JP2014196420A - Prepreg package and method of producing prepreg package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg package which can provide a prepreg having good wiring embedding properties on use and a method of producing a prepreg package.SOLUTION: A prepreg package 1 comprises a prepreg composite body 10 and a housing body 40 having a closed space 40A. The prepreg composite body 10 includes a prepreg 20 and protective films 30 laminated on both sides of the prepreg 20. The prepreg 20 consists of a laminate which includes a plurality of prepreg bodies 23 consisting of a fiber substrate 21 impregnated with a resin composition 22. The housing body 40 houses the prepreg composite body 10 in such a state as to hold the prepreg composite body 10 within the closed space 40A.

Description

  The present invention relates to a prepreg package and a method for manufacturing a prepreg package, and more particularly to a prepreg package that can provide a prepreg with high wiring embeddability when used, and a method for manufacturing a prepreg package.

  In recent years, demand for higher frequency and higher density of information transmission has increased, and development of high-performance multilayer circuit boards with higher precision, multilayers, and miniaturization is progressing. A multilayer circuit board used for information transmission in a high frequency region is required to have a material with a small transmission loss. As such a material, for example, Patent Document 1 discloses a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, and a reactive fluidizing agent.

When the polymerizable composition is used, for example, a multilayer circuit board is produced by the following procedure. That is, first, a fiber base material is impregnated with the polymerizable composition to obtain an impregnated product, and a cycloolefin monomer in the impregnated product is bulk-polymerized to prepare a prepreg (crosslinkable resin) comprising the cycloolefin polymer and the fiber base material. A molded body) is obtained. Next, a plurality of circuit boards are prepared, and a multilayer circuit board is manufactured by crosslinking the prepreg by hot pressing with the prepreg sandwiched between the circuit boards.
The multilayer circuit board is manufactured by the following procedure. That is, first, a plurality of arbitrary prepregs are laminated to obtain a laminated prepreg, and the prepreg is cured by a crosslinking reaction with a copper foil disposed on both sides of the laminated prepreg to cure the crosslinked prepreg and the copper A copper clad laminate comprising foil is obtained. Next, the copper foil of the obtained copper clad laminate is etched to form a pattern wiring to obtain a circuit board.

  Here, the reactive fluidizing agent contained in the polymerizable composition functions as a plasticizer not involved in the reaction at the time of the polymerization reaction, and is therefore blended for the purpose of imparting the fluidity of the crosslinkable prepreg. Accordingly, when the prepreg is cross-linked with the prepreg sandwiched between the circuit boards, the prepreg having high fluidity appropriately follows the wiring pattern formed on the surface of the circuit board. It can be securely embedded in the prepreg. Thus, the prepreg is required to have high wiring embedding properties.

International Publication WO2010 / 047348

  However, according to the present inventors, it has been confirmed that the fluidizing agent has a relatively high volatility as compared with other blending components. For this reason, when the prepreg containing the fluidizing agent is stored or left for a long period of time for a certain period or longer, the prepreg cannot ensure sufficient fluidity during actual use, and wiring embedding is sufficient. There was no case. Such a problem is not limited to the case where the fluidizing agent is included, but similarly occurs when other components having relatively high volatility are included. An object of the present invention is to provide a prepreg package that can provide a prepreg with high wiring embeddability when used, and a method for manufacturing the prepreg package.

According to this invention, the manufacturing method of the prepreg package of the following (1)-(11) or a prepreg package is provided.
(1) A prepreg comprising one or more prepreg bodies obtained by impregnating a fiber base material with a resin component, a prepreg composite comprising a protective film formed on at least one surface of the prepreg, and a sealed space A prepreg package including a storage body, wherein the storage body stores the prepreg composite in a state where the prepreg composite is held in the sealed space.
(2) The prepreg package in which the sealed space of the storage body is replaced by an inert gas.
(3) The prepreg package body in which the inside of the sealed space of the storage body is deaerated.
(4) The prepreg package, wherein the prepreg is a laminated body formed by laminating a plurality of the prepreg bodies.
(5) The prepreg composite is the prepreg package in which the protective film is formed on both surfaces of the prepreg.
(6) The prepreg package is formed of a film member including a barrier layer made of a material containing metal.
(7) The resin component is a polymerizable composition containing a monomer and a polymerization catalyst, and the prepreg body is formed by impregnating the polymerizable composition with the fibrous base material impregnated with the polymerizable composition. The said prepreg package which is a resin molding formed by superposition | polymerization.
(8) The resin component is a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a fluidizing agent, and the prepreg body impregnates the fibrous base material with the polymerizable composition. The prepreg package, which is a resin molded body having a crosslinkability obtained by polymerizing the polymerizable composition in a state where the prepreg is in a dry state.
(9) A prepreg composite forming step of forming a prepreg composite by forming a protective film on at least one surface of a prepreg including one or more prepreg bodies obtained by impregnating a fiber base with a resin component, and a sealed space And a prepreg package forming step for forming a prepreg package in which the prepreg composite is stored in the sealed space in the sealed body.
(10) The method for producing the prepreg package, further comprising a storage step of storing the prepreg package obtained in the prepreg package formation step at a temperature of 30 ° C. or lower.
(11) The prepreg composite forming step includes a prepreg forming step of forming a prepreg including one or more prepreg bodies, and a prepreg composite forming a prepreg composite by forming a protective film on at least one surface of the prepreg. A prepreg composite body forming step, wherein the prepreg composite body forming step is performed within 2 hours after the completion of the prepreg forming step.

