WO2018168461A1 - シアネートエステル樹脂組成物およびプリプレグ - Google Patents
シアネートエステル樹脂組成物およびプリプレグ Download PDFInfo
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- WO2018168461A1 WO2018168461A1 PCT/JP2018/007445 JP2018007445W WO2018168461A1 WO 2018168461 A1 WO2018168461 A1 WO 2018168461A1 JP 2018007445 W JP2018007445 W JP 2018007445W WO 2018168461 A1 WO2018168461 A1 WO 2018168461A1
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- cyanate ester
- ester resin
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
- C08K5/3155—Dicyandiamide
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C08L21/00—Compositions of unspecified rubbers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2421/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Definitions
- the present invention relates to a cyanate ester resin composition and a prepreg.
- Patent Document 1 discloses an epoxy resin composition containing an epoxy resin as a matrix, a thermoplastic resin for viscosity adjustment, a filler, and a curing agent.
- a prepreg obtained by combining is disclosed. Such prepregs are used in a wide range of fields such as structural materials such as aircraft and vehicles, reinforcement of concrete structures, golf clubs, tennis rackets, fishing rods and other sports fields because of their light weight and excellent mechanical properties.
- Cyanate ester resin is mentioned as resin which can substitute for an epoxy resin. Cyanate ester resins have better heat resistance than epoxy resins and can withstand heat up to, for example, around 300 ° C. However, the cyanate ester resin is difficult to dissolve the thermoplastic resin for adjusting the viscosity, and it is difficult to adjust the viscosity of the resin composition. is there. Due to this problem, when the prepreg is heated and cured, the resin composition flows out from the reinforcing fibers, resulting in a resin deficiency in the obtained fiber-reinforced composite material, resulting in uneven thickness.
- the object of the present invention is to suppress the resin flow at the time of heat curing without adding a thermoplastic resin for viscosity adjustment, to eliminate resin deficiency and uneven thickness, and to have excellent workability.
- An object of the present invention is to provide an ester resin composition and a prepreg using the same.
- the present inventor adds a curing agent or a curing accelerator, silica fine particles and core-shell rubber particles to the cyanate ester resin, and specifies the compounding ratio of the silica fine particles and the core-shell rubber particles to the cyanate ester resin.
- the present invention is as follows.
- Ester resin composition. 3. The cyanate ester resin composition according to 1, wherein the (A) cyanate ester resin is a novolac-type cyanate ester resin. 4). 2. The cyanate ester resin composition according to 1, wherein the amount of the silica fine particles (C) is 2 to 4 parts by mass with respect to 100 parts by mass of the (A) cyanate ester resin. 5). 2. The cyanate ester resin composition according to 1 above, wherein the amount of the (D) core-shell rubber particles based on 100 parts by mass of the (A) cyanate ester resin is 4 to 8 parts by mass. 6). 2.
- a prepreg comprising the cyanate ester resin composition according to any one of 1 to 6 above and a reinforcing fiber. 8). 8. The prepreg as described in 7 above, wherein the content of the cyanate ester resin composition in the prepreg is 30 to 60% by mass.
- (B) a curing agent or curing accelerator, (C) silica fine particles and (D) core-shell rubber particles are added to (A) cyanate ester resin, and (C) (C) for cyanate ester resin. Since the blending ratio of silica fine particles and (D) core-shell rubber particles is specified, the resin flow during heat curing can be suppressed without adding a thermoplastic resin for viscosity adjustment, resulting in resin defects and uneven thickness. Can be provided, and a cyanate ester resin composition having excellent workability can be provided.
- the cyanate ester resin composition of the present invention has a tan ⁇ of 1% strain of less than 1 and a tan ⁇ of 100% strain of 1 or more when viscoelasticity is measured on a parallel plate at a temperature of 70 ° C. and a frequency of 1 Hz. Is particularly excellent in suppression of resin flow during heat curing, elimination of resin deficiency and uneven thickness, and workability.
- the prepreg composed of the cyanate ester resin composition and the reinforcing fiber is excellent in heat resistance and also excellent in mechanical strength since resin deficiency and thickness nonuniformity are suppressed.
- (A) Cyanate ester resin The (A) cyanate ester resin used in the present invention is not particularly limited. Generally, cyanate ester resin is represented by the following formula. R— (O—C ⁇ N) n (In the formula, R represents a divalent or higher valent organic group having an aromatic ring, and n represents an integer of 2 or higher.) Examples of such cyanate ester resins include novolak type, bisphenol A type, bisphenol E type, and bisphenol F type cyanate ester resins. Among these, novolak-type cyanate ester resins are preferable. As the novolak type cyanate resin, commercially available ones can be used, and examples thereof include Lima Japan Co., Ltd., Primaset PT-30, Primaset PT-60 and the like.
