JP2014193534A - Laminate apparatus, production method of long shape laminate, and production method of long shape resin composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate apparatus that can efficiently produce a long shape laminate; a production method of a long shape laminate using the laminate apparatus; and a production method of a long shape resin composite.SOLUTION: A laminate apparatus is that while a long shape impregnation object B of a long shape fiber substrate impregnated with a coating liquid is transported from a lower side to an upper side of a vertical direction, a long shape substrate 81 is consecutively laminated to front and rear faces of the long shape impregnation object B respectively, the laminate apparatus 80 includes: a pair of guide rolls 88 that guides the long shape substrate 81 so that a winding off direction of the long shape substrate 81 wound off from a wind-off apparatus may approach to parallel to a vertical direction; and a laminate roll 86 in which the long shape substrate 81 guided by the pair of guide rolls 88 is laminated to these front and rear faces of the long shape impregnation object B respectively to obtain a long shape laminate C, and a production method of the long shape laminate C uses the laminate apparatus 80.

Description

  The present invention relates to a laminating apparatus, a method for producing a long laminate, and a method for producing a long resin composite, and in particular, a laminating apparatus capable of efficiently producing a long laminate, and this The present invention relates to a method for producing a long laminate using a laminating apparatus and a method for producing a long resin composite.

  Conventionally, a prepreg which is an impregnated material obtained by impregnating a fiber base material with a coating liquid has been widely used as a material for circuit boards. The long prepreg is obtained by, for example, impregnating a long fiber base material with a polymerizable composition containing a monomer to obtain a long impregnated product, and then polymerizing the impregnated product by heating or the like. Can be obtained. Specifically, for example, in Patent Document 1, a polymerizable composition is continuously applied to the front and back surfaces of a glass cloth using a double-sided die coater while conveying the glass cloth from the bottom to the top in the vertical direction. After obtaining the impregnated material, a laminate is obtained by laminating a protective film as a support on both surfaces of the impregnated material using a predetermined laminating apparatus, and then the laminated material is passed between a pair of rolls. Then, after the thickness is made constant, a method for producing a prepreg with a long support is disclosed by heating the laminate whose thickness has been adjusted to polymerize the polymerizable composition in the laminate. .

JP 2007-270083 A

  However, in the technique shown in Patent Document 1, since the long impregnated material is transported substantially vertically from the bottom to the top in the vertical direction, the long support is laminated on the long impregnated material. Depending on the coating conditions of the coating liquid and the transport conditions of the fiber base material, the coating liquid may sag toward the upstream side (downward in the vertical direction) of the pair of rolls, that is, liquid dripping may occur. . For this reason, continuous production of a long laminate may be hindered, and further productivity improvement is desired.

  An object of the present invention is to provide a laminating apparatus capable of efficiently producing a long laminate, a method for producing a long laminate using the laminating apparatus, and a method for producing a long resin composite. It is to be.

  In the present invention, the long impregnated material impregnated with the coating liquid in the long fiber base material is conveyed from the bottom to the top in the vertical direction, while the long impregnated material is conveyed on the front and back surfaces of the long impregnated material. A laminating apparatus for continuously laminating long supports, respectively, so that the unwinding direction of the long supports unwound from an unwinding apparatus approaches parallel to the vertical direction. A pair of guide rolls for guiding a long support, and a long support guided by the pair of guide rolls are stacked on the front and back surfaces of the long impregnated material, respectively. A laminate roll for obtaining a laminate.

  Here, the coating liquid is not particularly limited as long as it is a liquid material. For example, a resin (resin composition) or a liquid material containing a polymerizable composition can be used. As the resin, a thermoplastic resin and a curable resin (such as a thermosetting resin and a photocurable resin) can be used. Further, as the polymerizable composition, a composition containing at least a monomer can be used, and a polymerizable composition containing a monomer and a polymerization catalyst may be used. Moreover, the coating liquid may contain a solvent. Here, the viscosity of the coating solution is usually 20 to 1500 [mPa · s], and preferably 30 to 1000 [mPa · s]. The viscosity is measured in the range of a shear rate of 100 to 1000 [1 / s].

  According to the laminating apparatus of the present invention, the pair of guide rolls has the long support so that the unwinding direction of the long support unwound from the unwinding apparatus approaches the parallel to the vertical direction. In order to guide, when it laminates | stacks with a laminating roll, the conveyance direction of a elongate support body and the conveyance direction of a elongate impregnate will be in a substantially parallel state. For this reason, when a coating liquid having a predetermined viscosity is used, a gap having a width larger than necessary is not generated between the support and the impregnated material, and the width is small and the gap is long in the vertical direction. Therefore, it is possible to suppress the phenomenon that the coating liquid drips from the gap due to the surface tension, that is, the occurrence of liquid dripping. Therefore, a long laminated body can be manufactured efficiently.

Here, the viscosity η [Pa · s] of the coating liquid, the density ρ [kg / m ³ ] of the coating liquid, the conveyance speed Ls [m / min] of the impregnated product, and the pair of guides It is preferable that the relationship (α) of T ² <(2 × η × Ls) / (9.8 × ρ) is satisfied when the gap dimension T [mm] between the rolls is set. By configuring the laminating apparatus so as to satisfy such a mathematical formula, liquid dripping can be prevented more reliably, so that a laminate can be manufactured more efficiently.

The method for producing a long laminate of the present invention includes a step of transporting a long impregnated material impregnated with a coating liquid into a long fiber base material from the bottom to the top in the vertical direction; Using the laminating apparatus, and sequentially laminating a long support on the front and back surfaces of the conveyed long impregnated material to obtain a long laminated body.
In the method for producing a long resin composite according to the present invention, the coating liquid is a resin composition, and the long laminate obtained by the method for producing a long laminate is used. A semi-curing step of semi-curing the resin composition to obtain a long composite; Here, the resin composition includes a polymerizable composition containing a monomer and a polymer composition containing a polymer. The semi-curing step includes an aspect in which the polymerizable composition is polymerized to be in a semi-cured state and an aspect in which the polymer composition is dried to be in a semi-cured state. “Semi-cured” means that the resin component is in the state of a thermoplastic resin and has been cured only to such an extent that it can be further cured by heating, including that in an uncured state. Shall be. Preferably, the insulating polymer constituting the resin layer is partly dissolved in a solvent that can be dissolved, or the volume swelling ratio when the resin layer is immersed in the solvent for 24 hours. , 200% or more before immersion.
In addition, you may bridge | crosslink the semi-cured material in the composite_body | complex obtained by the semi-hardening process of this manufacturing method, and form a crosslinked body.