Moreover, according to the present invention,
(12) A prepreg composite taken out from the storage body of the prepreg package or the prepreg package obtained by the method for producing the prepreg package,
(13) A prepreg obtained by peeling the protective film from the prepreg composite,
(14) a crosslinked resin molded product obtained by crosslinking the prepreg, and
(13) A substrate having a conductor pattern layer formed on at least a part of at least one surface thereof is disposed so that the prepreg contacts the surface on which the conductor pattern layer is formed, and these are laminated. The resulting circuit board is provided.

  According to the prepreg package of the present invention or the method for producing a prepreg package, the prepreg composite having a protective film is formed on at least one surface of the prepreg, and the prepreg composite is held in the sealed space of the storage body. As a result, even when a volatile component is present in the prepreg, it is possible to prevent the volatile component from being volatilized outside the storage body due to the action of the protective film and the storage body. For this reason, when using the prepreg, there is an effect that it is possible to provide a prepreg having a high fluidity, that is, a high wiring embedding property, at the same level as in production. Further, when the internal space of the storage body is deaerated, for example, even when the prepreg package is subjected to vibration or the like, the powder as a component peels (drops) from the prepreg composite. There is an effect that the quality of the prepreg can be improved. Furthermore, when the inside of the sealed space is replaced with an inert gas, the material constituting the prepreg is not oxidized and deteriorated, so that the appearance of the prepreg can be kept good and the quality of the prepreg can be maintained. .

It is sectional drawing which shows the prepreg package which concerns on one Embodiment of this invention.

  Hereinafter, a prepreg package according to an embodiment of the present invention will be described in detail with reference to FIG. FIG. 1 is a cross-sectional view schematically showing a prepreg package 1 according to an embodiment of the present invention. As shown in FIG. 1, the prepreg package 1 is a form used when storing and transporting the prepreg composite 10, and includes a prepreg composite 10 and a storage body 40 that stores the prepreg composite 10. .

  The prepreg composite 10 is a member formed in a sheet shape, and includes a prepreg 20 and protective films 30 formed on both surfaces (front and back surfaces) of the prepreg 20.

  The prepreg 20 is configured as a laminate in which a plurality of sheet-like prepreg bodies 23 obtained by impregnating a fiber base material 21 with a resin component 22 are stacked. By setting it as such a laminated body, since the several prepreg main body 23 can be accommodated in the one storage body 40, the efficiency at the time of storage and conveyance of the prepreg main body 23 can be improved. The number of stacked prepreg bodies 23 can be 10 to 300. When the prepreg main body 23 is used, the prepreg main body 23 may be peeled off from the prepreg 20 that is a laminate and used one by one or plural. The shape of the prepreg body 23 is not particularly limited as long as it is a sheet shape, and may have a chamfered corner.

  The fiber base material 21 is a base material for reinforcing the prepreg main body 23, and is a member formed in a sheet shape such as a knitted fabric, a woven fabric, and a non-woven fabric of reinforcing fibers. The fiber base material 21 can be manufactured by appropriately cutting a long one (for example, 0.1 to 3000 m). The length dimension of the fiber base material 21 can be 10-2000 mm. Moreover, the width dimension of the fiber base material 21 can be 450-1300 mm, Preferably you can be 530-1280 mm. Although the thickness of the fiber base material 21 is not specifically limited, 5-100 micrometers, Preferably it can be set to 15-80 micrometers.

Examples of the reinforcing fibers include inorganic and / or organic fibers. Specific examples of these reinforcing 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. And inorganic fibers such as fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. 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 prepreg resulting from the density of the fiber bundles constituting the reinforcing fibers, it is preferable that the difference between the dielectric constant of the resin component 22 and the dielectric constant of the material constituting the reinforcing fibers is small. The material which comprises a reinforced fiber can be used individually by 1 type or in combination of 2 or more types. The shape of the fiber base material 21 is not specifically limited, For example, a mat | matte, cloth, a nonwoven fabric, etc. are mentioned. The reinforcing fiber may be used by opening a fiber bundle. The degree of opening of the reinforcing fiber is not particularly limited, but it is usually 20 cm ³ / cm ² / s or less, preferably 15 cm ³ / cm ² / s or less at the air permeability defined in JIS standard R 3420. As a specific method of opening, various methods such as a method using a high-pressure water jet, a method using a vibro washer, and a method using ultrasonic vibration can be used.

 The content of the reinforcing fiber in the prepreg body 23 is preferably 15% by volume or less, more preferably 2 to 10% by volume, and further preferably 5 to 10% by volume. When the content rate of the reinforcing fiber in the prepreg body 23 is within the above numerical range, when the circuit board is manufactured using the prepreg body 23, the transmission characteristics (SKEW is small) in the circuit board can be sufficiently enhanced. At the same time, sufficient mechanical strength can be secured.