- the (B) curing agent or curing accelerator used in the present invention is not particularly limited as long as it can accelerate the thermal curing of the cyanate ester resin.
- cobalt, copper And metal complexes such as alcohols, acids, amines and bases.
- Silica fine particles used in the present invention are preferably hydrophilic silica fine particles, and amorphous synthetic silica such as precipitated silica, gel silica, pyrolysis silica, and fused silica. Crystalline synthetic silica; natural silica and the like.
- the average primary particle diameter of the silica fine particles is preferably 5 nm to 100 nm.
- Core-shell rubber particles used in the present invention are known.
- a shell different from the core component is formed on the surface of a particulate core component mainly composed of a crosslinked rubber-like polymer. Particles obtained by graft polymerization of component polymers can be used.
- the core component include butadiene rubber, acrylic rubber, silicone rubber, butyl rubber, NBR, SBR, IR, EPR, and the like.
- the shell component include a polymer obtained by polymerizing a monomer selected from an acrylic ester monomer, a methacrylic ester monomer, an aromatic vinyl monomer, and the like.
- the average particle diameter of the core-shell rubber particles is, for example, 10 nm to 10 ⁇ m, preferably 100 nm to 500 nm.
- the cyanate ester resin composition of the present invention comprises (C) 1 to 5 parts by mass of silica fine particles and (D) 2 to 10 parts by mass of core-shell rubber particles with respect to 100 parts by mass of (A) cyanate ester resin.
- the mass ratio of silica fine particles and (D) core-shell rubber particles is required to be 1/1 to 1/5 as (C) / (D).
- the blending ratio of (C) silica fine particles is less than 1 part by mass or (D) the blending ratio of core-shell rubber particles is less than 2 parts by weight, the resin flow is not sufficiently suppressed, and the effects of the present invention can be achieved. Can not.
- the blending amount of (C) silica fine particles is more preferably 2 to 4 parts by weight with respect to 100 parts by weight of (A) cyanate ester resin, and (D) the blending amount of core-shell rubber particles is 4 to 8 parts by weight. More preferably, the mass ratio of (C) silica fine particles and (D) core-shell rubber particles is more preferably 1 / 1.5 to 1/4 as (C) / (D).
- the cyanate ester resin composition of the present invention has a strain of 1% tan ⁇ of less than 1 and a strain of 100% tan ⁇ of 1 or more when viscoelasticity is measured on a parallel plate at a temperature of 70 ° C. and a frequency of 1 Hz.
- the viscoelasticity can be measured by using a trade name ARES manufactured by TA Instruments Inc.
- the viscoelasticity can be achieved by appropriately setting the blending amounts of (C) silica fine particles and (D) core-shell rubber particles with respect to (A) cyanate ester resin as described above.
- the cyanate ester resin composition of the present invention can contain other additives as necessary.
- additives include fillers, anti-aging agents, solvents, flame retardants, reaction retarders, antioxidants, pigments (dyes), plasticizers, thixotropic agents, ultraviolet absorbers, and surfactants (leveling agents). ), Dispersants, dehydrating agents, adhesion-imparting agents, antistatic agents, and the like.
- the prepreg of the present invention comprises the cyanate ester resin composition of the present invention and a reinforcing fiber.
- the prepreg of the present invention is obtained by impregnating reinforcing fibers with the cyanate ester resin composition of the present invention.
- the reinforcing fiber used in the prepreg of the present invention is not particularly limited, and examples thereof include conventionally known fibers. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of carbon fiber, glass fiber, and an aramid fiber from a viewpoint of intensity
- the form of the fiber is not particularly limited, and examples thereof include roving, roving aligned in one direction, woven fabric, nonwoven fabric, knitted fabric, and tulle.
- the production method of the prepreg of the present invention is not particularly limited. Examples thereof include a wet method using a solvent and a hot melt method which is a solventless method. From the viewpoint of shortening the drying time, the amount of the solvent used is preferably 80 to 200 parts by mass with respect to 100 parts by mass of the solid content of the cyanate ester resin composition.
- the content of the cyanate ester resin composition is preferably 30 to 60% by mass in the prepreg from the viewpoint of the mechanical properties of the fiber-reinforced composite material obtained.
- the use of the prepreg of the present invention is not particularly limited.
- a conventionally known fiber reinforced composite material can be obtained.