  According to the manufacturing method of the long laminate and the manufacturing method of the long resin composite, the long laminate and the long resin composite are efficiently processed in the same manner as the laminating apparatus. The effect that it can be manufactured can be produced.

  According to the laminating apparatus of the present invention, there is an effect that a long laminate can be efficiently manufactured. Moreover, according to the manufacturing method of the elongate laminated body using this laminating apparatus, and the manufacturing method of an elongate resin composite, an elongate laminated body or an elongate resin composite is manufactured efficiently. There is an effect that can be done.

It is a schematic diagram which shows the prepreg manufacturing apparatus containing the laminating apparatus which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the double-side coating apparatus which comprises the said prepreg manufacturing apparatus. It is sectional drawing which shows typically the laminating apparatus which comprises the said prepreg manufacturing apparatus. It is a schematic diagram for demonstrating the conventional laminating apparatus.

  A prepreg manufacturing apparatus including a laminating apparatus according to an embodiment of the present invention will be described. FIG. 1 is a schematic view showing a prepreg manufacturing apparatus. As shown in FIG. 1, the prepreg manufacturing apparatus 1 is an apparatus that continuously manufactures a long prepreg D with a support, and the impregnated product manufacturing apparatus 10 and the long product obtained by the impregnated product manufacturing apparatus 10. A laminating apparatus 80 for continuously laminating a long support on the front and back surfaces of the impregnated product B, and a long laminate C (impregnated with a support) obtained by the laminating apparatus 80 in half And a semi-curing device 100 for obtaining a prepreg D with a long support by curing.

  As shown in FIG. 1, the impregnated material manufacturing apparatus 10 is an apparatus that continuously manufactures a long impregnated material B including a long fiber base material A and a coating liquid. A liquid supply device 20, a transport device 40 for transporting the long fiber substrate A, and a double-side coating device 60 for coating the coating liquid on the front and back surfaces of the transported long fiber substrate A; Is provided.

  The long fiber substrate A is a substrate for reinforcing the obtained impregnated material, and is a member formed into a sheet shape such as a knitted fiber, a woven fabric, and a non-woven fabric. Here, the long shape means a band shape having a width direction and a length direction longer than the width direction dimension, preferably 10 times or longer. Although the length (length of a longitudinal direction) of the fiber base material A is not specifically limited, Usually, it is 400-2000m. The width dimension of the fiber base material A (the length in the width direction as the direction orthogonal to the longitudinal direction) is not particularly limited, but is usually 450 to 1300 mm, preferably 530 to 1280 mm. Although the thickness of the fiber base material A is not specifically limited, Usually, 5-100 micrometers, Preferably it is 15-80 micrometers.

  Examples of the fibers used for the long fiber base A include inorganic and / or organic fibers. Specific examples of these fibers include, for example, organic fibers such as PET (polyethylene terephthalate) fibers, aramid fibers, ultrahigh molecular weight polyethylene fibers, polyamide (nylon) fibers, and liquid crystal polyester fibers; glass fibers, carbon fibers, and alumina fibers. And inorganic fibers such as tungsten fiber, molybdenum fiber, titanium fiber, steel fiber, boron fiber, silicon carbide fiber, and silica fiber. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. Moreover, as glass fiber, fibers, such as E glass, NE glass, S glass, D glass, H glass, Q glass, and T glass, can be used suitably. From the viewpoint of preventing local differences in the dielectric constant of the impregnation (prepreg) resulting from the density of the fiber bundle constituting the fiber, the dielectric constant of the layer made of the coating liquid and the dielectric constant of the material constituting the fiber substrate A smaller difference is preferable. The fiber may be used by opening a fiber bundle.

  The coating liquid is a liquid material to be impregnated into the long fiber base A. The coating liquid is not particularly limited as long as it is a liquid material. For example, a liquid material containing a resin (including a resin composition) or a polymerizable composition can be used. As the resin, for example, a curable resin (such as a thermosetting resin and a photocurable resin) can be used, and a thermosetting resin is particularly preferable. Examples of the thermosetting resin include an epoxy resin, an unsaturated polyester resin, a phenol resin, and a urea resin. Moreover, as a polymeric composition, the composition containing a monomer and the composition containing a monomer and a polymerization catalyst can be used, for example. In addition, the said coating liquid may contain the solvent.

  As the monomer, various monomers can be used. For example, a cycloolefin monomer can be used. The cycloolefin monomer is a compound having an alicyclic structure formed of carbon atoms and having a polymerizable carbon-carbon double bond in the alicyclic structure. As used herein, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond mainly involved in polymerization (metathesis ring-opening polymerization, addition polymerization, etc.).

  Examples of the alicyclic structure of the cycloolefin monomer include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combination polycyclic thereof. As the cycloolefin monomer, a polycyclic cycloolefin monomer is preferable from the viewpoint of improving the mechanical strength of the molded body, for example, when a molded body such as a circuit board is molded using the obtained prepreg. Although there is no limitation in particular in the carbon atom 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, and an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. Good.

  As the cycloolefin monomer, those having at least one crosslinkable carbon-carbon unsaturated bond are suitably used from the viewpoint of improving the mechanical strength of the molded article. In the present specification, the “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that hardly participates in the polymerization and mainly participates in a crosslinking reaction. “Crosslinking reaction” refers to a reaction that forms a bridge structure. The “crosslinking reaction” usually means a radical crosslinking reaction or a metathesis crosslinking reaction, particularly a radical crosslinking reaction.

Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, i.e., aliphatic carbon-carbon double bonds or triple bonds. -Refers to a carbon double bond. In the cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond, the position of the unsaturated bond is not particularly limited, and other than the alicyclic structure other than the alicyclic structure formed by carbon atoms. For example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond may exist as a vinyl group (CH ₂ ═CH—), a vinylidene group (CH ₂ ═C <), or a vinylene group (—CH═CH—). Since it exhibits radical crosslinkability, it preferably exists as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.

  As the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond, a norbornene monomer having at least one crosslinkable carbon-carbon unsaturated bond is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. Examples include norbornenes, dicyclopentadiene, and tetracyclododecene.

  Examples of the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond 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; Can be mentioned. Among these, norbornene monomers having at least one crosslinkable carbon-carbon unsaturated bond are preferable.

  As the cycloolefin monomer, in addition to the cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond, a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond is used.

