇ 10 8 Pa ⁇ s at 25 ° C., and some chipping occurred when it was lifted by hand, but sufficient handleability was obtained. It was something I had.
- thermosetting resin composition had a domain diameter of 87 ⁇ m. This thermosetting resin composition was excellent in the balance of high-speed curability and storage stability.
- thermosetting resin composition showed sufficient impregnatability. Seventeen samples were cut out uniformly from the fiber reinforced composite material, and as a result of measuring the Tg, there was almost no unevenness due to position, and a uniform fiber reinforced composite material was obtained.
- thermosetting resin composition (Examples 2 to 4) It implemented similarly to Example 1 except the pressure to apply the pressure at the time of preparing a thermosetting resin composition having been 10 MPa, 30 MPa, and 50 MPa, respectively. Both of the thermosetting resin compositions had a complex viscosity 2.3 * at 25 ° C. of 2.3 ⁇ 10 8 Pa ⁇ s, were not chipped when lifted by hand, and were excellent in handleability . Moreover, it was excellent in the balance of high-speed curability and storage stability.
- the fiber-reinforced composite material manufactured using the thermosetting resin composition and the dry reinforcing fiber base provided a uniform fiber-reinforced composite material having almost no voids inside and almost no unevenness. From such a fiber-reinforced composite material obtained, it was shown that the thermosetting resin composition is excellent in the impregnatability.
- Example 5 The procedure of Example 3 was repeated, except that the die used was 1.5 mm in diameter, and a granular thermosetting resin composition was used.
- the thermosetting resin composition had a complex viscosity ** of 2.3 ⁇ 10 8 Pa ⁇ s at 25 ° C., was not chipped when lifted by hand, and was excellent in handleability. Moreover, it was excellent in the balance of high-speed curability and storage stability.
- a fiber-reinforced composite material prepared using the above-mentioned thermosetting resin composition for 290 g and a dry reinforcing fiber base contains a few voids inside, but there is no non-impregnated part on the surface, and there is almost no unevenness, uniform fiber reinforcement A composite material was obtained. From such a fiber reinforced composite material obtained, it was shown that the thermosetting resin composition has sufficient impregnatability.
- thermosetting resin composition had a complex viscosity ** of 2.3 ⁇ 10 8 Pa ⁇ s at 25 ° C., was not chipped when lifted by hand, and was excellent in handleability. Moreover, it was excellent in the balance of high-speed curability and storage stability.
- a fiber-reinforced composite material produced using the above-mentioned thermosetting resin composition for 290 g and a dry reinforcing fiber base has almost no void inside, is excellent in impregnating property, and has almost no unevenness, and a uniform fiber-reinforced composite material was gotten. From such a fiber reinforced composite material obtained, it was shown that the thermosetting resin composition has sufficient impregnatability.
- Example 7 As shown in Table 2, the same procedure as in Example 2 was carried out except that the catalyst used was 0.5 parts by mass of 2-methylimidazole.
- the thermosetting resin composition had a complex viscosity ** at 25 ° C. of 2.2 ⁇ 10 8 Pa ⁇ s, was not chipped when lifted by hand, and was excellent in handleability. In addition, although the high-speed curability was slightly reduced, it had a balance between sufficient high-speed curability and storage stability.
- the fiber-reinforced composite material manufactured using the thermosetting resin composition and the dry reinforcing fiber base provided a uniform fiber-reinforced composite material having almost no voids inside and almost no unevenness. From such a fiber-reinforced composite material obtained, it was shown that the thermosetting resin composition is excellent in the impregnatability.
- thermosetting resin compositions had a complex viscosity ** at 25 ° C. of 2.2 ⁇ 10 8 Pa ⁇ s, were not chipped when lifted by hand, and were excellent in handleability . Moreover, it had a balance of sufficient high-speed curability and storage stability.
- the fiber-reinforced composite material manufactured using the thermosetting resin composition and the dry reinforcing fiber base provided a uniform fiber-reinforced composite material having almost no voids inside and almost no unevenness. From such a fiber-reinforced composite material obtained, it was shown that the thermosetting resin composition is excellent in the impregnatability.