  The resin component 22 is a normally liquid composition that is impregnated into the fiber base material 21. Examples of the resin component 22 include a liquid resin composition containing a curable resin. Examples of the curable resin include a thermosetting resin and a photocurable resin. Among these, a thermosetting resin is preferable because the process is simple. Examples of the thermosetting resin include epoxy resin, polyimide resin, polyester resin, polyphenylene ether resin, and cycloolefin resin. The resin component 22 may contain a solvent.

  Moreover, as the resin component 22, it is a polymerizable composition containing a monomer, Comprising: The composition which exhibits crosslinkability after the superposition | polymerization can be mentioned. As the polymerizable composition, for example, a post-crosslinkable composition containing a monomer or a post-crosslinkable composition containing a monomer and a polymerization catalyst can be used. Among these, as the polymerizable composition, a composition containing a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a fluidizing agent is preferable, and a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a crosslinking aid, and A composition containing a fluidizing agent is more preferred. Even if a component having a relatively high volatility is contained, such as a fluidizing agent, a decrease in fluidity can be suppressed by constituting the prepreg package 1 of the present invention, and the prepreg 20 can be used. Sometimes it can be suitably used. In addition, the said polymeric composition may contain the solvent.

  Various monomers can be used as the monomer constituting the polymerizable composition, and as described above, a cycloolefin monomer can be preferably 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 body. 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 Are, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5, 6 , 7a-tetrahydro-4,7-methano-1H-indene and derivatives thereof; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Non-conjugated dienes such as 1,7-octadiene; and the like. 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 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 by dissolving or suspending 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 reactive fluidizing agent as a fluidizing agent, You may mix | blend other compounding agents, such as a polymerization regulator, a polymerization reaction retarder, antioxidant, and a coloring agent. As these compounding agents, for example, compounds described in JP2009-242568A, compounds described in JP2010-10000683, and the like can be used.

  The filler is not particularly limited, and for example, an organic material or an inorganic material can be used, but an inorganic material is preferable from the viewpoint of obtaining the molded article having a higher elastic modulus. 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.

  Further, as described above, the polymerizable composition is preferably a crosslinkable resin composition containing a crosslinking agent, and more preferably a crosslinkable resin composition containing a crosslinking agent and a crosslinking aid. . With such a configuration, when the prepreg body is formed, the resin composition in the prepreg body can be configured as a post-crosslinkable resin composition, that is, a crosslinkable resin composition. Here, “after-crosslinking is possible” means that the prepreg body can be heated, for example, to advance the crosslinking reaction of the crosslinkable resin composition in the prepreg body to form a molded body.

  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. It is possible to arbitrarily control the glass transition temperature and the molten state of the resin component constituting the prepreg body by using two or more kinds of radical generators together and adjusting the amount ratio thereof. 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 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 molded product obtained by curing (crosslinking) the prepreg body has a sufficient crosslinking density, and a circuit board having desired physical properties can be efficiently obtained. It is.

  As the crosslinking assistant, a polyfunctional compound 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 polymerization is preferable. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group, particularly as an isopropenyl group or (meth) acryloyl group, in the compound constituting the crosslinking aid, (meth) More preferably it is present as an acryloyl group. The (meth) acryloyl group means to include both a methacryloyl group and an acryloyl group.

Examples of the polyfunctional compound having two or more isopropenyl groups include p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene and the like.
Examples of the polyfunctional compound having two or more (meth) acryloyl groups include ethylene di (meth) acrylate, 1,3-butylene di (meth) acrylate, 1,4-butylene di (meth) acrylate, and 1,6-hexanediol diene. (Meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, 2,2′-bis (4- (meth) acryloxydiethoxyphenyl) propane, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate And so on. 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.

  Moreover, as mentioned above, the polymerizable composition is preferably a composition containing a fluidizing agent. The fluidizing agent is a material that enhances the fluidity of the polymerizable composition, and among them, a reactive fluidizing agent that is a reactive fluidizing agent can be suitably used. The reactive fluidizing agent hardly participates in the polymerization reaction under the conditions of the polymerization reaction of the cycloolefin monomer. In the cycloolefin resin obtained by polymerizing the cycloolefin monomer, under the conditions of the crosslinking reaction induced by the crosslinking agent, It is a compound having a reactivity that mainly participates in the crosslinking reaction and binds to the resin.

 For example, when a prepreg is formed using a polymerizable composition containing the reactive fluidizing agent, the fluidity of the prepreg can be sufficiently ensured by being hardly involved in the reaction under the polymerization reaction conditions. In addition, the cycloolefin resin is mainly involved in the crosslinking reaction under the crosslinking reaction conditions of the cycloolefin resin obtained by polymerizing the polymerizable composition containing the cycloolefin monomer (temperature conditions for the crosslinking agent to function). In the cross-linked molded article, the reactive fluidizing agent substantially remains in a free state. For this reason, unlike the so-called plasticizer, there is no problem such as lowering the heat resistance of the obtained cross-linked molded product, but rather the effect of increasing the heat resistance and crack resistance of the cross-linked molded product can be achieved. For this reason, the quality of a crosslinked molded object can be improved.