- aircraft parts such as fairings, flaps, leading edges, floor panels, propellers, fuselage; motorcycle parts such as motorcycle frames, cowls, fenders; doors, bonnets, tailgates, side fenders, side panels, Auto parts such as fender, energy absorbing member, trunk lid, hard top, side mirror cover, spoiler, diffuser, ski carrier, engine cylinder cover, engine hood, chassis, air spoiler, propeller shaft; leading vehicle nose, roof, side panel, Vehicle outer panels such as doors, bogie covers, side skirts; railway vehicle parts such as luggage racks and seats; interior, wing inner panels, outer panels, roofs, floors, etc.
- Aero parts such as side skirts to be mounted on moving vehicles and single vehicles; Cases for notebook PCs, mobile phones, etc .; Medical uses such as X-ray cassettes and top plates; Applications for acoustic products such as flat speaker panels and speaker cones; Golf heads, Sports plate applications such as faceplates, snowboards, surfboards, protectors, etc .; general industrial applications such as leaf springs, windmill blades, elevators ( ⁇ panels, doors).
- a fiber reinforced composite material can be produced by laminating the prepreg of the present invention and another member (for example, a honeycomb core).
- another member for example, a honeycomb core.
- the fiber reinforced composite material that can be produced by laminating the prepreg of the present invention and other members include a honeycomb sandwich panel.
- each material was kneaded at 70 ° C. using a kneader to prepare various cyanate ester resin compositions. The following measurement was performed with respect to the obtained various cyanate ester resin compositions.
- Viscoelasticity tan ⁇ at a strain of 1% or 100% was measured under the conditions of a temperature of 70 ° C. and a frequency of 1 Hz using ARES manufactured by TA Instruments.
- Molding cyanate ester resin composition film of the prepreg (resin weight 104 g / m 2) impregnated into a glass fiber fabric (fiber basis weight 156 g / m 2) was molded prepreg.
- the cyanate ester resin composition in the molded prepreg is 40% by mass.
- the cyanate ester resin composition of each Example in which the blending ratio of silica fine particles and (D) core-shell rubber particles is specified in the range specified in the present invention is heat-cured without adding a thermoplastic resin for viscosity adjustment. It has been found that the resin flow at the time can be suppressed, the resin deficiency and the uneven thickness are eliminated, and the workability is excellent.
- the cyanate ester resin composition of each example has a tan ⁇ of 1% strain of less than 1 and a tan ⁇ of 100% strain of 1 or more when viscoelasticity measurement is performed on a parallel plate at a temperature of 70 ° C. and a frequency of 1 Hz. Therefore, it is low strain and solid (tan ⁇ ⁇ 1), can suppress the resin flow during heat curing, and is high strain and liquid (tan ⁇ ⁇ 1). Property is improved.
- the comparative example 1 did not add the (D) core shell rubber particle, the result of the resin flow and dimensional stability deteriorated.
- Comparative Example 2 since (C) silica fine particles were not added, the results of resin flow and dimensional stability were deteriorated.
- Comparative Example 3 since the blending amount of (D) core-shell rubber particles was less than the lower limit specified in the present invention, the results of resin flow and dimensional stability were deteriorated. In Comparative Example 4, since the blending amount of (C) silica fine particles and the blending amount of (D) core-shell rubber particles exceeded the upper limit defined in the present invention, workability deteriorated.