- Example 10 The same procedure as in Example 7 was carried out except that the amount of the catalyst 2-methylimidazole used was 30 parts by mass.
- the thermosetting resin composition had a complex viscosity ** at 25 ° C. of 2.2 ⁇ 10 8 Pa ⁇ s, was not chipped when lifted by hand, and was excellent in handleability. Moreover, it had a balance of sufficient high-speed curability and storage stability.
- the fiber-reinforced composite material manufactured using the thermosetting resin composition and the dry reinforcing fiber base material contained a few voids inside, but a uniform fiber-reinforced composite material with almost no unevenness was obtained. From such a fiber reinforced composite material obtained, it was shown that the thermosetting resin composition has sufficient impregnatability.
- thermosetting resin composition has a complex viscosity ** of 1.7 ⁇ 10 8 Pa ⁇ s at 25 ° C., and has sufficient handleability without chipping when lifted by hand.
- thermosetting resin composition has sufficient impregnatability.
- thermosetting resin composition (Example 12) It implemented similarly to Example 2 except the hardening agent to be used having been 80 mass parts of phthalic anhydrides.
- the thermosetting resin composition had a complex viscosity ** of 1.5 ⁇ 10 8 Pa ⁇ s at 25 ° C., was not chipped when lifted by hand, and was excellent in handleability. Moreover, it had a balance of sufficient high-speed curability and storage stability.
- the fiber reinforced composite material manufactured using this thermosetting resin composition and the dry reinforcing fiber base material gave a uniform fiber reinforced composite material with almost no unevenness. From such a fiber-reinforced composite material obtained, it was shown that the thermosetting resin composition is excellent in the impregnatability.
- thermosetting resin composition had a complex viscosity ** of 1.0 ⁇ 10 8 Pa ⁇ s at 25 ° C., was not chipped when lifted by hand, and was excellent in handleability. Moreover, it had a balance of sufficient high-speed curability and storage stability.
- the fiber-reinforced composite material produced using this thermosetting resin composition and the dry reinforcing fiber base contained a few voids inside, but a sufficiently uniform fiber-reinforced composite material was obtained.
- thermosetting resin compositions As shown in Table 3, the process was performed in the same manner as in Example 3 except that the size of the powdered raw material was changed such that the domain diameter was 1 ⁇ m, 15 ⁇ m, 284 ⁇ m, and 492 ⁇ m.
- Both of the thermosetting resin compositions had a complex viscosity 2.3 * at 25 ° C. of 2.3 ⁇ 10 8 Pa ⁇ s, were not chipped when lifted by hand, and were excellent in handleability . Moreover, it was excellent in the balance of high-speed curability and storage stability.
- the fiber-reinforced composite material manufactured using the thermosetting resin composition and the dry reinforcing fiber base provided a uniform fiber-reinforced composite material having almost no voids inside and almost no unevenness. From such a fiber-reinforced composite material obtained, these thermosetting resin compositions were shown to be excellent in the impregnatability.
- thermosetting resin composition (Comparative example 1) It implemented similarly to Example 1 except the pressure to which the pressure at the time of preparing a thermosetting resin composition was set to 1 Mpa. Although this thermosetting resin composition has a complex viscosity ** of 2.3 ⁇ 10 8 Pa ⁇ s at 25 ° C., when it is lifted by hand, it is easily chipped, resulting in poor handleability. there were. The fiber reinforced composite material produced using this thermosetting resin composition and the dry reinforcing fiber base material became a fiber reinforced composite material containing many voids.
- thermosetting resin composition When preparing a thermosetting resin composition, it is heated to the melting point or more of each component, melted and stirred, and sufficiently dissolved after compatiblizing, and then charged in a proper amount in a mold having a long diameter of 100 mm, followed by cooling and thermosetting. It carried out similarly to Example 1 except having prepared sex resin composition. Although this thermosetting resin composition has a complex viscosity ** of 2.5 ⁇ 10 8 Pa ⁇ s at 25 ° C. and is excellent in handleability, it has storage stability since the components are compatible with each other. It was lacking.