 The reactive fluidizing agent does not have a polymerizable aliphatic carbon-carbon unsaturated bond that can participate in the polymerization reaction, and is capable of binding to a polymer by participating in a crosslinking reaction induced by a crosslinking agent. A monofunctional compound having one functional group can be preferably used. Examples of the polymerizable aliphatic carbon-carbon unsaturated bond that can participate in the polymerization reaction include a polymerizable aliphatic carbon-carbon double bond and a vinyl group in a cycloolefin structure. In addition, examples of the crosslinkable functional group capable of binding to the polymer by participating in the crosslinking reaction induced by the crosslinking agent include a crosslinkable aliphatic carbon-carbon unsaturated bond and a crosslinkable organic group. be able to. The crosslinkable aliphatic carbon-carbon unsaturated bond is preferably present as a terminal vinylidene group in the compound constituting the reactive fluidizing agent, for example, as an isopropenyl group or a (meth) acryloyl group. More preferably, it is present as a (meth) acryloyl group. Examples of the crosslinkable organic group include an epoxy group, an isocyanate group, and a sulfo group.

 Examples of monofunctional compounds having one (meth) acryloyl group as a terminal vinylidene group that is a crosslinkable functional group include lauryl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and And methoxydiethylene glycol (meth) acrylate. In the present invention, the “(meth) acryloyl group” includes both a methacryloyl group and an acryloyl group. “(Meth) acrylate” includes both methacrylate and acrylate. Moreover, isopropenylbenzene etc. can be mentioned as a monofunctional compound which has one isopropenyl group as a terminal vinylidene group which is a crosslinkable functional group.

 These reactive fluidizing agents can be used alone or in combination of two or more. The blending amount of the reactive fluidizing agent may be appropriately selected as desired, but is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 100 parts by weight of the cycloolefin monomer to be blended. Is 1-30 parts by weight.

  The resin component can be used by appropriately mixing the components blended as desired. When a polymerizable composition is used as the resin component, 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 the compounding agent is used as a compound other than the monomer and the polymerization catalyst, the compounding agent may be added to the monomer solution or the catalyst solution, You may add to the liquid mixture of a monomer liquid and a catalyst liquid.

  The prepreg body 23 can be obtained as follows. That is, for example, when a polymerizable composition is used as the resin component, the prepreg body 23 obtains an impregnated product by impregnating the fiber composition 21 with the polymerizable composition, and the polymerizable property in the impregnated product is obtained. It can be obtained by polymerizing the composition. Here, when a post-crosslinkable composition is used as the polymerizable composition, the crosslinkable resin obtained by polymerizing the polymerizable composition may be arbitrarily replaced with another member (for example, a metal foil). By cross-linking in a laminated state, a cross-linked resin molded body or a cross-linked resin molded body and a laminate of the other member can be obtained.

 The polymerization method of the polymerizable composition may be appropriately selected according to the production method of the prepreg body 23, but bulk polymerization and solution polymerization can be used, and among these, molding defects due to volatile components are small. Bulk polymerization is preferred. As a method for impregnating the polymerizable composition into the fiber base material, for example, a predetermined amount of the polymerizable composition is applied to the fiber base material by a spray coating method, a dip coating method, a roll coating method, or a curtain coating method. The film is applied by a known method such as a die coating method and a slit coating method, and then, if desired, with a protective film laminated on at least one surface of the impregnated material, the impregnated material is pressed from above with a roller or the like. Can be obtained.

 Here, the polymerization of the polymerizable composition in the impregnated product can be performed by heating to a predetermined temperature. The heating temperature for polymerizing the polymerizable composition is in the range of 30 to 250 ° C, preferably 50 to 200 ° C, more preferably 90 to 150 ° C. In addition, the heating temperature is 1 minute or less half-life temperature of the radical generator as the crosslinking agent, preferably 10 ° C. or more lower than the 1-minute half-life temperature, more preferably 20 ° C. or more than 1-minute half-life temperature. The temperature is low. The polymerization time may be appropriately selected. As a heating method of the impregnated material, for example, a method in which the impregnated material is placed on a support and then heated, or a fiber base material is placed in advance in a mold, and the polymerizable composition is placed in the mold. A method of heating after impregnating a fiber base material to obtain an impregnated material can be exemplified.

  The obtained crosslinkable resin has substantially no crosslink structure, and for example, a resin that is soluble in toluene is suitable. Here, the molecular weight of the polymer is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5, It is in the range of 10,000 to 500,000, more preferably 10,000 to 100,000. Here, the weight average molecular weight of the polymer can be adjusted by appropriately changing the blending amounts of various blending agents such as the above-mentioned crosslinking aid and chain transfer agent, and the polymerization reaction conditions.

  The cross-linked resin portion in the cross-linked resin molded product obtained by cross-linking the cross-linkable resin preferably has a glass transition temperature of more than 160 ° C., more preferably more than 170 ° C., and is excellent in heat resistance. Further, when the polymerizable composition contains a cycloolefin monomer, it contains a cycloolefin resin obtained by polymerizing the cycloolefin monomer, so that the dielectric loss tangent is small and suitable as an insulating material for a circuit board. It is.