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Abstract
Description
しかし、シアネートエステル樹脂は、粘度調整のための熱可塑性樹脂が溶解しにくく、樹脂組成物の粘度調整が困難であり、室温では高い粘度を有するものの硬化加熱時に低粘度化してしまうという問題点がある。この問題点によって、プリプレグを加熱硬化する時に樹脂組成物が強化繊維から流れ出てしまい、得られた繊維強化複合材料に樹脂欠損が生じ、厚みが不均一となる。硬化時の樹脂流れを抑制するためには、樹脂組成物の粘度をより高くする必要があるが、この場合、室温時の樹脂組成物の粘度が高くなりすぎるため、プリプレグ成型時の作業性が悪化してしまう。
すなわち本発明は以下の通りである。
2.平行板にて温度70℃、周波数1Hzで粘弾性測定した際、歪1%のtanδが1未満であり、かつ歪100%のtanδが1以上であることを特徴とする前記1に記載のシアネートエステル樹脂組成物。
3.前記(A)シアネートエステル樹脂が、ノボラック型のシアネートエステル樹脂である、前記1に記載のシアネートエステル樹脂組成物。
4.前記(A)シアネートエステル樹脂100質量部に対する前記(C)シリカ微粒子の配合量が、2~4質量部である、前記1に記載のシアネートエステル樹脂組成物。
5.前記(A)シアネートエステル樹脂100質量部に対する前記(D)コアシェルゴム粒子の配合量が、4~8質量部である、前記1に記載のシアネートエステル樹脂組成物。
6.前記(C)シリカ微粒子と前記(D)コアシェルゴム粒子の質量比が、(C)/(D)として1/1.5~1/4である、前記1に記載のシアネートエステル樹脂組成物。
7.前記1~6のいずれかに記載のシアネートエステル樹脂組成物と強化繊維とからなるプリプレグ。
8.前記プリプレグ中の前記シアネートエステル樹脂組成物の含有量が、30~60質量%である、前記7に記載のプリプレグ。
また、平行板にて温度70℃、周波数1Hzで粘弾性測定した際、歪1%のtanδが1未満であり、かつ歪み100%のtanδが1以上である本発明の前記シアネートエステル樹脂組成物は、加熱硬化時の樹脂フローの抑制性、樹脂欠損や厚みの不均一の解消、並びに作業性にとくに優れたものとなる。
また、前記シアネートエステル樹脂組成物と強化繊維とからなるプリプレグは、耐熱性に優れ、また、樹脂欠損や厚みの不均一も抑制されていることから、機械的強度にも優れる。
本発明で使用される(A)シアネートエステル樹脂はとくに制限されない。一般的にシアネートエステル樹脂は、下記式で示される。
R-(O-C≡N)n
(式中、Rは芳香環を有する2価以上の有機基を表し、nは2以上の整数を表す。)
このようなシアネートエステル樹脂としては、ノボラック型、ビスフェノールA型、ビスフェノールE型、ビスフェノールF型のシアネートエステル樹脂等が挙げられる。これらの中でも、ノボラック型のシアネートエステル樹脂が好ましい。
ノボラック型シアネート樹脂としては、市販されているものを利用でき、例えばロンザジャパン株式会社製、プリマセットPT-30、プリマセットPT-60等が挙げられる。
本発明で使用される(B)硬化剤もしくは硬化促進剤としては、シアネートエステル樹脂の熱硬化を促進できるものであればとくに制限されないが、例えば、コバルト、銅等の金属錯体、アルコール類、酸、アミン、塩基等が挙げられる。
本発明で使用される(C)シリカ微粒子としては、親水性のシリカ微粒子が好ましく、沈殿法シリカ、ゲル法シリカ、熱分解法シリカ、溶融シリカのような非晶質合成シリカ;結晶合成シリカ;天然シリカ等が挙げられる。
(C)シリカ微粒子の平均一次粒子径は、5nm~100nmが好ましい。
本発明で使用される(D)コアシェルゴム粒子は公知であり、例えば架橋されたゴム状ポリマーを主成分とする粒子状コア成分の表面に、コア成分とは異種のシェル成分ポリマーをグラフト重合した粒子であることができる。
コア成分としては、例えばブタジエンゴム、アクリルゴム、シリコーンゴム、ブチルゴム、NBR、SBR、IR、EPR等が挙げられる。
シェル成分としては、例えばアクリル酸エステル系モノマー、メタクリル酸エステル系モノマー、芳香族系ビニルモノマー等から選択されたモノマーを重合させた重合体が挙げられる。
(D)コアシェルゴム粒子の平均粒子径は、例えば10nm~10μmであり、100nm~500nmが好ましい。
本発明のシアネートエステル樹脂組成物は、(A)シアネートエステル樹脂100質量部に対し、(C)シリカ微粒子を1~5質量部および(D)コアシェルゴム粒子を2~10質量部含み、(C)シリカ微粒子と(D)コアシェルゴム粒子の質量比が(C)/(D)として1/1~1/5であることが必要である。
(C)シリカ微粒子の前記配合割合が1質量部未満または(D)コアシェルゴム粒子の前記配合割合が2質量部未満では、樹脂フローの抑制が不十分であり、本発明の効果を奏することができない。