- thermosetting resin composition of the present invention is excellent in the balance between high-speed curing and storage stability, and is excellent in the impregnating property to the reinforcing fiber substrate, so that the adjusted resin can be stored for a long time,
- fiber reinforced composite materials can be provided more easily with high productivity.
- the application of fiber reinforced composite materials particularly to automobile and aircraft applications proceeds, and further weight reduction of these can be expected to contribute to the improvement of fuel efficiency and the reduction of global warming gas emissions.
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Abstract
Description
比重が0.90~1.30かつ、25℃での動的粘弾性測定における複素粘度η*が1×107Pa・s以上である、繊維強化複合材料用熱硬化性樹脂組成物。
空隙率が0.1~25%かつ、25℃での動的粘弾性測定における複素粘度η*が1×107Pa・s以上である、繊維強化複合材料用熱硬化性樹脂組成物。
0≦x×y≦15・・・(式2)
(式1)および(式2)において、xは0.1≦x≦300を満たす。また、yは0≦y≦50を満たす。
空隙率が0.1~25%であることにより、十分な常温での取扱い性を有しながら、強化繊維基材への含浸性にも優れる。
・Af:繊維基材1枚・1m2当たりの質量(g/m2)
・N:繊維基材の積層枚数(枚)
・ρf:強化繊維の密度(g/cm3)
・h:繊維強化複合材料(試験片)の厚み(mm)
強化繊維基材1枚・1m2当たりの質量Afや、繊維基材の積層枚数Nおよび強化繊維の密度ρfが明らかでない場合は、JIS K 7075(1991)に基づく燃焼法、硝酸分解法および硫酸分解法のいずれかにより、繊維強化複合材料の繊維体積含有率を測定することができるが、この中では硫酸分解法を優先的に選択できる。この場合に用いられる強化繊維の密度は、JIS R 7603(1999)に基づき測定した値を用いる。
各実施例の熱硬化性樹脂組成物を得るために、次の樹脂原料を用いた。表1~表3中の樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。
・“jER”(登録商標)YX4000(三菱化学(株)製):結晶性ビフェニル型エポキシ樹脂、融点=105℃
・“jER”(登録商標)1004AF(三菱化学(株)製):ガラス状固形ビスフェノールA型エポキシ樹脂、融点なし
2.硬化剤
・“リカシッド”(登録商標)TH(新日本理化(株)製):1,2,3,6-テトラヒドロ無水フタル酸、融点=101℃
・無水フタル酸(関東化学(株)製):融点=131℃
・TS-G(四国化成(株)製):グリコールウリル骨格チオール化合物、融点=78℃
3.触媒
・TPP(ケイ・アイ化成(株)製):トリフェニルホスフィン、融点=80℃
・2-メチルイミダゾール(関東化学(株)製):融点=142℃
<熱硬化性樹脂組成物の調製>
表1~表3に記載した樹脂原料を、それぞれハンマーミルにて、孔サイズ1mmのスクリーンを使用して粉砕した後、篩いを通すことで、粉末状原料を得た。また、10μm以下のさらに小さい粒子径の粉末状原料を得る場合にはジェットミルを使用して粉砕した。その後、得られた粉末状原料を用いて、表1~表3に記載のとおりの配合比で原料を十分に混合し、キャビティの長径が1.5mm、10mm、100mmである金型にキャビティ体積の70体積%の量を投入し、各実施例、比較例に記載の圧力で加圧することによって熱硬化性樹脂組成物を得た。
使用した各樹脂原料の融点は、JIS K 7121:2012に従って、示差走査熱量測定(DSC)により測定した。測定装置としてはPyris1 DSC(Perkin Elmer製)を使用した。結晶性成分をアルミサンプルパンに採取し、窒素雰囲気下において、10℃/minの昇温速度で測定を行った。得られたDSC曲線において、成分の融解による吸熱ピークの頂点の温度を融点として測定した。
<熱硬化性樹脂組成物の長径測定>
前記のように調製した熱硬化性樹脂組成物の長径をノギスによって測定した。5個の測定値の平均値をそのサンプルの長径とした。
<熱硬化性樹脂組成物の比重測定>