  Examples of the cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, tetracyclododecene, 1, , 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, 5,8,8a-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-octa Dronaphthalene, 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-dihydro Dicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene And norbornene monomers such as 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene and 5-cyanonorbornene. Among these, norbornene-based monomers having no crosslinkable carbon-carbon unsaturated bond are preferable.

  The above cycloolefin monomers can be used alone or in combination of two or more. As the cycloolefin monomer, for example, a mixture of a cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond can be used.

  Here, the polymerization catalyst is not particularly limited as long as it is a catalyst capable of polymerizing the monomer. For example, when the monomer is the cycloolefin monomer, an addition polymerization catalyst or a ring-opening polymerization catalyst can be used. .

  In producing a polymer by polymerizing a cycloolefin monomer with the above polymerization catalyst, the cycloolefin monomer is polymerized in the presence of the cycloolefin monomer and another monomer copolymerizable with the cycloolefin monomer, and the cycloolefin monomer is contained. A copolymer may be obtained.

  In the case of obtaining an addition copolymer containing a cycloolefin monomer by addition polymerization in the presence of another monomer copolymerizable with the cycloolefin monomer, as the other monomer copolymerizable with the cycloolefin monomer Is an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and derivatives thereof; 1,4-hexadiene, 4-methyl-1,4-hexadiene, And non-conjugated dienes such as 5-methyl-1,4-hexadiene and 1,7-octadiene; Among these, α-olefins are preferable and ethylene is particularly preferable.

  As the addition polymerization catalyst, for example, a known catalyst such as a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound can be used.

  Any ring-opening polymerization catalyst may be used as long as it can cause ring-opening polymerization of a cycloolefin monomer. For example, a metathesis polymerization catalyst can be used. Examples of the metathesis polymerization catalyst include a metal complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long-period periodic table, the same shall apply hereinafter) are used. The atoms of each group are not particularly limited, and 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 ruthenium and osmium. Is mentioned.

  Among these, as the metathesis polymerization catalyst, a complex having a group 8 ruthenium or osmium as a central atom is preferable, and a ruthenium carbene complex is particularly preferable. A ruthenium carbene complex is a complex having a structure (Ru = C) in which a carbene carbon is double-bonded to a ruthenium atom, and has excellent catalytic activity during polymerization. For this reason, when a crosslinkable resin molded product is produced by polymerizing a polymerizable composition containing a ruthenium carbene complex as a metathesis polymerization catalyst, the resulting crosslinkable resin molded product has little odor derived from unreacted monomers. Therefore, a high-quality molded product with high productivity can be obtained. In addition, ruthenium carbene complexes are relatively stable to oxygen and moisture in the air and are not easily deactivated, so that they can be used even in the atmosphere. These metathesis polymerization catalysts may be used alone or in combination of two or more. In addition, the compounding quantity etc. of a metathesis polymerization catalyst can be made into the content of Unexamined-Japanese-Patent No. 2009-242568, for example.

  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 , Cycloaliphatic hydrocarbons such as decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as indene, benzene, toluene and xylene; nitrogen-containing compounds such as nitromethane, nitrobenzene and acetonitrile Hydrocarbons; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; and the like. Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Further, as long as the activity as a metathesis polymerization catalyst is not lowered, a liquid anti-aging agent, a liquid plasticizer, or a liquid elastomer may be used as a solvent.

  The metathesis polymerization catalyst can be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity and improving the polymerization reaction rate. As the activator, aluminum, scandium, tin alkylates, halides, alkoxylates, aryloxylates, and the like can be used. Specific examples thereof include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium. The use amount of the activator is usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1 in terms of a molar ratio of (metal atom in the catalyst: activator). : It is the range of 0.5-1: 10.

  In addition, when using a complex of transition metal atoms of Group 5 and Group 6 as the metathesis polymerization catalyst, it is preferable that both the metathesis polymerization catalyst and the activator are used by dissolving them in the monomer. As long as it is essentially not damaged, it can be suspended or dissolved in a solvent.

  In addition to the monomer and the polymerization catalyst, the polymerizable composition may optionally include a filler, a chain transfer agent, a crosslinking agent, a crosslinking aid, a flame retardant, a polymerization regulator, a polymerization reaction retarder, a reactivity. You may mix | blend other compounding agents, such as a fluidizer, a flame retardant, antioxidant, and a coloring agent.

  The filler is not particularly limited, and for example, an organic substance or an inorganic substance can be used. From the viewpoint of obtaining the molded article having a higher elastic modulus, an inorganic substance is preferable. The shape of the filler is not particularly limited, and any shape such as a spherical shape, a granular shape, an indefinite shape, a dendritic shape, a needle shape, a rod shape, and a flat shape can be employed. The average particle diameter of the filler is not particularly limited, and is a median diameter containing 50% by volume of all particles measured by a laser scattering diffraction particle size distribution meter, and is usually 0.001 to 70 μm, preferably 0.00. It is 01-50 micrometers, More preferably, it is 0.05-15 micrometers, Most preferably, it is 0.1-5 micrometers.

  Specific examples of the filler include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide, Examples include barium sulfate, silica, talc, and clay.

  The content of the filler is usually 50 to 600 parts by weight, preferably 100 to 550 parts by weight, and more preferably 200 to 500 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the content of the filler is within such a range, the dispersibility of the filler in the polymerizable composition is excellent, and the impregnation property to the fiber base material is good.

  Examples of chain transfer agents include chain olefins that may have a substituent. Specific examples of the chain transfer agent include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, and 4- Chain transfer agents without aliphatic carbon-carbon double bond groups such as vinylaniline; divinylbenzene, vinyl methacrylate, hexenyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, acrylic acid Chain transfer agent having one aliphatic carbon-carbon double bond group such as styryl and ethylene glycol diacrylate; two or more aliphatic carbon-carbon double bond groups such as allyltrivinylsilane and allylmethyldivinylsilane Chain transfer agents, and the like. The amount of the chain transfer agent used is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  Moreover, the said polymeric composition may contain a crosslinking agent from a viewpoint that the said molded object obtained can be comprised as a resin layer which can be post-crosslinked. Here, “after-crosslinking is possible” means that the molded body can be formed into a crosslinked molded body by, for example, heating the molded body to advance a crosslinking reaction. As the crosslinking agent, a radical generator is usually preferably used. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. These radical generators can be used alone or in combination of two or more. By using two or more kinds of radical generators together and adjusting the quantity ratio, it is possible to arbitrarily control the glass transition temperature and the molten state of the coating liquid constituting the impregnated product. The 1-minute half-life temperature of the radical generator is not particularly limited, but is usually in the range of 150 to 300 ° C, preferably 180 to 250 ° C. Here, the 1-minute half-life temperature is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fat Co., Ltd.). The amount of the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of the crosslinking agent is within the above range, a cured product obtained by curing the prepreg as a molded product has a sufficient crosslinking density, and a circuit board having desired physical properties can be efficiently obtained. It is.