(C)シリカ微粒子の前記配合割合が5質量部を超える、または(D)コアシェルゴム粒子の前記配合割合が10質量部を超えると、樹脂組成物の粘度が上昇し、作業性が悪化し、また、硬化物の機械的特性(主に弾性率)が低下する。
(C)シリカ微粒子と(D)コアシェルゴム粒子の質量比が(C)/(D)として1/1を超える場合、すなわち(C)成分に対して(D)成分の配合量が少ない場合、樹脂フローの抑制が不十分であり、本発明の効果を奏することができない。
(C)シリカ微粒子と(D)コアシェルゴム粒子の質量比が(C)/(D)として1/5未満の場合、すなわち(C)成分に対して(D)成分の配合量が多すぎる場合、樹脂フロー抑制効果が高くなりすぎるため、プリプレグ成型時の作業性が悪化する。
具体的には、本発明のプリプレグは、本発明のシアネートエステル樹脂組成物を強化繊維に含浸させることにより得られるものである。
本発明のプリプレグに使用される強化繊維は、特に制限されず、例えば、従来公知のものが挙げられる。なかでも、強度の観点から、炭素繊維、ガラス繊維及びアラミド繊維からなる群から選ばれる少なくとも1種であるのが好ましい。
繊維は、その形態について特に制限されず、ロービング、ロービングを一方向に引きそろえたもの、織物、不織布、編物、チュールなどが挙げられる。
(A)シアネートエステル樹脂:ロンザジャパン株式会社製、プリマセットPT-30、プリマセットPT-60(ノボラック型のシアネートエステル樹脂)
(B)硬化剤または硬化促進剤:三菱化学株式会社製DICY-15(ジシアンジアミド)
(C)シリカ微粒子:キャボット社製CAB-O-SIL M5(親水性ヒュームドシリカ)
(D)コアシェルゴム粒子:株式会社カネカ製MX-154(エポキシ樹脂/コアシェルゴム粒子マスターバッチ;ブタジエン系コアシェルゴム粒子を40質量%含む)
得られた各種シアネートエステル樹脂組成物に対し、次の測定を行った。
シアネートエステル樹脂組成物フィルム(樹脂重量104g/m2)をガラス繊維織物(繊維目付量156g/m2)に含浸させてプリプレグを成型した。成型したプリプレグ中のシアネートエステル樹脂組成物は、40質量%である。
樹脂フロー(%) = (はみ出した樹脂硬化物重量)/ (プレス前の積層物重量)×100
○:フィルム作製が良好かつガラス繊維織物への含浸性良好
×:フィルム作製が困難のため、プリプレグの成型ができない
結果を表1に示す。
これに対し、比較例1は、(D)コアシェルゴム粒子を添加していないので、樹脂フローおよび寸法安定性の結果が悪化した。
比較例2は、(C)シリカ微粒子を添加していないので、樹脂フローおよび寸法安定性の結果が悪化した。
比較例3は、(D)コアシェルゴム粒子の配合量が本発明で規定する下限未満であるので、樹脂フローおよび寸法安定性の結果が悪化した。
比較例4は、(C)シリカ微粒子の配合量および(D)コアシェルゴム粒子の配合量ともに本発明で規定する上限を超えているので、作業性が悪化した。
Claims (8)
- (A)シアネートエステル樹脂、
(B)硬化剤もしくは硬化促進剤、
(C)シリカ微粒子、および
(D)コアシェルゴム粒子を含有し、
前記(A)シアネートエステル樹脂100質量部に対し、前記(C)シリカ微粒子を1~5質量部および前記(D)コアシェルゴム粒子を2~10質量部含み、
前記(C)シリカ微粒子と前記(D)コアシェルゴム粒子の質量比が(C)/(D)として1/1~1/5である、
ことを特徴とするシアネートエステル樹脂組成物。 - 平行板にて温度70℃、周波数1Hzで粘弾性測定した際、歪1%のtanδが1未満であり、かつ歪100%のtanδが1以上であることを特徴とする請求項1に記載のシアネートエステル樹脂組成物。
- 前記(A)シアネートエステル樹脂が、ノボラック型のシアネートエステル樹脂である、請求項1に記載のシアネートエステル樹脂組成物。
- 前記(A)シアネートエステル樹脂100質量部に対する前記(C)シリカ微粒子の配合量が、2~4質量部である、請求項1に記載のシアネートエステル樹脂組成物。
- 前記(A)シアネートエステル樹脂100質量部に対する前記(D)コアシェルゴム粒子の配合量が、4~8質量部である、請求項1に記載のシアネートエステル樹脂組成物。
- 前記(C)シリカ微粒子と前記(D)コアシェルゴム粒子の質量比が、(C)/(D)として1/1.5~1/4である、請求項1に記載のシアネートエステル樹脂組成物。
- 請求項1~6のいずれかに記載のシアネートエステル樹脂組成物と強化繊維とからなるプリプレグ。
- 前記プリプレグ中の前記シアネートエステル樹脂組成物の含有量が、30~60質量%である、請求項7に記載のプリプレグ。
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