前記のように調製した熱硬化性樹脂組成物の、常温においての空気中及び水中での重量を測定し、アルキメデス法によって比重を算出した。なお、測定するサンプルは、サンプルのサイズによらず、空気中の重量で約3gとなる量とした。5個の測定値の平均値をそのサンプルの比重とした。
<熱硬化性樹脂組成物の空隙率>
前記のように調製した熱硬化性樹脂組成物中に含まれる各成分の比重をアルキメデス法によって算出した。算出した各成分の比重を熱硬化性樹脂組成物に含まれる配合比の体積分率で足し合わせることにより、実質的に空隙のない熱硬化性樹脂組成物の比重を算出した。得られた比重から、前記した(式3)式を用いて熱硬化性樹脂組成物の空隙率を算出した。
<熱硬化性樹脂組成物のドメイン径測定>
前記のように調製した熱硬化性樹脂組成物を試料として、試料表面の赤外分光(全反射測定法)により、各成分特有の赤外吸収のピーク強度から二次元の化学組成マッピングを得た。得られた二次元の化学組成マッピングにおいて、各成分の赤外吸収ピーク強度が連続的に最大値の1/3以上となる範囲をその成分のドメインと見なし、マッピング図に引いた任意のX軸方向の直線上でのドメインの幅を計測した。ドメイン幅を100カ所計測し、その平均値をドメイン径として採用した。
<熱硬化性樹脂組成物の粘度測定>
前記のように調製した熱硬化性樹脂組成物を試料として、動的粘弾性測定により測定した。測定装置にはARES-G2(TA Instruments社製)を使用した。試料を8mmのパラレルプレートにセットし、0.5Hzの牽引周期を加え、25℃での複素粘度η*を測定した。
<熱硬化性樹脂組成物の150℃硬化時間xの測定>
前記のように調製した熱硬化性樹脂組成物の高速硬化性確認のため、150℃加熱時の硬化時間を誘電測定により確認した。誘電測定装置として、Holometrix―Micromet社製のMDE-10キュアモニターを使用した。TMS-1インチ型センサーを下面に埋め込んだプログラマブルミニプレスMP2000の下面に内径32mm、厚さ3mmのバイトン製Oリングを設置し、プレスの温度を150℃に設定し、Oリングの内側に樹脂組成物をセット、プレスを閉じ、樹脂組成物のイオン粘度の時間変化を追跡した。誘電測定は1、10、100、1000、および10000Hzの各周波数で行い、付属のソフトウェアを用いて、周波数非依存のイオン粘度の対数Log(α)を得た。
キュアインデックス:(単位:%)
αt:時間tにおけるイオン粘度(単位:Ω・cm)
αmin:イオン粘度の最小値(単位:Ω・cm)
αmax:イオン粘度の最大値(単位:Ω・cm)。
<熱硬化性樹脂組成物の40℃・1週間保管時反応進行率yの測定>
前記のように調製した熱硬化性樹脂組成物の保管安定性確認のため、40℃環境で1週間保管後の硬化反応進行率を測定した。測定には、示差走査熱量測定(DSC)を使用した。調製直後の樹脂組成物の硬化反応による発熱量(E1)、40℃に設定した熱風オーブン内で1週間保管後の樹脂組成物の硬化反応による発熱量(E2)を測定した。以下の(式6)により、40℃・1週間反応進行率y(%)を算出した。
<熱硬化性樹脂組成物の室温での取り扱い性>
前記のように調製した熱硬化性樹脂組成物の室温での取り扱い性を次の3段階で比較評価した。熱硬化性樹脂組成物を手で持ち上げた際に、破壊、変形がないものを「A」、一部欠けたり、僅かに変形があるものを「B」、持ち上げた際に容易に割れたり変形してしまうものを「C」とした。
下記のプレス成形法によって繊維強化複合材料を製造した。350mm×700mm×2mmの板状キャビティを有し、所定の温度(成形温度)に保持した金型内にて、強化繊維として炭素繊維織物CO6343(炭素繊維:T300-3K、組織:平織、目付:198g/m2、東レ(株)製)を9枚積層した基材の上に、前記のように調製した熱硬化性樹脂組成物を約290gをセットした。その後、プレス装置で型締めを行った。この時、金型内を真空ポンプにより大気圧-0.1MPaに減圧した後、最大4MPaの圧力でプレスした。金型温度は、使用する熱硬化性樹脂組成物中に含まれる結晶性成分の内で最も高い融点を有する成分の融点よりも10℃高い温度に設定した。プレス開始後30分で金型を開き、脱型して、繊維強化複合材料を得た。
前記の繊維強化複合材料を作製する際の樹脂の強化繊維への含浸性について、繊維強化複合材料中のボイド量を基準に次の3段階で比較評価した。
前記のようにして得られた繊維強化複合材料の組成ムラについて、次の3段階で比較評価した。
表1に示したように、結晶性ビフェニル型エポキシ樹脂「“jER”(登録商標)YX4000」100質量部、1,2,3,6-テトラヒドロ無水フタル酸「“リカシッド”(登録商標)TH」83質量部、トリフェニルホスフィン「TPP」5質量部のそれぞれの粉末状原料を十分に混合し、直径100mmの円状の金型に適量投入後、5MPaの圧力で加圧することにより、板状の熱硬化性樹脂組成物を調製した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.3×108Pa・sであり、手で持ち上げた際に、一部欠けが生じたが、十分な取り扱い性を有するものであった。また、この熱硬化性樹脂組成物は、成分のドメイン径は87μmであった。この熱硬化性樹脂組成物は、高速硬化性と保管安定性のバランスに優れるものであった。