  As the crosslinking aid, a compound having a crosslinkable carbon-carbon unsaturated bond that does not participate in the polymerization and can participate in a crosslinking reaction induced by the crosslinking agent is preferable. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group, particularly as an isopropenyl group or (meth) acryl group, in the compound constituting the crosslinking aid, (meth) More preferably it exists as an acrylic group. The (meth) acryl group means that both a methacryl group and an acryl group are included.

  Specific examples of the crosslinking aid include polyfunctional compounds having two or more isopropenyl groups such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; lauryl methacrylate, benzyl methacrylate, tetrahydro Monofunctional compounds having one methacryl group such as furfuryl methacrylate and methoxydiethylene glycol methacrylate; monofunctional compounds having one acrylic group such as lauryl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, and methoxydiethylene glycol acrylate; 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, tricyclodecane dimethanol dimethacrylate, 2,2′-bis (4-methacryloxydiethoxyphenyl) propane, trimethylol Examples thereof include polyfunctional compounds having two or more methacrylic groups such as propane trimethacrylate and pentaerythritol trimethacrylate. The crosslinking assistants can be used alone or in combination of two or more. As a compounding quantity of a crosslinking adjuvant, it is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.5-50 weight part, More preferably, it is 1-30 weight part.

  The flame retardant is not particularly limited, and from known flame retardants, for example, halogen flame retardants, phosphorus-nitrogen flame retardants, phosphate ester flame retardants, nitrogen flame retardants, and inorganic flame retardants, It can be appropriately selected and used. What is necessary is just to adjust the compounding quantity suitably so that a desired effect may be acquired.

  The said coating liquid can mix and use the said component suitably. When a polymerizable composition is used as the coating liquid, the polymerizable composition can be prepared by mixing a monomer (for example, a cycloolefin monomer) and a polymerization catalyst. The method for preparing the polymerizable composition is not particularly limited, and examples thereof include a method in which a monomer liquid containing the monomer and a catalyst liquid containing a polymerization catalyst are separately prepared and mixed. Here, when using the said compounding agent, the said compounding agent may be added to the said monomer liquid, may be added to the said catalyst liquid, and is added to the liquid mixture of a monomer liquid and a catalyst liquid. May be.

  When preparing the catalyst solution, a small amount of an inert solvent may be used as necessary. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, decahydronaphthalene, and bicycloheptane. Alicyclic hydrocarbons such as tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as indene, benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether, tetrahydrofuran and the like Of ethers; and the like. Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Moreover, as long as the activity as a polymerization catalyst is not lowered, a liquid anti-aging agent, a plasticizer or an elastomer may be used as a solvent.

  In the present invention, a polymerizable composition liquid containing the monomer liquid and the catalyst liquid may be prepared in advance, and the prepared liquid may be applied to a fiber substrate as a coating liquid. Alternatively, the monomer liquid and the catalyst liquid may be used. It is good also as a structure which prepares these separately and mixes both liquids on a fiber base material.

  The viscosity of the coating solution is usually 20 to 1500 [mPa · s], preferably 30 to 1000 [mPa · s]. The viscosity is a measurement result in a range of a shear rate of 100 to 1000 [1 / s]. Even if the viscosity of the coating liquid is within the above range, the fiber base material can be sufficiently impregnated with the coating liquid. The coating amount can be appropriately determined in accordance with the purpose, but for example, it can be set to an amount capable of forming a coating film of about 60 to 160 μm immediately after coating. In addition, the temperature of the coating liquid at the time of coating is 0-40 degreeC normally. If the temperature during coating is too high, it may be difficult to obtain an impregnated material having a uniform thickness.

  In addition, as a polymerizable composition constituting the coating liquid of the present invention, a composition containing a cycloolefin monomer and a polymerization catalyst has been described as an example. However, the present invention is not limited to this, and other compositions other than the cycloolefin monomer are described. The case where the monomer is mainly used can be considered similarly to the case of the cycloolefin monomer.

  The coating liquid supply apparatus 20 is an apparatus that supplies the coating liquid to the double-side coating apparatus 60, and includes a tank 22 and a mixer 28 that conveys the coating liquid in the tank 22 to the double-side coating apparatus 60. In the present embodiment, a method is used in which a monomer liquid containing a monomer and a catalyst liquid containing a polymerization catalyst are separately prepared and mixed immediately before coating to prepare a coating liquid.

  The tank 22 includes a tank main body 24 that stores the coating liquid, and a pump 26 that sends the coating liquid in the tank main body 24 to the mixer 28. The tank body 24 includes a monomer liquid tank 24A that stores a monomer liquid containing a monomer and a catalyst liquid tank 24B that stores a catalyst liquid containing a polymerization catalyst. The tanks 24A and 24B each have a temperature adjustment function, and it is preferable to cool each liquid in the tanks 24A and 24B to, for example, −10 to + 20 ° C.

  The pump 26 includes a pump 26A that sends out the monomer liquid in the monomer liquid tank 24A at a predetermined flow rate, and a pump 26B that sends out the catalyst liquid in the catalyst liquid tank 24B at a predetermined flow rate. Although it does not specifically limit as pump 26A, 26B, For example, a diaphragm pump, a plunger pump, a gear pump, a snake pump etc. can be used.

  The mixer 28 includes a mixer main body 29 that prepares a coating liquid, and a coating liquid sending unit 30 that sends the prepared coating liquid to the double-side coating apparatus 60. The mixer body 29 prepares a coating liquid made of a polymerizable composition by mixing the monomer liquid sent out by the pump 26A and the catalyst liquid sent out by the pump 26B at a predetermined ratio. The coating liquid delivery unit 30 delivers the coating liquid prepared by the mixer main body 29 from the front side of the fiber base A, and sends the coating liquid from the back side of the fiber base A. And a delivery mechanism (not shown) that feeds the double-sided coating device 60 at a predetermined flow rate via these delivery routes 31 and 32. As the delivery mechanism, for example, a mechanism including a pump such as a diaphragm pump, a plunger pump, a gear pump, and a snake pump can be used. The mixer body 29 preferably includes a temperature adjustment mechanism from the viewpoint of adjusting the viscosity of the coating liquid.

