JP2010083080A - Honeycomb core laminate and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a honeycomb core laminate having superior mechanical strength and water resistance and a method of manufacturing it with high productivity. <P>SOLUTION: The method comprises joining a fiber-reinforced resin layer containing a cycloolefin polymer and a cross-linking agent with at least one of the open end surfaces of a honeycomb core to manufacture a honeycomb core laminate having superior mechanical strength and water resistance. The honeycomb core laminate having superior mechanical strength and water resistance can be manufactured with high productivity by polymerizing a polymerizable composition comprising cycloolefin monomer, a polymerization catalyst and a cross-linking agent in the presence of a reinforcing fibers to obtain a prepreg, laminating the prepreg on at least one of the open end surfaces of the honeycomb core and cross-linking the resultant product. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a honeycomb core laminate comprising a honeycomb core and a fiber reinforced resin layer and a method for producing the same, and more specifically, a honeycomb core and a prepreg comprising a cycloolefin polymer and a crosslinking agent are laminated on the reinforcing fiber, The present invention relates to a honeycomb core laminate obtained by crosslinking and a production method excellent in productivity.

A fiber reinforced resin obtained by reinforcing a resin such as an epoxy resin with a fiber material having excellent mechanical strength, such as carbon fiber, is used in a wide range of applications such as vehicle structures for automobiles and aircraft, and general industrial applications.
In aircraft structural materials and interior materials, honeycomb sandwich panels in which fiber reinforced resin skin panels are provided on both sides of a honeycomb core, which is an aggregate of hollow cells, have been used from the viewpoint of weight reduction.

As the honeycomb core of the honeycomb sandwich panel, an aramid honeycomb, a glass honeycomb, an aluminum honeycomb or the like is used. A honeycomb sandwich panel is generally manufactured by cocure molding in which prepreg is laminated on both sides of a honeycomb core and cured to simultaneously bond the prepreg and the honeycomb core.
For example, in Patent Document 1, a prepreg is produced by bonding a resin composition film containing a thermosetting resin such as an epoxy resin and a curing agent to carbon fibers from both sides, and then the prepreg is bonded via an adhesive. A method of manufacturing a honeycomb core laminated body by curing after being laminated on an aluminum honeycomb is disclosed. However, in this method, there is a problem that the obtained honeycomb core laminate is inferior in adhesiveness at high temperature and high humidity, and the prepreg is cured by two-stage heating in the curing reaction, so that the molding time becomes long and production There were problems such as inferiority.

Further, in Patent Document 2, a prepreg formed by impregnating carbon fiber with a resin composition containing a thermosetting resin such as an epoxy resin, a thermoplastic resin such as a phenoxy resin, and a curing agent, and A honeycomb sandwich panel in which the prepreg and an aramid honeycomb core are laminated is disclosed. In this method, the prepreg is cured by one-step heating, but the molding time is still long.
JP 2007-099966 A JP 2004-292594 A

  The present invention consists of a honeycomb core and a fiber reinforced resin layer comprising a reinforced fiber and a crosslinked product of cycloolefin polymer, and has a mechanical strength, an appearance, and an excellent adhesiveness at high temperature and high humidity, and a honeycomb core laminate and An object of the present invention is to provide a manufacturing method excellent in productivity of the honeycomb core laminated body.

  According to the knowledge of the present inventors, in the prepreg obtained in Patent Documents 1 and 2, the resin in the prepreg is very brittle before curing, particularly when the reinforcing fiber is used in the unidirectionally aligned reinforcing fiber. It was discovered that cracks occurred from the end of the prepreg, and the strength of the honeycomb sandwich panel after curing was lowered and the appearance was deteriorated. We also found a problem that the obtained honeycomb sandwich panel had poor adhesion at high temperature and high humidity. As a result of intensive studies in view of the above problems, the present inventors have determined that at least one surface of a reinforced fiber and a honeycomb core made of a cross-linked cycloolefin polymer as a matrix resin, such as a metal or a fiber reinforced resin, is used. When the honeycomb core laminated body laminated | stacked on this was manufactured, it discovered that this honeycomb core laminated body was excellent in characteristics, such as mechanical strength, an external appearance, and adhesiveness at the time of high temperature / humidity. Further, a honeycomb core laminate excellent in properties such as mechanical strength, appearance, and adhesion at high temperature and high humidity is obtained by laminating a prepreg comprising a cycloolefin polymer, a crosslinking agent and reinforcing fibers on the honeycomb core, and then crosslinking. In particular, a prepreg obtained by polymerizing a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst and a crosslinking agent in the presence of reinforcing fibers is laminated on the honeycomb core, and then crosslinked, resulting in extremely high productivity. It has been found that a honeycomb core laminate can be produced. Based on these findings, the present inventors have completed the present invention.

Thus, according to the present invention, the following (1) to (4) are provided.
(1) A honeycomb core laminate in which a fiber reinforced resin layer containing reinforcing fibers and a crosslinked product of cycloolefin polymer is provided on at least one of the opening end faces of the honeycomb core.
(2) A method for manufacturing a honeycomb core laminated body, wherein a prepreg comprising a cycloolefin polymer, a crosslinking agent and reinforcing fibers is laminated on at least one of the opening end faces of the honeycomb core and then crosslinked.
(3) The method for producing a honeycomb core laminated body according to (2), wherein the prepreg is obtained by polymerizing a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst, and a crosslinking agent in the presence of reinforcing fibers. .
(4) The method for manufacturing a honeycomb core laminated body according to (3), wherein the cycloolefin monomer includes a cycloolefin monomer having two or more carbon-carbon unsaturated bonds in a molecule.