熱硬化性樹脂組成物を調製する際の加圧する圧力を、それぞれ10MPa、30MPa、50MPaとしたこと以外は、実施例1と同様に実施した。いずれの熱硬化性樹脂組成物とも、25℃での複素粘度η*が2.3×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、高速硬化性と保管安定性のバランスに優れるものであった。これらの熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドがほぼなく、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が含浸性に優れていることが示された。
使用する金型の直径が1.5mmのものを用い、顆粒状の熱硬化性樹脂組成物としたこと以外は、実施例3と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.3×108Pa・sであり、手で持ち上げた際にも欠けることはなく、取り扱い性に優れていた。また、高速硬化性と保管安定性のバランスに優れるものであった。上記熱硬化性樹脂組成物290g分とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドを若干含むものの、表面に未含浸部は無く、ムラがほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が十分な含浸性を有することが示された。
使用する金型の直径が10mmのものを用い、塊状の熱硬化性樹脂組成物としたこと以外は、実施例3と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.3×108Pa・sであり、手で持ち上げた際にも欠けることはなく、取り扱い性に優れていた。また、高速硬化性と保管安定性のバランスに優れるものであった。上記熱硬化性樹脂組成物290g分とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドがほぼなく、含浸性に優れており、ムラがほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が十分な含浸性を有することが示された。
表2に示したように、使用する触媒を、2-メチルイミダゾール0.5質量部としたこと以外は、実施例2と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.2×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、高速硬化性がやや低下するものの、十分な高速硬化性と保管安定性のバランスを有するものであった。これらの熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドがほぼなく、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が含浸性に優れていることが示された。
使用する触媒2-メチルイミダゾールの配合量を、それぞれ1質量部、15質量部としたこと以外は、実施例7と同様に実施した。これらの熱硬化性樹脂組成物は、25℃での複素粘度η*が2.2×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、十分な高速硬化性と保管安定性のバランスを有するものであった。これらの熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドがほぼなく、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が含浸性に優れていることが示された。
使用する触媒2-メチルイミダゾールの配合量を、30質量部としたこと以外は、実施例7と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.2×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、十分な高速硬化性と保管安定性のバランスを有するものであった。これらの熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドを若干含んだが、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が十分な含浸性を有することが示された。
表2に示したように、結晶性ビフェニル型エポキシ樹脂「“jER”(登録商標)YX4000」50質量部、ガラス状固形ビスフェノールA型エポキシ樹脂「“jER”(登録商標)1004AF」50質量部、1,2,3,6-テトラヒドロ無水フタル酸「“リカシッド”(登録商標)TH」49質量部、トリフェニルホスフィン「TPP」5質量部のそれぞれの粉末状原料を十分に混合し、実施例3と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が1.7×108Pa・sであり、手で持ち上げた際に、欠けることなく、十分な取り扱い性を有するものであった。また、高速硬化性と保管安定性のバランスに優れるものであった。この熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドを若干含むものの、表面に未含浸部は無かった。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が十分な含浸性を有することが示された。