  The protective film 30 is a sheet-like member that protects the front and back surfaces of the prepreg 20 that is a laminate. As a method of obtaining the prepreg composite 10 by forming the protective film 30 on the prepreg 20, for example, (1) the protective film 30 is laminated on the uppermost surface and the lowermost surface of the prepreg 20 that is a laminate by a lamination method or the like. (2) A prepreg composite comprising a protective film 30 as a support, a prepreg main body 23 formed on the protective film 30 as the support, and a single prepreg main body 23 and the protective film. 10 is obtained, and a plurality of the prepreg composites 10 are stacked to finally obtain a laminate of the prepreg composites 10 laminated so that the protective film 30 is positioned on the uppermost surface and the lowermost surface, etc. Can be mentioned. In the case of the method (2), the laminate of the obtained prepreg composite 10 is configured as a composite in which the protective film 30 is sandwiched between the plurality of prepreg main bodies 23.

 Here, the thickness of the protective film 30 can be 5 to 300 μm. Moreover, each area of the front and back surfaces of the protective film 30 can be 0.95 to 1.05 times as large as each area of the front and back surfaces of the prepreg main body 23 that abuts. By setting it as such an area, it can prevent that a volatile component volatilizes from the prepreg main body 23 more than necessary.

 Examples of the protective film 30 include a resin film and a metal foil such as a copper foil. Examples of the material used for the resin film include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, acrylic resin, polycycloolefin (cycloolefin resin), triacetyl cellulose, polyether sulfide, polyether ketone, and polyimide. it can. Among these, as the material, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is preferable from the viewpoint of peelability.

  The protective film 30 may be a single layer or a multilayer. Further, a release layer, an antistatic layer, and / or a colored layer may be formed on the surface of the protective film 30. As the material constituting the release layer, known materials can be adopted, for example, thermosetting resins such as silicone resin, fluororesin, epoxy resin, melamine resin, alkyd resin, and acrylic resin, and cellulose resin. Can be mentioned.

  The storage body 40 has a sealed space 40A. The storage body 40 is a member that stores and holds the prepreg composite 10 in the sealed space 40A. As the storage body 40, for example, a film member (including a sheet shape) is preferably used that is formed into a bag shape or a box shape having a sealed space 40A inside. Thus, by making the storage body 40 into a bag shape or a box shape, the manufacture of the storage body 40 is simple, and it is advantageous at the time of storage and transportation. Furthermore, the storage body 40 is more preferably formed in a bag shape from the viewpoint of workability when forming the sealed space 40A.

  The film member may be a single layer or a multilayer. The thickness of the film member can be 10 to 500 μm. It is preferable to use a film having a resin layer as the film member. As the resin layer, a stretched polyester resin film, a stretched polyolefin resin film, and a stretched polyamide resin film can be used. More specifically, a polyamide film, a polyester film, a polyolefin film, a nylon film, etc. A resin film can be mentioned.

  The film having the resin layer preferably includes various functional layers in addition to the resin layer. Examples of the functional layer include a barrier layer and a sealant layer. The barrier layer is a layer that functions as a layer that does not transmit oxygen, water (water vapor), light, and the like. Examples of the material for forming the barrier layer include inorganic materials and organic materials, but inorganic materials are preferable from the viewpoint of improving moisture resistance, and materials including metals such as aluminum are particularly preferable.

  Here, when forming the barrier layer using the material containing the metal, as a method of forming the barrier layer, for example, a method of depositing a metal on the resin layer or an adhesive is used to form the barrier layer. Examples thereof include a method of laminating a metal foil, a method of applying a metal-containing composition to the resin layer, and the like.

  The sealant layer is a layer constituting the innermost layer of the bag when the container 40 is formed in a bag shape, for example, using the film having the resin layer. The sealant layer is a layer having a melting point lower than that of the resin layer and functioning as a heat seal layer that can be melted by heating and melt-bonded between the sealant layers. The material for forming the sealant layer is preferably a material having heat sealability, high heat seal strength (adhesiveness), and suitable strength and piercing strength so as to have durability against stress. Specifically, for example, polyethylene or polypropylene can be used.

Next, a method for manufacturing the prepreg package 1 will be described.
First, the prepreg composite 10 is manufactured. Specifically, for example, the case where the polymerizable composition is used as the resin component 22 will be described as an example. First, a polymerizable composition is applied on the fiber base material 21 to obtain an impregnation product in which the fiber base material 21 is impregnated with the polymerizable composition. Next, the impregnated product is heated to a predetermined temperature to polymerize the monomers in the polymerizable composition, thereby forming a prepreg body 23 as a crosslinkable resin composition (prepreg forming step). Similarly, a plurality of prepreg main bodies 23 are formed, and, for example, 50 prepreg main bodies 23 are laminated to obtain a prepreg 20 as a laminated body. Next, the protective film 30 is laminated on both sides of the prepreg 20 to form the prepreg composite 10 (prepreg composite forming step).