  According to the present invention, a honeycomb core laminate excellent in mechanical strength, appearance, and adhesiveness at high temperature and high humidity can be easily produced with high productivity. Further, since the honeycomb core laminate of the present invention is excellent in mechanical strength, appearance, and adhesion at high temperature and high humidity, it is suitably used in fields such as automobiles, aircrafts, and sports, civil engineering, and architecture. be able to.

(Honeycomb core laminate)
In the present invention, the honeycomb core laminate is formed by bonding a fiber reinforced resin layer using a cross-linked cycloolefin polymer to at least one of the open end faces of the honeycomb core. Such a honeycomb core laminated body is obtained by superimposing at least one of the opening end faces of the honeycomb core on the prepreg and then joining and crosslinking. FIG. 1 shows a state in which fiber reinforced resin layers (broken lines) are bonded to both surfaces of the opening end face of the honeycomb core as an example of the honeycomb core laminated body.
The joining and crosslinking methods may be in accordance with conventional methods, for example, known press machines having a press frame mold for flat plate molding, press molding machines such as sheet mold compound (SMC) and bulk mold compound (BMC), Examples thereof include a method using an autoclave and an oven. The pressure is usually 0.01 to 1 MPa, preferably 0.05 to 0.5 MPa. Further, the hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The heating temperature is equal to or higher than the temperature at which a crosslinking reaction is induced by a crosslinking agent described below, and is typically in the range of 100 to 300 ° C, preferably 150 to 250 ° C. When a radical generator is used as the crosslinking agent, it is at least one minute half-life temperature of the radical generator, preferably at least 5 ° C. above the one-minute half-life temperature, more preferably at least 10 ° C. above the one-minute half-life temperature. High temperature. The heating time is in the range of 0.1 to 180 minutes, preferably 1 to 120 minutes, more preferably 2 to 20 minutes.

(Honeycomb core)
The honeycomb core used in the present invention constitutes the honeycomb core laminated body, and is a plate-like material in which hollow cells are continuously formed adjacent to each other in the outer peripheral direction. The shape of the hollow cell is not particularly limited, and examples thereof include a polyhedron such as a triangle, a quadrangle, a pentagon, a hexagon, a heptagon, an octagon, a trapezoid, and an unequal side polygon, and a circle such as a circle and an ellipse. Among these, a polyhedron is preferable, and a hexagon is particularly preferable.
The material of the honeycomb core used in the present invention is not particularly limited, and examples thereof include metal, paper, flame retardant paper, resin, fiber reinforced resin, ceramics, ceramic paper, and the like, preferably metal, resin, A fiber reinforced resin, more preferably a fiber reinforced resin.

Examples of the metal include aluminum, aluminum alloy, titanium, stainless steel, steel, and the like. Among these, aluminum is preferable.
Examples of paper include kraft paper, vegetable fiber such as pulp, or paper made of synthetic fiber such as polyester, polyamide, rayon, polyvinyl alcohol, paper made of organic or inorganic fiber such as aramid paper, graphite paper, glass paper, etc. .
Flame retardant paper is a flame retardant paper in which magnesium silicate, aluminum hydroxide, antimony oxide, phosphorus compound, halogen compound, boron compound, etc. are mixed and added to the fiber raw material used in the above paper. Or, a flame-retardant paper obtained by post-impregnation after forming into a paper or after forming into a honeycomb can be mentioned.
Examples of the resin include vinyl chloride, polypropylene, polyethylene, polyurethane, polyimide, polyetherimide, and polycarbonate.
Examples of fiber reinforced resins include the above-mentioned various papers and / or glass, graphite, aramid, thermoplastic polyester, rayon, polyamide, polyvinyl alcohol, pulp, and other inorganic and organic fiber woven or non-woven fabrics, phenol, polyimide, polyester, A composite material in which a thermosetting resin such as epoxy or a thermoplastic resin such as nylon or polyimide is impregnated, for example, a resin-impregnated honeycomb core in which an aramid paper is impregnated with a phenol resin may be used.
Examples of the ceramic include cordierite and mullite, and examples of the ceramic paper include paper made of alumina, alumina silica fiber, and the like.

The hollow cell size of the honeycomb core used in the present invention is appropriately selected according to the purpose of use and the structure, but is usually 0.1 to 100 mm, preferably 0.5 to 50 mm, more preferably 1 to 20 mm. It is.
The porosity of the honeycomb core used in the present invention is represented by a calculated value of (volume occupied by the honeycomb core−volume of the partition material of the honeycomb core) ÷ volume occupied by the honeycomb core, and is generally 80 to 99.9%, preferably Is in the range of 90-99%.
The thickness of the honeycomb core used in the present invention is appropriately selected according to the purpose of use, but is usually 1 to 150 mm, preferably 5 to 100 mm, more preferably 5 to 50 mm.

(Fiber reinforced resin layer)
The fiber reinforced resin layer used in the present invention is bonded to a honeycomb core to constitute a honeycomb core laminate. The fiber reinforced resin layer includes a reinforced fiber and a crosslinked product of a cycloolefin polymer, and is obtained by heating a fiber reinforced molded product according to the crosslinking conditions.

(Reinforced fiber)
The reinforcing fiber used in the present invention is not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultrahigh molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; Examples thereof include inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, organic fiber, glass fiber, and carbon fiber are preferable, and carbon fiber is more preferable. In particular, the carbon fiber is excellent in compatibility with the crosslinked product of the cycloolefin polymer, and highly improves the properties of the obtained honeycomb core laminate, such as mechanical strength, appearance, adhesion at high temperature and high humidity, and heat resistance. This is preferable. The type of carbon fiber is not particularly limited. For example, carbon fibers produced by various conventionally known methods such as acrylic, pitch, and rayon can be used. Among them, acrylic fiber (polyacrylonitrile fiber) Acrylic carbon fiber, which is a carbon fiber produced using as a raw material, is suitable because it does not inhibit metathesis polymerization and can improve properties such as mechanical strength, toughness, and heat resistance.