使用する硬化剤を無水フタル酸80質量部としたこと以外は、実施例2と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が1.5×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、十分な高速硬化性と保管安定性のバランスを有するものであった。この熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、熱硬化性樹脂組成物が含浸性に優れていることが示された。
使用する硬化剤をグリコールウリル骨格チオール化合物51質量部とし、触媒を除いたこと以外は、実施例3と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が1.0×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、十分な高速硬化性と保管安定性のバランスを有するものであった。この熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドを若干含んだが、十分に均一な繊維強化複合材料が得られた。
表3に示したように、ドメイン径が1μm、15μm、284μm、492μmとなるよう、粉末状原料のサイズを変更したこと以外は、実施例3と同様に実施した。いずれの熱硬化性樹脂組成物とも、25℃での複素粘度η*が2.3×108Pa・sであり、手で持ち上げた際に欠けることはなく、取り扱い性に優れるものであった。また、高速硬化性と保管安定性のバランスに優れるものであった。これらの熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、内部にボイドがほぼなく、ムラもほぼない均一な繊維強化複合材料が得られた。このような繊維強化複合材料が得られたことから、これらの熱硬化性樹脂組成物は含浸性に優れていることが示された。
熱硬化性樹脂組成物を調製する際の加圧する圧力を、1MPaとしたこと以外は、実施例1と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.3×108Pa・sであるが、手で持ち上げた際に容易に欠けてしまい、取り扱い性が不足するものであった。この熱硬化性樹脂組成物とドライ強化繊維基材を用いて作製した繊維強化複合材料は、ボイドを多く含む繊維強化複合材料となった。
熱硬化性樹脂組成物を調製する際に各成分の融点以上に加熱し、溶融・攪拌して、十分に相溶させた後、長径100mmとなる金型に適量投入後、冷却して熱硬化性樹脂組成物を調製したこと以外は、実施例1と同様に実施した。この熱硬化性樹脂組成物は、25℃での複素粘度η*が2.5×108Pa・sであり、取り扱い性に優れるものの、各成分が相溶しているため、保管安定性が不足するものであった。
Claims (8)
- [A]主剤、並びに、[B]硬化剤及び/又は[C]触媒の各成分のドメインを有し、
比重が0.90~1.30かつ、
25℃での動的粘弾性測定における複素粘度η*が1×107Pa・s以上である、繊維強化複合材料用熱硬化性樹脂組成物。 - [A]主剤、並びに、[B]硬化剤及び/又は[C]触媒の各成分のドメインを有し、
空隙率が0.1~25%かつ、
25℃での動的粘弾性測定における複素粘度η*が1×107Pa・s以上である、繊維強化複合材料用熱硬化性樹脂組成物。 - 長径が1.5mm以上である、請求項1または2に記載の繊維強化複合材料用熱硬化性樹脂組成物。
- 150℃での硬化時間x(分)と、40℃環境で1週間保管時の硬化反応進行率y(%)との積が、以下の(式1)を満たす、請求項1~3のいずれかに記載の繊維強化複合材料用熱硬化性樹脂組成物。
0≦x×y≦40・・・(式1)
((式1)において、xは0.1≦x≦300を満たす。また、yは0≦y≦50を満たす。) - [C]触媒を有し、繊維強化複合材料用熱硬化性樹脂組成物100質量%に対してその含有量が1~30質量%である、請求項1~4のいずれかに記載の繊維強化複合材料用熱硬化性樹脂組成物。
- 請求項1~5のいずれかに記載の繊維強化複合材料用熱硬化性樹脂組成物とドライ強化繊維基材とを有する、繊維強化複合材料用プリフォーム。
- 請求項1~5のいずれかに記載の繊維強化複合材料用熱硬化性樹脂組成物が強化繊維基材に含浸されてなる成形体であって、
該成形体において該熱硬化性樹脂組成物が硬化物として存在する、繊維強化複合材料。 - 請求項1~5のいずれかに記載の繊維強化複合材料用熱硬化性樹脂組成物を溶融し、ドライ強化繊維基材に含浸させながら成形する成形工程、及び、