  Here, when the protective film 30 is laminated on the prepreg 20, the protective film 30 is preferably formed on both surfaces of the prepreg 20 within 2 hours after the prepreg 20 is formed, and more preferably within 1 hour. With such a configuration, it is possible to prevent the volatile component from volatilizing from the prepreg 20.

  Moreover, while manufacturing the accommodating body 40 using the said film member which has the said resin layer and the said sealant layer, the prepreg package 1 which accommodated the obtained prepreg composite_body | complex 10 in the sealed space 40A of this accommodating body 40. FIG. Is manufactured (prepreg package forming step). More specifically, for example, the prepreg package 1 is manufactured by the following method (1) or (2).

(1) The bag-shaped storage body 40 is formed by heat-sealing the sealant layer at a predetermined location so that an opening opened at only one location remains. Next, the obtained prepreg composite 10 is stored in a bag-shaped storage body 40, and the interior of the bag is deaerated from the opening (deaeration step). Finally, the vicinity of the opening is heat-sealed by a heat seal process to form a sealed space 40A in the storage body 40, and the prepreg package 1 in which the prepreg composite 10 is stored in the sealed space 40A is manufactured. To do.

(2) The periphery of the obtained prepreg composite 10 is covered with the film member, and in this state, the sealant layer at a predetermined place is heat-sealed so as to leave an opening that is opened only at one place. . Next, the internal space is degassed from the opening (deaeration process), and in this state, the vicinity of the opening is heat-sealed by heat sealing, thereby forming a sealed space 40A in the housing 40. At the same time, the prepreg package 1 in which the prepreg composite 10 is housed in the sealed space 40A is manufactured.

  As a method for the deaeration treatment, for example, when the opening is provided, a suction device such as a so-called vacuum cleaner is installed in the opening, thereby sucking gas (air) in the internal space of the storage body 40. This method is preferable because it is simple.

  Here, it is preferable to replace the interior space with an inert gas and / or a reducing gas before the deaeration process of the interior space of the storage body 40 (gas replacement step). According to such a configuration, discoloration of the prepreg body 23 stored in the internal space of the storage body 40 can be suppressed. Examples of the inert gas include nitrogen, helium, carbon dioxide, argon, xenon, and krypton. Examples of the reducing gas include hydrogen, methane, and ethylene.

  Finally, the obtained prepreg package 1 is stored at a relatively low temperature (storage process). Specifically, the storage temperature of the prepreg package 1 is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and even more preferably 10 ° C. or lower. When the storage temperature of the prepreg package 1 is in the above range, it is possible to prevent the blended component from bleeding out from the prepreg body 23. The prepreg package 1 is manufactured by the above procedure.

Next, the usage method of the obtained prepreg package 1 is demonstrated.
First, the storage body 40 of the stored prepreg package 1 is opened to take out the prepreg composite 10, and the protective film 30 is peeled off from the prepreg composite 10 to obtain the prepreg 20. Next, one or more prepregs 20 are sandwiched between substrates having a conductor pattern layer formed on at least a part of at least one surface, and the prepreg 20 and each conductor pattern layer are in contact with each other. 20 is arranged, and in this state, the prepreg 20 is heated to the above-mentioned predetermined temperature and crosslinked to obtain a multilayer circuit board.

  In addition, copper clad laminates (CCL: Copper Clad Laminates) as a laminate in which the prepreg 20 is crosslinked in a state where the prepreg 20 and the copper foil are laminated can also be obtained. Furthermore, the circuit board which formed the pattern wiring by masking and etching the metal foil of this copper clad laminated board by a known method can be manufactured. This pattern wiring may include a pair of transmission lines (differential wiring).

 In addition, the obtained prepreg (prepreg main body) can implement | achieve a low dielectric constant and a low dielectric loss tangent by forming using the said polymeric composition containing a cycloolefin monomer. Specifically, the prepreg has a dielectric constant at a frequency of 1 GHz, preferably reduced to 4.0 or less, more preferably 3.5 or less. The dielectric loss tangent at a frequency of 1 GHz is preferably reduced to 0.005 or less, more preferably 0.001 or less.

According to this embodiment, the following effects can be achieved.
That is, the prepreg composite 10 having the protective film 30 is formed on at least one surface of the prepreg 20, and the prepreg composite 10 is held in the sealed space 40 </ b> A of the container 40. Even when there is a component that is easy to do, the action of the protective film 30 and the storage body 40 can suppress the evaporation of the easily volatile component outside the prepreg 20 and the storage body 40. For this reason, when using the prepreg 20 (prepreg main body 23), it is possible to provide the prepreg 20 (prepreg main body 23) having a high fluidity, that is, having a high wiring embedding property, at the same level as in production.

In addition, this invention is not limited to the said embodiment.
For example, in the above-described embodiment, the protective film 30 is formed on both surfaces of the prepreg 20, but the present invention is not limited thereto, and the protective film 30 may be formed only on one surface of the prepreg 20. Moreover, in the said embodiment, although the prepreg 20 was comprised as the laminated body 24 which consists of several prepreg main body 23, you may comprise not only this but the prepreg 20 with the prepreg main body 23 of 1 sheet.