  The transport device 40 transports the long fiber base A at a predetermined transport speed, and the long support-supported prepreg D as a processed fiber base that has been subjected to a coating process or the like on the surface. A device for winding. The conveying device 40 is fed from a feeding roll 42 as a winding device that sequentially feeds the long fibrous base material A from a roll wound body of the fibrous base material A wound in a roll shape, and sent from the sending roll 42. The winding roll 44 which winds up the prepreg D with the elongate support body by which the process etc. were made, and the conveyance part which is not shown in figure which adjusts the conveyance state of the fiber base material A suitably are provided.

  The delivery roll 42 and the take-up roll 44 are rolls that rotate at a predetermined speed. The transport unit controls the transport speed of the long fiber base A while adjusting the tension applied to the long fiber base A based on the number of rotations of the feed roll 42 and the take-up roll 44. It is a part to do. The conveyance speed of the fiber base material A is 8-333 mm / second, Preferably it is 17-167 mm / second. In this embodiment, after the fiber base A sent out from the sending roll 42 is transported from the bottom to the top in the vertical direction, the transport direction is changed by, for example, 90 degrees by the roll 43 disposed on the transport path. In the horizontal direction, it is then wound up in a roll shape by a winding roll 44. In this embodiment, the conveyance direction is changed to 90 degrees once in the middle. However, the present invention is not limited to this, and the conveyance direction may not be changed or may be changed a plurality of times. The change angle may be an angle other than 90 degrees.

FIG. 2 is a cross-sectional view schematically showing a double-side coating apparatus.
As shown in FIG. 2, the double-side coating apparatus 60 applies the coating liquid to the front and back surfaces of the long fiber substrate A that is conveyed in the direction of the arrow P, that is, from the bottom to the top in the vertical direction. And it is an apparatus which obtains the elongate impregnation B, and is provided with the 1st coating device 62 and the 2nd coating device 64. FIG. The material of each coating device 62, 64 is not particularly limited, and examples thereof include metals and synthetic resins. From the viewpoint of excellent durability, metals are preferable, and stainless steel is more preferable. The first coating device 62 includes a first discharge port 62 </ b> A that discharges (coats) the coating liquid supplied via the delivery path 31 to the surface side of the fiber base material A. The second coating device 64 includes a second discharge port 64 </ b> A that discharges (coats) the coating liquid supplied via the delivery path 32 to the back surface side of the fiber base material A.

  62 A of 1st discharge ports are formed in the slit shape extended along the width direction of the elongate fiber base material A. As shown in FIG. 64 A of 2nd discharge outlets are formed in the slit shape extended along the width direction of the elongate fiber base material A. As shown in FIG. Here, as the discharge ports 62A and 64A and the structure around the discharge ports 62A and 64A, the same as a known die generally used when applying the coating liquid to the long fiber base A is used. it can. Specific examples of such a die include those described in JP-A Nos. 2001-170541, 2004-290771, and 2009-018227. In the present embodiment, the discharge ports 62A and 64A are formed in a slit shape, but the present invention is not limited to this. Further, only one of the discharge ports may be formed in a slit shape.

  Further, as shown in FIG. 2, the first discharge port 62A is located on the upstream side (lower side in FIG. 2) of the second discharge port 64A. A position where the coating liquid is discharged from the first discharge port 62A to the fiber base material A is a position X, and a position where the coating liquid is discharged from the second discharge port 64A to the fiber base material A is a position Y. In this case, the distance S between the position X and the position Y with respect to the direction of the arrow P, which is the conveyance direction of the fiber base material, is preferably 10 to 400 mm, more preferably 20 to 200 mm. By setting the distance within the above range, bubbles in the impregnation B can be removed more efficiently, and as a result, an impregnation with less voids can be produced efficiently.

In the present embodiment, the conveying speed of the fiber base material A has the formula _{(A): L S ≦ S} , it is preferable to satisfy the. L _S represents the conveyance speed [mm / second] of the fiber base A, and S represents the interval [mm] between the first discharge port 62A and the second discharge port 64A. By satisfy | filling Formula (A), the bubble in the impregnation B can be removed much more efficiently.

FIG. 3 is a cross-sectional view schematically showing a laminating apparatus.
As shown in FIG. 3, the laminating apparatus 80 has a long laminated body C in which a long support body 81 (81 </ b> A, 81 </ b> B) is continuously laminated on the front and back surfaces of the long impregnated material B. The unwinding roll 84 which unwinds the elongate support body 81, the laminating roll 86 which laminates the elongate support body 81 and the elongate impregnation B, the unwinding roll 84, and A pair of guide rolls 88 disposed between the laminate rolls 86.

  The unwinding roll 84 is a pair of rolls arranged with a predetermined gap size, and the first unwinding roll 84A for unwinding the first support 81A to the surface side of the elongated impregnation B, And a second unwinding roll 84B for unwinding the second support 81B to the back side of the long impregnation B.

  The pair of guide rolls 88 is arranged with a predetermined gap size, and is arranged on the first guide roll 88A arranged on the front surface side of the long impregnated material B and on the back surface side of the long impregnated material B. Second guide roll 88B. The first guide roll 88A is a long support so that the unwinding direction (horizontal direction) of the long support 81A unwound from the first unwinding roll 84A approaches parallel to the vertical direction. Guide 81A. The second guide roll 88B is a long support body so that the unwinding direction (horizontal direction) of the long support body 81B unwound from the second unwinding roll 84B approaches the vertical direction in parallel. Guide 81B. In other words, the conveying direction of the long supports 81A and 81B is changed to the direction along the conveying direction P of the long impregnated material B by the guide rolls 88A and 88B. The first support 81 </ b> A, the long impregnated material B, and the long second support 81 </ b> B are brought into a substantially parallel state in this order and conveyed to the laminating roll 86.

  The gap dimension T between the pair of guide rolls 88 is preferably 0.1 to 20 mm, more preferably 0.1 to 10 mm. In addition, from the viewpoint that liquid dripping can be more effectively prevented, a long support 81 (81A, 81B) guided by a pair of guide rolls 88 (88A, 88B) and a long impregnated material The angle θ formed by B is preferably more than 0 ° and not more than 10 °, more preferably more than 0 ° and not more than 5 °. The material of the pair of guide rolls 88 is not particularly limited, and examples thereof include metals and synthetic resins. Among these, metals are preferable and stainless steel is more preferable because of excellent durability.