  The strength characteristic of the reinforcing fiber used in the present invention is not particularly limited and is appropriately selected according to the purpose of use. The tensile strength is a strand tensile strength measured according to JIS R7601, and is usually 0.5 to 50 GPa, preferably 1 to 10 GPa, more preferably 2 to 8 GPa. The tensile modulus is a strand tensile modulus measured according to JIS R7601, and is usually in the range of 100 to 1,000 GPa, preferably 200 to 800 GPa, more preferably 300 to 700 GPa. The elongation is a strand tensile elongation measured according to JIS R7601, and is usually 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 3%. When the strength characteristics of the reinforcing fibers are within these ranges, the mechanical strength and appearance characteristics of the resulting honeycomb core laminate are highly balanced, which is preferable.

  The cross-sectional shape of the reinforcing fiber used in the present invention is not particularly limited, but is preferably substantially circular. This is because, when the cross-sectional shape is circular, the filaments are easily rearranged when impregnated with the below-described polymerizable composition, and the penetration of the polymerizable composition between the fibers becomes easy. Furthermore, since the thickness of the fiber bundle can be reduced, there is an advantage that it is easy to obtain a prepreg excellent in drapeability. Note that the cross-sectional shape is substantially circular when the ratio of the circumscribed circle radius R to the inscribed circle radius r (R / r) of the cross section is defined as the degree of deformation. Meaning one or less.

  The length of the reinforcing fiber used in the present invention is appropriately selected according to the purpose of use without any particular limitation, and either a short fiber or a long fiber can be used, but a honeycomb having higher mechanical strength and toughness. When it is desired to obtain a core, the length of the fiber is 1 cm or more, preferably 2 cm or more, more preferably 3 cm or more, and most preferably continuous fiber.

The form of the reinforcing fiber used in the present invention is not particularly limited, and the unidirectional material in which the reinforcing fibers are aligned in one direction, the woven fabric, the knit, the braid, the long fiber such as the roving, the short fiber, and the processing thereof. The product can be appropriately selected from chopped, milled, non-woven fabric, mat, and the like. Among these, in order to obtain a fiber reinforced resin having higher levels of toughness and impact resistance, it is preferably in the form of continuous fibers such as unidirectional materials, woven fabrics, and rovings.
As the woven form, conventionally known ones can be used. For example, all of woven structures in which fibers such as plain weave, satin weave, twill weave, and triaxial weave are interlaced can be used. Moreover, as a woven fabric form, not only two-dimensional but also a stitch woven fabric and a three-dimensional woven fabric in which fibers are reinforced in the thickness direction of the woven fabric can be used.

The carbon fiber used in the present invention is used as a fiber bundle yarn when used in a woven fabric or the like. In this case, the number of filaments in one fiber bundle yarn is not particularly limited, but is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 10, The range is from 000 to 30,000.

These reinforcing fibers can be used alone or in combination of two or more, and the amount used is appropriately selected according to the purpose of use, but the reinforcing fibers in the obtained prepreg or in the fiber reinforced resin layer The content is usually selected to be in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. When the reinforcing fiber content is in this range, the properties of mechanical strength and toughness are highly balanced and suitable.

(Cross-linked product of cycloolefin polymer)
The crosslinked product of cycloolefin polymer used in the present invention is obtained by crosslinking molecular chains of cycloolefin polymer and does not dissolve in a solvent. Such a solvent is appropriately selected from solvents such as aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as dichloromethane and chloroform. The crosslinking method can employ any of radical crosslinking, ionic crosslinking, metathesis crosslinking, and the like, and is not limited, but radical crosslinking is preferred.

(Fiber-reinforced molded product and prepreg)
The honeycomb core laminate used in the present invention is manufactured in such a form as shown in FIG. 1 by heating and pressure-bonding the following fiber-reinforced molded body on the honeycomb core. The fiber reinforced molded body is a molded body having an arbitrary shape such as a sheet shape, a film shape, a column shape, a column shape, or a polygonal column shape, and is formed by impregnating a reinforcing fiber with a cycloolefin polymer. In particular, when the fiber-reinforced molded product is a sheet, this is used as a prepreg. When the fiber reinforced molded body is a prepreg, the mechanical strength of the resulting honeycomb core laminate is improved, which is preferable. Further, in particular, when a fiber reinforced molded body further containing a crosslinking agent in addition to the cycloolefin polymer and the reinforcing fiber is used, the mechanical strength, appearance, and adhesiveness at high temperature and high humidity of the resulting honeycomb core laminate are improved. Excellent and preferred. The fiber reinforced molded product used in the present invention is preferably obtained by polymerizing a polymerizable composition in the presence of reinforced fibers. The polymerization method is not particularly limited, but bulk polymerization is preferred. Fiber reinforced resin of various shapes can be obtained by bulk polymerization. Here, “in the presence” means that the polymerization is performed in a state where the reinforcing fiber and the polymerizable composition are in contact with each other. Specifically, when the reinforcing fiber is a woven fabric, there is a method in which the reinforcing fiber is impregnated with a polymerizable composition and then bulk polymerization is performed. The impregnation of the polymerizable composition into the reinforcing fiber can be performed in a mold, and when the fiber reinforced molded body is a prepreg, it can be performed in a normal mold or on a protective film, but on a protective film. Is preferred.

  When impregnation is performed on a protective film, for example, a predetermined amount of the polymerizable composition is reinforced by a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method. It can be performed by applying to a fiber, overlaying a protective film on it if desired, and pressing with a roller or the like from above. After impregnating the polymerizable composition into the reinforcing fiber, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, whereby a prepreg is obtained. Examples of the protective film used herein include resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; metal materials such as iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver; The thing which consists of is mentioned.