  The prepreg composite 10 may be manufactured as follows. That is, the fiber base material 21 is disposed on the protective film 30, and then the impregnated product obtained by impregnating the fiber base material 21 with the polymerizable composition is obtained. Next, the impregnated product is heated to a predetermined temperature to polymerize the monomer in the polymerizable composition to form a prepreg body 23 as a crosslinkable resin composition. At the same time, a protective film 30 is formed on one surface of the prepreg body 23. The formed prepreg composite 10 is formed. According to such a process, since the prepreg formation step and the prepreg complex formation step are performed at substantially the same timing, it is possible to reliably prevent the volatile components from the prepreg 20 from being volatilized.

  Further, an impregnated material obtained by impregnating the long fiber base material 21 with the resin component 22 is obtained, and a long protective film 30 is disposed on at least one surface of the impregnated material. By laminating by passing a roll or the like, a long prepreg composite having a protective film 30 on at least one surface of the impregnated material is obtained. Next, the prepreg composite 10 may be manufactured by cutting the long prepreg composite into an appropriate size. According to such a process, there exists an advantage which can manufacture the prepreg composite_body | complex 10 efficiently.

  In the above embodiment, a film member having a sealant layer is used and heat sealed by heat sealing treatment to form the sealed space 40A in the storage body 40. However, no gas flows in and out in the opening. For example, the opening of the storage body 40 may be sealed using various bonding means such as an adhesive tape to form the sealed space 40A in the storage body 40.

  In the above embodiment, after the inside of the sealed space 40A is replaced with an inert gas and / or a reducing gas, the inner space of the storage body 40 is deaerated, but the gas replacement process in the sealed space 40A is performed. It is good also as a structure which does not perform a deaeration process only. Further, only the deaeration process may be performed without performing the gas replacement process. Further, if there is no particular problem in quality, a configuration in which neither the deaeration process nor the gas replacement process is performed may be employed.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Part” in each example is based on weight unless otherwise specified.
In addition, the evaluation method of each characteristic is as follows.

(1) Fluidity Using a 100 mm × 100 mm prepreg body, the weight change before and after pressing was determined according to the following criteria according to JIS C6521-1996. In addition, about press conditions, it was set as the temperature of 170 degreeC, the pressure of 1.4 MPa, and 10 minutes, and the prepreg main body after a press was cut out into the square of 70.7 mm on one side, and it was set as the sample piece.
A: 10% or more B: Less than 10%

(2) Powder fall 50 340mm x 510mm prepreg bodies are stacked, dropped 5 times from the position of 20mm height with the long side down, and the other long side is dropped 5 times in the same way, for a total of 10 Compared with the amount of powder falling when the same test was performed in a commercial prepreg (R1661 thickness 0.15 mm GG type: manufactured by Panasonic Corporation) Judged by the criteria of.
A: The amount of powder falling is less than 1/2 of the commercial product B: The amount of powder falling is 1/2 or more of the commercial product

(3) Bleed-out The prepreg package was opened, the prepreg composite was taken out, and the presence or absence of deposits on the inner surface of the prepreg package was visually confirmed.
A: No deposit B: There is deposit

(4) Appearance The prepreg package was opened, the prepreg composite was taken out, the protective film was peeled off from the prepreg composite, and the appearance of the prepreg was visually observed.
A: No discoloration B: Yellow discoloration

<Example 1>
(Preparation of polymerizable composition as resin component)
As a metathesis polymerization catalyst, 0.05 part of benzylidene (1,3-dimesitylmimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 0.01 part of triphenylphosphine are added to 1.51 parts of indene. A catalyst solution was prepared by dissolution. Further Separately, a tetracyclododecene (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodeca-4-ene / TCD) 100 parts of a cycloolefin monomer, with a crosslinking agent 2,3,5,7,7-pentamethyl-1,2,4-trioxepane (1 minute half-life temperature 205 ° C.) as a radical generator, 20 parts benzyl diacrylate as a crosslinking aid, A monomer liquid is prepared by mixing 100 parts of silicon oxide particles (average particle size 0.5 μm) as a filler, 0.74 parts of styrene as a chain transfer agent, and 10 parts of benzyl methacrylate as a reactive fluidizing agent. Prepared. Next, a polymerizable composition was obtained by mixing the catalyst solution with the obtained monomer solution.

(Manufacture of prepreg)
A fiber base material (E glass fiber) having a thickness of 25 μm and a width of 630 mm subjected to the fiber opening treatment was prepared, and the fiber base material was impregnated with the fiber base material to produce a prepreg body. The obtained prepreg main body was cut out to a size of 340 mm × 510 mm, and 50 cut out prepreg main bodies were stacked to obtain a prepreg made of a laminate. Next, a polyethylene terephthalate film having a size of 340 mm × 510 mm was bonded to both sides of the obtained prepreg to obtain a prepreg composite. The time required from the completion of the prepreg molding to the completion of the application of the protective film was within 2 hours.