  The laminating roll 86 is a pair of rolls arranged with a predetermined gap size. The laminating first support 81 </ b> A guided by the first guide roll 88 </ b> A is used as a long impregnation B. The first laminating roll 86A for laminating on the surface of the sheet and the second laminating roll 81B for laminating the long second support 81B guided by the second guide roll 88B on the back of the long impregnated material B 86B. That is, the laminating roll 86 is formed by laminating the long first support 81A, the long impregnation B, and the long second support 81B in this order, and corresponds to the gap size. A long laminate C having a thickness is obtained.

  The gap dimension between the rolls in the laminate roll 86 is preferably 0.03 to 0.5 mm, and more preferably 0.05 to 0.3 mm. The material of the laminate roll 86 is not particularly limited, and examples thereof include metals and synthetic resins. Among these, metals are preferable because of excellent durability, and stainless steel is more preferable.

Here, from the viewpoint of preventing liquid dripping more effectively, the viscosity η [Pa · s] of the coating liquid, the density ρ [kg / m ³ ] of the coating liquid, When the transport speed Ls [m / min] of the impregnated material B and the gap dimension T [mm] between the pair of guide rolls 88 are set, T ² <(2 × η × Ls) / (9.8 × It is preferable that a pair of guide rolls is disposed so as to satisfy the relationship (α) of ρ).

Formula (α) defines the conditions under which the elongated impregnated material B can pass between the laminate rolls 86 before dripping due to the excess coating liquid occurs. That is, when the long impregnated material B having a thickness of 2 × y [mm] is disposed along the vertical direction, the velocity v [m / min] at which the coating liquid drips is v = (9.8 × It can be obtained from the relationship (β) of ρ × y ² ) / (2 × η). The thickness 2 × y can be regarded as the gap dimension T between the guide rolls 88 before passing through the laminate roll 86. By controlling the thickness 2 × y with the guide roll gap T so that v calculated based on the relationship (β) is smaller than the speed (Ls) for conveying the long impregnated material B, Generation can be further suppressed. Formula (α) represents this.

  Here, the material of the elongated supports 81A and 81B is not particularly limited, but a resin film, a metal foil such as a copper foil, or the like can be used. In the case where the long supports 81A and 81B are resin films, those having releasability from the impregnation B are preferable. For example, polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, poly An arylate film, a nylon film, a polytetrafluoroethylene film, etc. can be mentioned.

  Returning to FIG. 1, the semi-curing apparatus 100 includes a heating unit that heats the long laminate C to a semi-cured state. Although it does not specifically limit as said heating means, For example, a heating roll, a heating plate, and a heating furnace can be used. By using the heating means, a prepreg D with a support excellent in smoothness and thickness accuracy can be obtained continuously and efficiently. The heating temperature is usually 100 to 300 ° C, preferably 100 to 250 ° C, more preferably 110 to 200 ° C, and still more preferably 120 to 180 ° C. In the present embodiment, the semi-curing apparatus includes a heating unit. However, the semi-curing apparatus may be semi-cured by means other than heating, such as light irradiation or addition of an additive.

  Next, a method for continuously producing a long prepreg D with a support will be described with reference to FIGS. As shown in FIG. 1, the prepreg D with a long support is a transporting process for transporting the long fiber base A from the bottom to the top in the vertical direction, and a preparation process for preparing a coating liquid. , The impregnated product manufacturing step of applying the prepared coating liquid on the front and back surfaces of the fiber substrate A being conveyed to obtain a long impregnated material B, and the long surface of the long impregnated material on the front and back surfaces Laminating step of obtaining a long laminate C by laminating each of the substrate-like supports, semi-curing step of obtaining a prepreg D with a support by semi-curing the impregnation in the obtained laminate C, and obtaining And a winding step for winding the prepreg D with the support. Hereinafter, each process will be described in more detail.

  As shown in FIG. 1, a wound body in which a long fiber base A is wound is prepared, and this wound body is attached to a delivery roll 42 of a conveying device 40, and a double-side coating device 60 and a laminating device are provided. 80 and the respective devices are arranged so as to pass through the semi-curing device 100 in this order. Subsequently, the rotational speed of the delivery roll 42 and the take-up roll 44, the position of the roll 43, and the like are adjusted by the transport unit, and the long fiber base A is transported at a predetermined speed (transport process).

  Further, the monomer liquid in the monomer liquid tank 24A is sent to the mixer body 29 at a predetermined flow rate by the pump 26A, and the catalyst liquid in the catalyst liquid tank 24B is sent to the mixer body 29 at a predetermined flow speed by the pump 26B. In 29, the monomer liquid sent out by the pump 26A and the catalyst liquid sent out by the pump 26B are mixed at a predetermined ratio to prepare a coating liquid made of a polymerizable composition (preparation step).

  Next, as shown in FIG. 2, the prepared coating liquid is guided to the first discharge port 62 </ b> A of the double-side coating apparatus 60 via the delivery path 31, and the prepared coating liquid is guided to the both sides via the delivery path 32. It leads to the second discharge port 64A of the coating apparatus 60. More specifically, when a specific arbitrary part of the fiber base material A is described, the coating liquid is applied to the surface of the fiber base material A that has been conveyed from the first discharge port 62A to the part. Then, the coating liquid is leached on the surface of the fiber base A. Next, when the fiber base A is conveyed downstream, the portion moves to the vicinity of the second discharge port 64A, and the coating liquid is supplied from the second discharge port 64A to the portion on the back surface of the fiber base A. The impregnated material B which is coated and applies the coating liquid to the long front and back surfaces is obtained (impregnated material manufacturing process). Thus, since the coating liquid has already leached on the surface of the fiber base A, it is possible to prevent bubbles from remaining in the fiber base A.

  Next, as shown in FIG. 3, the first guide is arranged so that the unwinding direction (horizontal direction) of the long support 81A unwound from the first unwinding roll 84A approaches parallel to the vertical direction. The roll 88A guides the long support 81A, and the unwinding direction (horizontal direction) of the long support 81B unwound from the second unwinding roll 84B approaches parallel to the vertical direction. In this way, the long support body 81B is guided. For this reason, the conveying direction of the long supports 81A and 81B is changed to the direction along the conveying direction P of the long impregnated material B by the guide rolls 88A and 88B. (86A, 86B) is a long laminate obtained by laminating a long first support 81A, a long impregnation B, and a long second support 81B in this order. C is manufactured (lamination process).