  In the case where the impregnation is performed in a mold, it can be performed by placing reinforcing fibers in the mold and pouring the polymerizable composition into the mold. According to this method, a fiber-reinforced molded body having an arbitrary shape including a prepreg can be obtained. Examples of the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape. As the mold used here, a conventionally known mold, for example, a mold having a split mold structure, that is, a core mold and a cavity mold, can be used, and a polymerizable composition is injected into these voids (cavities). And bulk polymerization is performed. The core mold and the cavity mold are produced so as to form a void that matches the shape of the target fiber-reinforced molded body. Further, the shape, material, size and the like of the mold are not particularly limited. Also, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. A prepreg can also be obtained by polymerization in the mold.

The amount of reinforcing fibers of the fiber-reinforced molded body thus obtained is appropriately selected according to the purpose of use, but is usually 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. is there.
The thickness of the prepreg when the fiber reinforced molded product used in the present invention is a prepreg is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.01 to 1 mm, more preferably. Is in the range of 0.05 to 0.5 mm. Within this range, it is easy to follow the shape of the honeycomb core to be laminated, and the properties such as mechanical strength and energy absorption are sufficiently exhibited.
The amount of volatile components of the fiber reinforced molded product used in the present invention is an amount volatilized at 200 ° C. for 1 hour, and is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less. . If the amount of volatile components in the fiber reinforced molded product is excessively large, stickiness of the fiber reinforced molded product will occur, resulting in poor operability, and voids will be generated in the fiber reinforced resin layer after crosslinking, resulting in reduced mechanical strength. There is a possibility that problems such as bleeding and a decrease in heat resistance may occur. Such a fiber reinforced molded article having a small amount of volatile components and few voids can be easily obtained by the direct polymerization method. In the wet method, a large amount of both volatile components and voids may remain. In addition, a large amount of voids may remain even in the hot melt method.

  In the present invention, a fiber reinforced resin layer can be obtained by laminating a plurality of the prepregs and cross-linking as desired. In such a case, a plurality of prepregs are preliminarily stacked before being crosslinked, and are bonded by a hot press machine, a molding machine, etc., and the prepregs are laminated with each other using the melting of the cycloolefin polymer. It is preferable to prepare a body. The heating temperature is usually in the range of 100 to 180 ° C, preferably 120 to 170 ° C, more preferably 140 to 160 ° C. The heating time is usually in the range of 1 to 30 minutes, preferably 2 to 20 minutes, more preferably 5 to 15 minutes. When the heating temperature and time are within this range, the crosslinking reaction does not proceed and the adhesion between layers is improved.

  Moreover, in this invention, when the reinforced fiber used for a prepreg is a unidirectional material, it is preferable that a prepreg is used as a laminated body of 4 layers or 8 layers. The prepreg constituting each layer is laminated with the direction of each reinforcing fiber being shifted from the angle with respect to the prepreg constituting the other layer of the laminate. When the laminate of prepregs is four layers, one reference line is taken, and the angle (smaller one) between the reference line and the reinforcing fiber of each layer is θ, and θ = −45 ° and 45 ° in order. , 45 °, and −45 ° are preferably laminated. Moreover, when the laminated body of prepreg is 8 layers, it is preferable to laminate | stack in order with (theta) = 0 degree, 90 degrees, -45 degrees, 45 degrees, 45 degrees, -45 degrees, 90 degrees, 0 degrees. When each layer of the prepreg laminate is configured as described above, it is preferable that the prepreg laminate and the honeycomb core laminate have no warp and have no mechanical strength anisotropy.

(Cycloolefin polymer)
The cycloolefin polymer used in the present invention constitutes a fiber reinforced molded article, and is a polymer of cycloolefin monomer. Specific examples include ring-opening polymers, addition polymers of cycloolefin monomers, addition copolymers of cycloolefin monomers and chain olefin monomers, and hydrides thereof. Among these, a ring-opening polymer or an addition polymer is preferable, and a ring-opening polymer is more preferable. The polymerization methods include solution polymerization and bulk polymerization, and bulk polymerization that can be molded simultaneously with the polymerization without requiring steps such as solvent drying and polymer purification is preferred because of its high productivity. In the present invention, the cycloolefin polymer does not have a cross-linked structure and is soluble in a solvent. Such a solvent is appropriately selected from solvents such as aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and chloroform.
The molecular weight of the cycloolefin polymer is a polystyrene-reduced weight average molecular weight of a tetrahydrofuran solution measured by gel permeation chromatography, and is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, More preferably, it is the range of 10,000-100,000.

(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a cycloolefin polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Accordingly, the cycloolefin polymer becomes a post-crosslinkable thermoplastic resin. In the present invention, a radical generator is usually preferably used as the crosslinking agent. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and organic peroxides and nonpolar radical generators are preferable.

Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3, And cyclic peroxides such as 6,9-trimethyl-1,4,7-triperoxonane and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; In particular, when a metathesis polymerization catalyst is used as the polymerization catalyst, cyclic peroxides, dialkyl peroxides, and peroxyketals are preferred in that the inhibition of the metathesis polymerization reaction is small and there are few obstacles to the polymerization reaction.
Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4′-azidobenzal) cyclohexanone, and the like.
Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.

When the crosslinking agent used in the present invention is a radical generator, the 1-minute half-life temperature is appropriately selected depending on the conditions of curing (crosslinking of the cycloolefin polymer), but is usually 100 to 300 ° C., preferably 150 to It is 250 degreeC, More preferably, it is the range of 160-230 degreeC. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. For the 1 minute half-life temperature of the radical generator, refer to, for example, a product catalog (http://www.nof.co.jp/upload_public/sogo/B0100.pdf) introduced on the homepage of Nippon Oil & Fats Co., Ltd. Good.
These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is usually in the range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. .