(Manufacture of storage body)
As a film member, a packaging material having a three-layer structure of a polyethylene layer, a layer made of aluminum (barrier layer), and a polyethylene layer (sealant layer) was prepared. Using this packing material, a 600 × 600 mm bag having an opening at one location is prepared, the prepreg composite is stored in the bag, and nitrogen gas is filled in the bag to fill the bag. After nitrogen substitution, the nitrogen gas in the bag was degassed, and then the vicinity of the opening was heat-sealed (heat-sealed) to produce a prepreg package 1 having a sealed space. The obtained prepreg package 1 was stored in an environment of 23 ° C. for 45 days, and then taken out to evaluate the characteristics of the prepreg body.

<Example 2>
A prepreg package 2 was obtained in the same manner as in Example 1 except that the storage environment was changed from 23 ° C. to 30 ° C. in Example 1.

<Example 3>
A prepreg package 3 was obtained in the same manner as in Example 1 except that nitrogen substitution was not performed in Example 1.

<Example 4>
A prepreg package 4 was obtained in the same manner as in Example 1 except that the deaeration process was not performed in Example 1.

<Comparative Example 1>
In Example 1, a prepreg package 5 was obtained in the same manner as in Example 1 except that the prepreg was stored (leaved) for 45 days without sealing with a packing material.

<Comparative example 2>
In Example 1, a prepreg package 6 was obtained in the same manner as in Example 1 except that no protective film was used, nitrogen replacement was not performed, deaeration treatment was not performed, and the storage environment was 10 ° C. It was.

<Comparative Example 3>
A prepreg package 7 was obtained in the same manner as in Comparative Example 1 except that the protective film was not used.

  As shown in Table 1, when a prepreg composite having a protective film is formed and this prepreg composite is sealed in the sealed space of the container (Examples 1 to 4), the prepreg body is used. In doing so, it was found that the prepreg body had sufficient fluidity. On the other hand, when it is set as the structure which does not have a protective film (comparative examples 2 and 3), or the structure which does not store a prepreg complex in sealed space (comparative examples 1 and 3), the fluidity | liquidity of a prepreg main body is inadequate. Met. Moreover, it turned out that the structure (Examples 1-3) which carried out the deaeration process of the internal space of a storage body has few powder fall compared with the structure (Example 4, Comparative Examples 1-3) which does not carry out a deaeration process. . Furthermore, the configuration in which the internal space of the container is replaced with nitrogen gas (Examples 1, 2, and 4) has a better appearance of the prepreg than the configuration in which nitrogen gas is not replaced (Examples 3 and Comparative Examples 1 to 3). Met. It was found that the bleed out from the prepreg was small in the configuration (Examples 1, 3 and 4) stored at 23 ° C.

DESCRIPTION OF SYMBOLS 1 ... Prepreg packing body 10 ... Prepreg composite 20 ... Prepreg 21 ... Fiber base material 22 ... Resin component 23 ... Prepreg main body 30 ... Protective film 40 ... Storage body 40A ... Sealed space

Claims (11)

A prepreg comprising one or more prepreg bodies obtained by impregnating a fiber substrate with a resin component, and a prepreg composite comprising a protective film formed on at least one surface of the prepreg;
A prepreg package including a storage body having a sealed space,
The storage body is a prepreg package that stores the prepreg composite in a state of being held in the sealed space.   The prepreg package according to claim 1, wherein the sealed space of the storage body is replaced with an inert gas.   The prepreg package according to claim 1 or 2, wherein the sealed space of the storage body is deaerated.   The prepreg package according to any one of claims 1 to 3, wherein the prepreg is a laminate formed by laminating a plurality of the prepreg bodies.   The prepreg composite body according to any one of claims 1 to 4, wherein the protective film is formed on both surfaces of the prepreg composite.   The prepreg package according to any one of claims 1 to 5, wherein the storage body is formed of a film member including a barrier layer made of a metal-containing material. The resin component is a polymerizable composition containing a monomer and a polymerization catalyst,
The prepreg body according to any one of claims 1 to 6, wherein the prepreg body is a resin molded body obtained by polymerizing the polymerizable composition in a state where the fibrous base material is impregnated with the polymerizable composition. Packing body. The resin component is a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a fluidizing agent,
The prepreg body is a resin molded body having crosslinkability obtained by polymerizing the polymerizable composition in a state where the fibrous base material is impregnated with the polymerizable composition. The prepreg package described in 1. A prepreg composite forming step of forming a prepreg composite by forming a protective film on at least one surface of a prepreg including one or more prepreg bodies obtained by impregnating a fiber base with a resin component;
A prepreg package forming process for forming a prepreg package in which the prepreg composite is stored in the sealed space of the container having a sealed space; and
A method for producing a prepreg package comprising:   The manufacturing method of the prepreg package of Claim 9 further equipped with the storage process which stores the prepreg package obtained at the said prepreg package formation process at the temperature of 30 degrees C or less. The prepreg composite forming step includes a prepreg forming step of forming a prepreg including one or more prepreg bodies, and a prepreg composite forming step of forming a prepreg composite by forming a protective film on at least one surface of the prepreg. And comprising
The method for producing a prepreg package according to claim 9 or 10, wherein the prepreg composite forming step is performed within 2 hours after the completion of the prepreg forming step.

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