  Next, as shown in FIG. 1, the obtained long laminate C is heated by the heating means of the semi-curing device 100 to semi-cur the coating liquid in the impregnated material, thereby producing a long A prepreg D with a long support as a resin composite is obtained (semi-curing step). Next, this long prepreg D with a support is wound up by a take-up roll 44 to produce a long prepreg D with a support formed as a wound body (winding step).

According to this embodiment, there are the following effects.
(1) The pair of guide rolls 88A, 88B are long so that the unwinding direction of the long supports 81A, 81B unwound from the pair of unwinding rolls 84A, 84B approaches the parallel to the vertical direction. When laminating with the laminating rolls 86A and 86B in order to guide the long supports 81A and 81B, the transport direction of the long supports 81A and 81B and the transport direction of the long impregnated material B are substantially the same. It becomes a parallel state. For this reason, a gap larger than necessary (a gap having a large horizontal dimension in FIG. 4) does not occur between the elongated supports 81A and 81B and the elongated impregnation B. In the case of using a coating liquid having the above, it is possible to suppress the phenomenon that the coating liquid drips from the gap, that is, the occurrence of liquid sag. Therefore, the long laminated body C can be manufactured efficiently. As a result, the prepreg D with a long support body can also be manufactured efficiently. Further, when the viscosity of the coating liquid, the density of the coating liquid, the conveyance speed of the impregnated material B, and the roll gap size of the pair of guide rolls 86 satisfy the above relationship (α), it is further increased. Since liquid dripping can be reliably prevented, the laminate C can be manufactured more efficiently.

  Here, as described above, the laminating apparatus of the present invention suppresses the occurrence of liquid dripping by installing a guide roll on the upstream side of the laminating roll and changing the conveying direction of the elongated supports 81A and 81B. Thus, the laminate can be manufactured efficiently. This point will be described in more detail. FIG. 4 is a schematic diagram for explaining a conventional laminating apparatus. As shown in FIG. 4A, the conventional laminating apparatus does not include a guide roll, and the conveying direction of the long supports 5a and 5b is changed by about 90 ° by the laminating rolls 1a and 1b. As a result, a relatively large gap (a gap having a large horizontal dimension in FIG. 4) is formed between the elongated supports 5a, 5b and the elongated impregnated material B. A liquid reservoir 7 in which the coating liquid is accumulated is formed. However, depending on the conveying speed of the fiber base material B, the viscosity of the coating liquid, the coating amount, and the like, an appropriate amount of liquid pool cannot be formed due to the void being too large, and FIG. As shown in FIG. On the other hand, according to the present laminating apparatus 80, since the conveying direction of the support 81 is approaching parallel to the conveying direction of the impregnation B by the guide roll 88, the long support 81 and the long Although it is relatively small, a long gap in the vertical direction is formed between the impregnations B. For this reason, although the coating liquid collected in the gap forms a liquid pool, such a liquid pool is less likely to cause liquid dripping due to surface tension. Therefore, by using the laminating apparatus 80, the laminate C and the prepreg D with the support can be efficiently manufactured.

(2) The long fiber substrate A is conveyed in a certain direction without bending between the application position X of the first application device 62 and the application position Y of the second application device 64, The long impregnated material B can be produced with good productivity without reducing the conveying speed.

(3) In addition to the first discharge port 62 </ b> A, the second discharge port 64 </ b> A that discharges the coating liquid is provided on the back surface side of the fiber base material A, so that the coating liquid is reliably formed on both surfaces of the fiber base material A. A layer can be provided, and the impregnation B of good quality can be reliably produced without any trouble such as the fiber base A being exposed from the impregnation B.

(4) Since the first discharge port 62A and the second discharge port 64A are each formed in a slit shape extending along the width direction of the fiber base material A, the coating liquid is surely applied to the end in the width direction of the fiber base material A. And the quality of the impregnated material B can be improved.

(5) Between a position X at which the coating liquid is discharged from the first discharge port 62A to the fiber base A and a position Y at which the coating liquid is discharged from the second discharge port 64A to the fiber base A Since the predetermined distance S is provided, the coating liquid is discharged from the first discharge port 62A to apply the coating liquid to the surface of the fiber base A. As time passes, the surface of the fiber base A The coating liquid is gradually impregnated into the fiber base A from the back to the back side, and in this state, the coating liquid is discharged from the second discharge port 64A to apply to the back of the fiber base A. Since the liquid is applied, it is possible to reliably remove bubbles remaining in the impregnation B and improve the quality of the impregnation B.

(6) Since the monomer liquid and the catalyst liquid are stored in separate tanks 24A and 24B and mixed in the mixer body 29 immediately before the coating, the coating liquid is prepared. Compared with the case where the liquid is mixed in advance, it is possible to suppress problems such as unintentionally starting polymerization and curing of the coating liquid, and the productivity of the prepreg D with the support can be improved.

The present invention is not limited to the embodiment.
In the above-described embodiment, the position of the first discharge port and the position of the second discharge port are shifted along the transport direction. However, the positions may not be shifted.

In the embodiment, the monomer liquid and the catalyst liquid are stored in separate tanks 24A and 24B, and mixed in the mixer body 29 immediately before the coating to prepare the coating liquid. For example, a catalyst is supported on a fiber base material in advance, and the fiber base material supported by such a catalyst is conveyed, and a monomer liquid is applied to the surface of the catalyst-supporting fiber base material, thereby It is good also as a structure which prepares a coating liquid on a base material. According to such a configuration, since the monomer liquid and the catalyst are mixed on the fiber base material, the polymerization reaction does not proceed before and during coating under normal conditions, and thus the viscosity of the coating liquid increases. This can reduce productivity and improve productivity.
Moreover, according to the said structure, since only the monomer liquid which does not contain a catalyst is applied on a fiber base material, since a polymerization reaction does not advance easily even if a monomer liquid is heated, for example, a monomer liquid is stored. By providing the tank with a temperature adjusting mechanism, the monomer liquid can be heated and used. By adjusting the temperature of the monomer solution in this way, the viscosity of the monomer solution can be adjusted appropriately to further improve productivity.

  In the above embodiment, the monomer liquid and the catalyst liquid are stored separately in two tanks and mixed immediately before the coating to prepare the coating liquid. May be stored in one tank. Further, the coating liquid includes a monomer and a catalyst. However, the coating liquid may be liquid and is not limited thereto.