(Polymerizable composition)
The fiber-reinforced molded article used in the present invention is preferably produced by polymerization and molding from the polymerizable composition shown below. The polymerizable composition typically comprises a cycloolefin monomer, a polymerization catalyst, and a crosslinking agent. Further, the polymerizable composition may include a crosslinking agent in a solution obtained by dissolving a cycloolefin polymer in a solvent. If desired, a polymerization regulator, a polymerization reaction retarding agent, a chain transfer agent, a crosslinking aid, a filler, an anti-aging agent, an elastomer material, and other compounding agents can be added to the polymerizable composition.
The polymerizable composition of the present invention has a low viscosity as compared with conventional epoxy resin solutions and the like, and is excellent in impregnation properties for reinforcing fibers, so that the reinforcing fibers can be uniformly impregnated with the resin obtained by polymerization. .
In addition, when bulk polymerization is performed, the polymerizable composition has a low content of a solvent or the like that does not participate in the reaction. Therefore, a process such as removing the solvent after impregnating the reinforcing fiber is not required, which increases productivity. Excellent, no odor or swelling due to residual solvent, and excellent heat resistance.

When the reinforcing fiber is a short fiber such as chopped, a method of mixing the reinforcing fiber with the polymerizable composition and then performing polymerization can be mentioned. The carbon fiber may be added to the monomer liquid and / or the catalyst liquid before mixing the monomer liquid and the catalyst liquid, or may be added after mixing the monomer liquid and the catalyst liquid. Examples of the polymerization method include a method of performing bulk polymerization in a mold in the same manner as described above. Alternatively, short fibers and long fibers may be used in combination, and a polymerizable composition containing reinforcing fibers of short fibers may be impregnated into the long fibers in the same manner as described above before polymerization.
In any of the above methods, the heating temperature for polymerizing the polymerizable composition is usually in the range of 50 to 300 ° C, preferably 100 to 250 ° C, more preferably 120 to 220 ° C. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes. Heating the polymerization composition under the conditions in this range is preferable because a fiber-reinforced molded body with less unreacted monomer can be obtained.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having a ring structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the ring structure. As used herein, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of chain polymerization (ring-opening polymerization). There are various types of ring-opening polymerization, such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it usually refers to metases ring-opening polymerization.

Examples of the ring structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. Although there is no limitation in particular in carbon number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. However, from the viewpoint of improving the water resistance of the resulting honeycomb core laminate, those having no polar group, that is, comprising only carbon atoms and hydrogen atoms are preferred.

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the heat resistance, mechanical strength, and water resistance of the resulting honeycomb core laminate, a polycyclic cycloolefin monomer is preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecene and the like can be mentioned.

  Cycloolefin monomers are divided into those having no crosslinkable carbon-carbon unsaturated bonds and those having one or more crosslinkable carbon-carbon unsaturated bonds. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction. In particular, it refers to a radical crosslinking reaction. Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and within the ring structure formed of carbon atoms, any other than the ring structure For example, at the end or inside of the side chain.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. , Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and other monocyclic cycloolefin monomers; norbornene, 5-methylnorbornene, 5-ethylnorbornene 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 1,4,5,8-dimethano 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5 8-Dimethano-1,2,3,4,4a, 5,8,8-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1 5-Dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5 -Chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxene Norbornene monomers such as silnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene and the like can be mentioned, and norbornene monomers having no crosslinkable carbon-carbon unsaturated bond are preferable.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene Norbornene monomers such as 2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylnorbornene, 5-allylnorbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene; Preferably crosslinkable carbon- The containing unsaturated bonds is a norbornene-based monomer having one or more.
These cycloolefin monomers can be used alone or in combination of two or more.

As the cycloolefin monomer used in the present invention, one containing a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds is preferable because the mechanical strength is improved in the obtained honeycomb core laminate.
In the cycloolefin monomer blended in the polymerizable composition of the present invention, a blend of a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds The ratio is appropriately selected as desired, but in a weight ratio (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond), usually, It is in the range of 5/95 to 100/0, preferably 10/90 to 90/10, more preferably 15/85 to 70/30. If the blending ratio is within such a range, the obtained honeycomb core laminate is suitable because properties such as mechanical strength, interlayer adhesion, and water resistance are highly balanced.

(Polymerization catalyst)
The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize the cycloolefin monomer, but the polymerizable composition of the present invention is directly subjected to bulk polymerization in the production of a fiber-reinforced molded article. In general, it is preferable to use a metathesis polymerization catalyst.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6 and Group 8 (according to the long-period periodic table; the same shall apply hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum. Examples of the Group 6 atom include molybdenum and tungsten. Examples of the Group 8 atom include Examples thereof include ruthenium and osmium. Among them, group 8 ruthenium and osmium are preferable as the transition metal atom. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the fiber-reinforced molded body is obtained by subjecting the polymerizable composition of the present invention to bulk polymerization, the resulting fiber-reinforced molded body is derived from unreacted monomers. A high-quality fiber-reinforced molded product with low odor and good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  As the ruthenium carbene complex, since the mechanical strength and impact resistance of the obtained fiber-reinforced molded body and the honeycomb core laminate can be highly balanced, at least one carbene compound having a heterocyclic structure is used as a ligand. Are preferably included. As a hetero atom which comprises a heterocyclic structure, an oxygen atom, a nitrogen atom, etc. are mentioned, for example, Preferably it is a nitrogen atom. Moreover, as a heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable. Specific examples of the compound having such a heterocyclic structure include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3- Di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene, 1 , 3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3-dimesitylimidazolidine-2-ylidene, 1,3-dicyclohexylimidazolidine 2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzii Such as imidazole-2-ylidene and the like.

  Specific examples of a suitable ruthenium carbene complex used as a metathesis polymerization catalyst in the present invention include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3- Hydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4- Triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene ) Ruthenium carbene complexes having a carbene compound having a heterocyclic structure and other neutral electron donors as ligands such as pyridine ruthenium dichloride. Here, the “neutral electron donor” refers to a ligand having a neutral charge when separated from the central metal atom. A carbene compound having a heterocyclic structure is also a kind of neutral electron donor.