該ドライ強化繊維基材に含浸され、成形された該熱硬化性樹脂組成物を硬化させる硬化工程を有する、繊維強化複合材料の製造方法。
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KR1020197038958A KR20200055689A (ko) | 2017-09-28 | 2018-09-20 | 섬유 강화 복합 재료용 열 경화성 수지 조성물, 프리폼, 섬유 강화 복합 재료 및 섬유 강화 복합 재료의 제조방법 |
JP2018549989A JP6493633B1 (ja) | 2017-09-28 | 2018-09-20 | 繊維強化複合材料用熱硬化性樹脂組成物、プリフォーム、繊維強化複合材料及び繊維強化複合材料の製造方法 |
AU2018343713A AU2018343713A1 (en) | 2017-09-28 | 2018-09-20 | Thermosetting resin composition for fiber-reinforced composite material, preform, fiber-reinforced composite material, and method for producing fiber-reinforced composite material |
CN201880059507.0A CN111094409B (zh) | 2017-09-28 | 2018-09-20 | 纤维强化复合材料用热固性树脂组合物、预成型体、纤维强化复合材料以及纤维强化复合材料的制造方法 |
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US (1) | US20200131324A1 (ja) |
EP (1) | EP3689947A4 (ja) |
JP (1) | JP6493633B1 (ja) |
KR (1) | KR20200055689A (ja) |
CN (1) | CN111094409B (ja) |
AU (1) | AU2018343713A1 (ja) |
BR (1) | BR112019027562A2 (ja) |
CA (1) | CA3067532A1 (ja) |
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- 2018-09-20 AU AU2018343713A patent/AU2018343713A1/en not_active Abandoned
- 2018-09-20 BR BR112019027562-2A patent/BR112019027562A2/pt not_active Application Discontinuation
- 2018-09-20 US US16/623,924 patent/US20200131324A1/en not_active Abandoned
- 2018-09-20 CN CN201880059507.0A patent/CN111094409B/zh active Active
- 2018-09-20 CA CA3067532A patent/CA3067532A1/en not_active Abandoned
- 2018-09-20 WO PCT/JP2018/034754 patent/WO2019065432A1/ja unknown
- 2018-09-20 JP JP2018549989A patent/JP6493633B1/ja active Active
- 2018-09-20 KR KR1020197038958A patent/KR20200055689A/ko unknown
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Also Published As
Publication number | Publication date |
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CN111094409A (zh) | 2020-05-01 |
EP3689947A1 (en) | 2020-08-05 |
JP6493633B1 (ja) | 2019-04-03 |
RU2020111913A (ru) | 2021-10-28 |
AU2018343713A1 (en) | 2020-01-16 |
US20200131324A1 (en) | 2020-04-30 |
EP3689947A4 (en) | 2021-06-30 |
JPWO2019065432A1 (ja) | 2019-11-14 |
BR112019027562A2 (pt) | 2020-07-07 |
KR20200055689A (ko) | 2020-05-21 |
CN111094409B (zh) | 2023-01-03 |
CA3067532A1 (en) | 2019-04-04 |
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