  The prepreg D with a long support obtained by the present invention may be cut into an appropriate size and used by continuously laminating with another support (resin film, metal foil, etc.). May be. At this time, at least one of the supports constituting the prepreg with a support may be peeled off and laminated with the other support, or the support may be laminated with the other support without being peeled off. Also good. The prepreg is useful as an insulating material for circuit boards.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples. Parts and% in each example are based on weight unless otherwise specified.

[Production Example 1] Preparation of monomer liquid As cycloolefin monomer, 50 parts of dicyclopentadiene and 50 parts of tetracyclododecene, 100 parts of silica as inorganic filler, 10 parts of trimethylolpropane trimethacrylate as a crosslinking aid, chain transfer agent 2 parts of vinyl methacrylate and 1.5 parts of di-t-butyl peroxide (1 minute half-life temperature: 186 ° C.) as a crosslinking agent were mixed with stirring to prepare a monomer solution.

[Production Example 2] Preparation of catalyst solution As a metathesis polymerization catalyst, 5 parts of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride was dissolved in 100 parts of indene to prepare a catalyst solution. Was prepared.

[Example 1]
The monomer solution and the catalyst solution obtained above were placed in the monomer solution tank 24A and the catalyst solution tank 24B of the continuous production apparatus shown in FIG. 1, and each tank was cooled to 10 ° C. A diaphragm pump as a pump 26A and a plunger pump as a pump 26B are connected to the monomer liquid tank 24A and the catalyst liquid tank 24B, respectively, and a small static mixer (spiral) is used as the mixer 28 at flow rates of 60 g / min and 0.32 g / min, respectively. The composition was sent to a type, an element length of 3.18 mm, and the number of elements was 24) to prepare a polymerizable composition (coating solution) at a temperature of 10 ° C. Subsequently, the obtained polymerizable composition having a temperature of 10 ° C. was fed to the double-side coating apparatus 60. The upstream side in the transport direction of the fiber substrate A so that the distance between the first discharge port 62A and the second discharge port 64A of the double-side coating apparatus 60 is 53 mm in the transport direction of the glass cloth that is the fiber substrate A. And shifted downstream.

On the other hand, from the substrate feed roll 42, a long glass substrate A having a thickness of 75 μm and a width of 530 mm (2112/530 / AS891AW: manufactured by Asahi Schavel), which is a long fiber substrate A, is 17 mm / second. The above-mentioned polymerizable composition was continuously applied from the double-sided coating device 60 to both sides of the glass cloth so that the thickness after coating was 110 μm from the double-sided coating device 60, and a long impregnation B was obtained. Obtained. The polymerizable composition had a density ρ of 1500 kg / m ³ and a viscosity of 0.05 Pa · s (measured at a shear rate of 1000 [1 / S]).

  Next, using the laminating apparatus 80 (the gap dimension of the laminate roll 86 is 0.15 mm, the gap dimension between the guide rolls 88 is 0.65 mm, and the angle θ in the figure is 0.3 °), the unwinding roll 84A. , 84B, a long polyethylene naphthalate film (Q51: manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 25 μm and a width of 630 mm is fed out as a long support 81, and the conveying direction thereof is approximately 90 by a guide roll 88. In the state changed, the film thickness was set to 100 μm through a pair of laminating rolls 86A and 86B that were respectively overlapped on the front and back surfaces of the long impregnation B and the gap was adjusted to 150 μm. A long laminate C (impregnated material with support) was obtained.

  Next, the long laminate C was continuously sent to a heating furnace constituting the semi-curing apparatus 100 maintained at 125 ± 5 ° C. In the heating furnace, the long laminate C was heated for 3 minutes to bulk polymerize the polymerizable composition to obtain a prepreg D with a long support. The obtained long prepreg D with a support was wound up by a winding roll 44. In Example 1, the lamination process could be performed without causing dripping.

1: Prepreg manufacturing apparatus 1a, 1b: Laminate roll 5a, 5b: Support 7: Liquid reservoir 8: Liquid dripping 10: Impregnation manufacturing apparatus 20: Coating liquid supply apparatus 22: Tank 24: Tank body 24A: Monomer liquid tank 24B: Catalyst liquid tank 26 (26A, 26B): Pump 28: Mixer 29: Mixer body 30: Coating liquid delivery unit 31, 32: Delivery path 40: Conveying device 42: Delivery roll 43: Roll 44: Winding roll 60 : Double-side coating device 62: First coating device 62A: First discharge port 64: Second coating device 64A: Second discharge port 80: Laminating device 81: Support 81A: First support 81B: Second support Body 84: Unwinding roll 84A: First unwinding roll 84B: Second unwinding roll 86: Laminating roll 86A: First laminating roll 86B: Second laminating roll 88: Pair Guide roll 88A: First guide roll 88B: First guide roll 100: Semi-curing device A: Fiber base material B: Impregnation C: Laminate D: Prepreg P with support P: Direction S: Distance T: Gap size X, Y: position

Claims (4)

While conveying the long impregnated material impregnated with the coating liquid into the long fiber base material from the bottom to the top in the vertical direction, the long impregnated material is formed on the front and back surfaces of the long impregnated material. A laminating apparatus for continuously laminating each support,
A pair of guide rolls for guiding the elongate support so that the unwinding direction of the elongate support unwound from the unwinding device approaches parallel to the vertical direction;
A laminating roll for obtaining a long laminate by laminating the long support guided by the pair of guide rolls on the front and back surfaces of the long impregnated material,
A laminating apparatus comprising: The viscosity η [Pa · s] of the coating liquid, the density ρ [kg / m ³ ] of the coating liquid, the transport speed Ls [m / min] of the impregnated product, and between the pair of guide rolls upon the gap dimension T ^{(mm), T 2 <(2 × η} × Ls) / laminating apparatus according to claim 1 that satisfies (9.8 × ρ) relationship (alpha). A step of transporting a long impregnated material impregnated with a coating liquid into a long fiber base material from the bottom to the top in the vertical direction;
Using the laminating apparatus according to claim 1 or 2, a long support is continuously laminated on the front and back surfaces of the conveyed long impregnated material to obtain a long laminate. Process,
A method for producing a long laminate comprising: The coating liquid is a resin composition,
A long-sized step comprising a semi-curing step of semi-curing the resin composition in a long-sized laminated body obtained by the method for producing a long-sized laminated body according to claim 3 to obtain a long composite. Method for manufacturing a resin composite.

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