  The metathesis polymerization catalysts may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used is a molar ratio (metal atom in the metathesis polymerization catalyst: cycloolefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1. : 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.

  If desired, the metathesis polymerization catalyst can be used dissolved or suspended in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane , Decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; indene, tetrahydronaphthalene and other alicyclic and aromatic rings A nitrogen-containing hydrocarbon such as nitromethane, nitrobenzene, and acetonitrile; an oxygen-containing hydrocarbon such as diethyl ether and tetrahydrofuran; and the like. Among these, it is preferable to use a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.

  The polymerization regulator is blended for the purpose of controlling the metathesis polymerization activity or improving the metathesis polymerization reaction rate. For example, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, Examples include trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium. These polymerization regulators can be used alone or in combination of two or more. The amount of the polymerization regulator used is, for example, a molar ratio of (metal atom in the metathesis polymerization catalyst: polymerization regulator), usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20. More preferably, it is in the range of 1: 0.5 to 1:10.

It is preferable that the polymerizable composition used in the present invention contains a polymerization reaction retarder because the increase in viscosity can be suppressed and the polymerizable composition can be uniformly impregnated into the reinforcing fiber. Polymerization retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used.
Among these polymerization reaction retarders, a phosphine compound is preferable because of its great effect of suppressing the progress of the polymerization reaction at room temperature or lower, and triphenylphosphine, triethylphosphine, dicyclohexylphosphine, and vinyldiphenylphosphine are more preferable. The compounding amount is a molar ratio of (metal atom in the metathesis polymerization catalyst: polymerization reaction retarder), usually 1: 0.01 to 1: 100, preferably 1: 0.1 to 1:10, more preferably It is in the range of 1: 0.1 to 1: 5.
The chain transfer agent is a compound that can participate in ring-opening polymerization and has one aliphatic carbon-carbon double bond that can be bonded to the terminal of a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. . Examples of the double bond include a terminal vinyl group. The chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds.

Specific examples of such chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, 4- Chain transfer agents without crosslinkable carbon-carbon unsaturated bonds, such as vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol A chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as diacrylate; a chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane; Na And the like. Among these, a chain having one or more crosslinkable carbon-carbon unsaturated bonds in the molecule from the viewpoint of highly balancing the properties such as mechanical strength, formability, and interlayer adhesion of the obtained honeycomb core laminate. Transfer agents are preferred, and those having one crosslinkable carbon-carbon unsaturated bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, undecenyl methacrylate, and the like are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent added to the polymerizable composition of the present invention is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the cycloolefin monomer to be added. More preferably, it is the range of 0.2-5 weight part.

  In the present invention, by adding a crosslinking aid to the polymerizable composition, the impregnation property of the polymerizable composition into the reinforcing fibers can be highly improved, and the shapeability of the honeycomb core laminate obtained by crosslinking can be increased. The mechanical strength is highly balanced, which is preferable. As the crosslinking aid, a polyfunctional crosslinking aid having two or more crosslinkable carbon-carbon unsaturated bonds that can participate in the crosslinking reaction induced by the crosslinking agent without involving in the ring-opening polymerization is suitably used. . Such a crosslinkable carbon-carbon unsaturated bond is preferably present in the compound constituting the crosslinking aid, for example, as a terminal vinylidene group, particularly as an isopropenyl group or methacryl group, particularly as a methacryl group.

  Specific examples of the crosslinking aid include polyfunctional crosslinking aids having two or more isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2′-bis (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc. Polyfunctional coagent having more; and the like. Among these, as the crosslinking aid, a polyfunctional crosslinking aid having two or more methacryl groups is preferable. Of the polyfunctional crosslinking aids having two or more methacrylic groups, polyfunctional crosslinking aids having three methacrylic groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate are more preferred.

  The crosslinking aids can be used alone or in combination of two or more. As a compounding quantity of the crosslinking adjuvant to the polymeric composition of this invention, it is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin monomers to mix | blend, Preferably 0.5-50 weight part, More preferably, it is 1-30 weight part.

The filler is not particularly limited as long as it is generally used industrially, and either an inorganic filler or an organic filler can be used, but an inorganic filler is preferred. Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate, Aluminum nitride, silicon carbide particles Whiskers, and the like. Examples of the organic filler include particulate compounds such as wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more, and the blending amount is usually 1 to 1,000 parts by weight, preferably 10 to 100 parts by weight with respect to 100 parts by weight of the cycloolefin polymer. The amount is in the range of 500 parts by weight, more preferably 50 to 350 parts by weight.
When the filler is in this range, the honeycomb core laminate can be remarkably improved in properties such as mechanical strength, heat resistance and chemical resistance, which is preferable.

  Moreover, as an anti-aging agent, blending at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent is a cross-linking. It is preferable because the heat resistance of the resulting honeycomb core laminate can be improved to a high degree without hindering the reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. The amount of the anti-aging agent is appropriately selected as desired, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer to be blended. Is in the range of 0.01 to 2 parts by weight.

  By adding an elastomer material to the polymerizable composition used in the present invention, it is possible to improve the toughness of the resulting honeycomb core laminate. Examples of the elastomer material include natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, chloroprene, acrylonitrile-butadiene copolymer, styrene-isoprene-styrene block copolymer, and styrene-butadiene-styrene block copolymer. , Ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, and hydrogenated products thereof. These elastomer materials can be used alone or in combination of two or more. The compounding quantity is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin polymers, Preferably it is 1-50 weight part, More preferably, it is the range of 3-30 weight part. It is preferable because the toughness of the fiber reinforced resin layer obtained when the elastomer material is within this range can be improved to a high degree. Other materials can be appropriately added to the polymerizable composition according to the purpose of use.

  Other compounding agents are not particularly limited and are appropriately selected according to the purpose of use, and examples thereof include flame retardants, colorants, light stabilizers, foaming agents, and polymer modifiers. Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxides such as aluminum hydroxide, and antimony compounds such as antimony trioxide. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The polymerizable composition used in the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a solution (catalyst solution) in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent, a cycloolefin monomer, and a crosslinking agent, and other additives as required. It can be prepared by adding to the blended liquid (monomer liquid) and stirring.

  The honeycomb core laminate of the present invention thus obtained is excellent in mechanical strength, appearance, and adhesion at high temperature and high humidity. For example, OA and AV equipment, vehicle members such as automobiles and railways, aircraft interior parts, etc. First, it is suitably used for sports applications such as golf shafts and fishing rods, and other general industrial applications. Specific applications include, for example, fishing rods, golf club shafts, tennis rackets, ski stocks, and other sports applications; displays, FDD carriages, chassis, HDD, MO, motor brush holders, parabolic antennas, laptop computers, mobile phones, Electric / electronic devices such as digital still cameras, PDAs, portable MDs, liquid crystal displays, plasma displays; telephones, facsimiles, VTRs, photocopiers, televisions, irons, hair dryers, rice cookers, microwave ovens, audio equipment, vacuum cleaners, toiletries Supplies, leather discs, compact discs, lighting, refrigerators, air conditioners, typewriters, word processors, office automation equipment and household appliances; undercovers, scuff plates, pillar trims, professionals Automobiles such as rubber shafts, drive shafts, wheels, wheel covers, fenders, door mirrors, room mirrors, feshers, bumpers, bumper beams, bonnets, trunk hoods, aero parts, platforms, cowl louvers, roofs, instrument panels, spirals and various modules Parts; aircraft parts such as landing gear pods, wing reds, spoilers, edges, ladders, and failings; and building materials such as panels. Among these, it is particularly suitable as a member for vehicles such as automobiles and airplanes.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

Each characteristic in an Example and a comparative example is measured and evaluated according to the following method.
(1) Mechanical strength: The obtained honeycomb core laminate was placed in a constant temperature and humidity chamber kept constant at a temperature of 25 ° C. and a humidity of 55% for 24 hours, and the mechanical strength (shear strength) before and after installation was determined as MIL. -Measured in the W direction of FIG. 3 based on STD-401, and the rate of decrease is determined according to the following criteria.
Good: Decreasing rate of less than 20% Poor: Decreasing rate of 20% or more (2) Appearance: The appearance of the obtained prepreg and honeycomb core laminate is observed and evaluated according to the following criteria.
Good: Disturbance of reinforcing fiber, resin flow, etc. are not recognized. Bad: Disturbance of reinforcing fiber, resin flow, etc. are observed. (3) Adhesion at high temperature and high humidity: The resulting honeycomb core laminate is at a temperature of 85.degree. The change in the adhesion between the fiber reinforced resin layer and the honeycomb core before and after being left for 72 hours in an 85% high temperature and high humidity tester is evaluated according to the following criteria by measuring the change in shear strength according to ASTM D2344.
Good: Decreasing rate of less than 20% Poor: Decreasing rate of 20% or more (4) Productivity: The time required for heating the prepreg (fiber reinforced molded product) laminate is evaluated according to the following criteria.
Good: 1 hour less than 30 minutes Slightly good: 1 hour 30 minutes or more and less than 3 hours Defect: 3 hours or more

Example 1
Benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 51 parts as a polymerization catalyst and 79 parts of triphenylphosphine as a polymerization reaction retarder were dissolved in 952 parts of toluene. To prepare a catalyst solution. Separately, 100 parts of dicyclopentadiene (DCP) as a cycloolefin monomer, 0.74 parts of allyl methacrylate as a chain transfer agent, and di-t-butyl peroxide as a crosslinking agent (1 minute half-life temperature 186 ° C.) 1.2 15 parts of trimethylolpropane trimethacrylate as a crosslinking aid and 1.0 part of 3,5-di-t-butyl-4-hydroxyanisole as a phenolic antioxidant are mixed to prepare a monomer solution. The above catalyst solution is added at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.

  Next, 100 parts of the resulting polymerizable composition was cast on a polyethylene naphthalate film (thickness 75 μm), and carbon fiber pyrofil TR 30S 3L (manufactured by Mitsubishi Rayon Co., Ltd.) arranged in one direction on the polyethylene naphthalate film. Then, 80 parts of the polymerizable composition is cast thereon, and a polyethylene naphthalate film is further covered thereon, and a carbon fiber is impregnated with the polymerizable composition using a roller. Next, this is heated in a heating furnace heated to 130 ° C. for 1 minute to bulk polymerize the polymerizable composition to obtain a prepreg having a thickness of 125 μm. The obtained four prepreg polyethylene naphthalate films are peeled off, and the carbon fibers of each layer are stacked so that θ = −45 ° / 45 ° / 45 ° / −45 ° in order from the bottom, and 150 ° C. for 5 minutes to 3 MPa. The laminate of prepregs is obtained by heating and pressing.

  An adhesive denatite (Nagase Chemtex) was applied to the opening end of honeycomb core Hanikome-A AL-60 (manufactured by Nippon Nihon Feather Core), and a prepreg laminate was placed on both sides. The temperature was raised at 1 MPa at 6 ° C./min, heat-pressed at 200 ° C. for 15 minutes, and the temperature was similarly lowered at 6 ° C./min to obtain a honeycomb core laminate. Further, it is confirmed that there is no weight change after the honeycomb core laminate obtained is immersed in chloroform and left at room temperature for 30 minutes, and that sufficient crosslinking has occurred. The evaluation results are shown in Table 1.

(Example 2)
A honeycomb core laminate is obtained in the same manner as in Example 1 except that the laminate of the prepreg laminate and the honeycomb core is heated in an autoclave at 0.3 MPa and 180 ° C. for 30 minutes. The resulting honeycomb core laminate is dipped in chloroform, and after standing at room temperature for 30 minutes, there is no change in weight, and it is confirmed that sufficient crosslinking has occurred. The evaluation results are shown in Table 1.

(Example 3)
A 250 μm prepreg is obtained in the same manner as in Example 1 except that carbon fiber woven pyrofil TR 3110M (manufactured by Mitsubishi Rayon Co., Ltd.) is used as the reinforcing fiber. The obtained two prepreg polyethylene naphthalate films are peeled and overlapped, and heated and pressed at 3 MPa at 150 ° C. for 5 minutes to obtain a laminate of prepregs.

  An adhesive denatite (Nagase Chemtex) was applied to the opening end of honeycomb core Hanikome-A AL-60 (manufactured by Nippon Nihon Feather Core), and a prepreg laminate was placed on both sides. The temperature was raised at 1 MPa, 6 ° C./min, heat-pressed at 200 ° C. for 15 minutes, and the temperature was similarly lowered at 6 ° C./min to obtain a honeycomb core laminate. Further, it is confirmed that there is no weight change after the honeycomb core laminate obtained is immersed in chloroform and left at room temperature for 30 minutes, and that sufficient crosslinking has occurred. The evaluation results are shown in Table 1.

(Comparative Example 1)
47 parts of liquid bisphenol A type epoxy resin Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.), 37 parts of epoxy resin Araldite AER4152 (manufactured by Asahi Kasei Co., Ltd.) having an oxazolidone ring skeleton, 28 parts of bisphenol A type epoxy resin Epicote 1002 (manufactured by Japan Epoxy Resin Co., Ltd.) 28 Parts, 20 parts of polyphenylmethane type epoxy resin EPPN502H (manufactured by Nippon Kayaku Co., Ltd.), 5 parts of phenoxy resin phenototo YP70 (manufactured by Tohto Kasei Co., Ltd.), (3- (3,4-dichlorophenyl) -1,1 as a curing agent -Dimethylurea A resin film comprising 6 parts of DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.) and 4 parts of dicyandiamide Dicy7 (manufactured by Japan Epoxy Resin Co., Ltd.) is applied onto a release paper to produce a resin film. Next, the resin film is superposed on both sides of the carbon fiber on carbon fiber pyrofil TR 30S 3L (Mitsubishi Rayon Co., Ltd.) arranged in one direction, heated and pressurized to transfer the resin onto the carbon fiber, and then separated. A prepreg having a thickness of 125 μm is obtained by laminating the pattern paper and the protective film. The obtained four prepreg polyethylene naphthalate films are peeled off, and the carbon fibers of each layer are stacked so that θ = −45 ° / 45 ° / 45 ° / −45 ° in order from the bottom, and 100 ° C. for 5 minutes to 3 MPa. The laminate of prepregs is obtained by heating and pressing.

  An adhesive denatite (Nagase Chemtex) was applied to the opening end of honeycomb core Hanikome-A AL-60 (manufactured by Nippon Nihon Feather Core), and a prepreg laminate was placed on both sides. .3 MPa, raised from room temperature to 80 ° C. at 3 ° C./min, held at 80 ° C. for 30 minutes, further raised to 130 ° C. at 3 ° C./min, then heated at 130 ° C. for 90 minutes, The temperature is lowered at 3 ° C./min to cure the adhesive and obtain a honeycomb core laminate.

(Comparative Example 2)
A 250 μm prepreg is obtained in the same manner as in Comparative Example 1 except that carbon fiber woven pyrofil TR 3110M (manufactured by Mitsubishi Rayon Co., Ltd.) is used as the reinforcing fiber. By peeling off the two polyethylene naphthalate films of the obtained prepreg, raising the temperature at 3 ° C./min, holding at 100 ° C. for 5 min, lowering the temperature at 3 ° C./min, and hot pressing at 3 MPa To obtain a prepreg laminate.

  An adhesive denatite (Nagase Chemtex) was applied to the opening end of honeycomb core Hanikome-A AL-60 (manufactured by Nippon Nihon Feather Core), and a prepreg laminate was placed on both sides. .3 MPa, raised from room temperature to 80 ° C. at 3 ° C./min, held at 80 ° C. for 30 minutes, further raised to 130 ° C. at 3 ° C./min, then heated at 130 ° C. for 90 minutes, The temperature is lowered at 3 ° C./min to cure the adhesive and obtain a honeycomb core laminate. The resulting honeycomb core laminate is dipped in chloroform, and after standing at room temperature for 30 minutes, there is no change in weight, and it is confirmed that sufficient crosslinking has occurred. The evaluation results are shown in Table 1.

As an example of the honeycomb core laminated body, a state in which fiber reinforced resin layers (broken lines) are bonded to both surfaces of the opening end face of the honeycomb core is shown.

Claims (4)

  A honeycomb core laminate in which a fiber reinforced resin layer containing reinforcing fibers and a crosslinked product of cycloolefin polymer is bonded to at least one of the opening end faces of the honeycomb core.   A method for producing a honeycomb core laminate, comprising: laminating a prepreg comprising a cycloolefin polymer, a crosslinking agent, and reinforcing fibers on at least one of the opening end faces of the honeycomb core, and then crosslinking the prepreg.   The method for manufacturing a honeycomb core laminate according to claim 2, wherein the prepreg is obtained by polymerizing a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst, and a crosslinking agent in the presence of reinforcing fibers.   The method for manufacturing a honeycomb core laminate according to claim 3, wherein the cycloolefin monomer comprises a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds.

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