[go: up one dir, main page]

WO2015098620A1 - Procédé de production de composition polymérisable - Google Patents

Procédé de production de composition polymérisable Download PDF

Info

Publication number
WO2015098620A1
WO2015098620A1 PCT/JP2014/083254 JP2014083254W WO2015098620A1 WO 2015098620 A1 WO2015098620 A1 WO 2015098620A1 JP 2014083254 W JP2014083254 W JP 2014083254W WO 2015098620 A1 WO2015098620 A1 WO 2015098620A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerizable composition
producing
inorganic compound
composition according
compound particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/083254
Other languages
English (en)
Japanese (ja)
Inventor
佳奈子 國井
勉 長宗
和晃 濱田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2015554766A priority Critical patent/JPWO2015098620A1/ja
Publication of WO2015098620A1 publication Critical patent/WO2015098620A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention provides a polymerizable composition capable of sufficiently crushing aggregates (secondary particles) of inorganic compound particles and reducing the metal concentration derived from the apparatus when mixing the liquid polymerizable monomer and the inorganic compound particles.
  • the present invention relates to a method for manufacturing a product.
  • Patent Document 1 Patent No. 5010112
  • a solvent-based varnish of an epoxy resin composition containing an epoxy resin, a curing agent, and an inorganic filler is kneaded selected from a ball mill, a bead mill, and a roll mill composed of a plurality of rolls.
  • the dispersibility of the resin composition is improved by kneading by means.
  • Such ball mills, bead mills, roll mills and the like are generally made of metal.
  • a metal derived from the apparatus may be mixed in the resin composition.
  • the mixing of the metal is caused by the fact that the inner wall of the metal apparatus is scraped when the resin composition is ground by a mechanism inside the apparatus (hard sphere in a ball mill or bead mill, or roll in a roll mill).
  • This invention is made
  • a method for producing a polymerizable composition comprising (a) a liquid polymerizable monomer and (b) inorganic compound particles, (A) In the liquid polymerizable monomer (b) under the condition that the maximum flow velocity at the orifice in the orifice type shear generation type disperser is 1.8 m / s or more using an orifice type shear generation type disperser.
  • composition according to any one of [1] to [5], wherein the polymerizable composition comprises (b) 1 to 1000 parts by mass of inorganic compound particles with respect to 100 parts by mass of the liquid polymerizable monomer.
  • a prepreg for a printed wiring board having a metal concentration of 0.1 mg / m 2 or less which is obtained by impregnating the polymerizable composition according to [13] above into a fibrous reinforcing material and then polymerizing the fibrous reinforcing material.
  • the method for producing a polymerizable composition since the aggregate of (b) inorganic compound particles can be easily crushed, the solid content mass captured when the liquid obtained in the dispersion step is filtered. Can be reduced. As a result, the dispersibility of the inorganic compound particles (b) in the polymerizable composition is improved, the bulk polymerization reaction can be performed uniformly, and the moldability and storage stability of the resulting crosslinkable resin molded product are improved. . Moreover, according to the manufacturing method of the polymeric composition which concerns on this invention, it can suppress that the metal derived from an apparatus mixes in a polymeric composition. As a result, the resulting crosslinkable resin molded article is excellent in insulation.
  • the method for producing a polymerizable composition uses an orifice type shear-generating disperser under the condition that the maximum flow velocity at the orifice in the orifice-type shear generating disperser is 1.8 m / s or more ( a) a dispersion step of dispersing (b) inorganic compound particles in the liquid polymerizable monomer;
  • Orifice-type shear generator Disperser in the present invention is an orifice-type shear generator-type disperser in which a flow path branches and merges in a pipe, and a plurality of orifices (small holes through which a processing fluid passes) along the flow path
  • the solid component in the processing fluid is pulverized and dispersed in the liquid by the energy of collision and shear when the processing fluid passes through.
  • the size of the orifice in the soot-orifice type shear generator is reduced along the flow direction of the processing fluid. For this reason, the size of the most downstream orifice is minimized, and the flow velocity (that is, linear velocity) of the processing fluid is maximized.
  • the size of the most downstream orifice may be determined as appropriate so that the maximum flow velocity of the processing fluid falls within the scope of the present invention in accordance with the scale (that is, the flow rate) of the processing fluid to be dispersed.
  • the dispersion step in the present invention under the condition that the maximum flow velocity (that is, the maximum linear velocity) at the orifice in the orifice-type shear-generating disperser is 1.8 m / s or more, (a) b) Disperse the inorganic compound particles.
  • the maximum flow velocity that is, the maximum linear velocity
  • the inorganic compound particles By passing through such a dispersion step, when (a) the liquid polymerizable monomer and (b) inorganic compound particles are mixed, (b) aggregates of inorganic compound particles (aggregates of primary particles, hereinafter May be simply referred to as “secondary particles”). If there are many residues containing uncrushed secondary particles, the bulk polymerization reaction of the polymerizable composition may not be performed uniformly.
  • the secondary particles can be sufficiently crushed.
  • grains in polymeric composition can be improved.
  • the bulk polymerization reaction of the polymerizable composition can be performed uniformly, it is possible to obtain a crosslinkable resin molded article in which residual unreacted polymerizable monomer is suppressed and moldability and storage stability are excellent. it can.
  • the secondary particles are not sufficiently crushed.
  • the dispersibility of the inorganic compound particles (b) in the polymerizable composition being reduced, a uniform bulk polymerization reaction cannot be performed, and unreacted polymerizable monomers remain.
  • the moldability and storage stability of the resulting crosslinkable resin molded product are lowered.
  • the life of the filtration filter in the filtration step for removing secondary particles having a relatively large particle size is reduced.
  • the maximum flow velocity at the orifice in the orifice type shear generating disperser is preferably 1.8 to 20 m / s, more preferably 1.8 to 15 m / s, still more preferably 1.8 to 10 m / s, Particularly preferred is 1.8 to 6.0 m / s. If the maximum flow rate is too large, the disperser may be scraped by the pressure of the liquid passing through the orifice, or the disperser may be damaged in some cases.
  • an orifice type shear generating type disperser when using other dispersers (for example, a high-speed rotating rotor / stator mill type disperser, a planetary type triaxial agitator / emulsifier, a ball mill, a bead mill, a roll mill, etc.)
  • dispersers for example, a high-speed rotating rotor / stator mill type disperser, a planetary type triaxial agitator / emulsifier, a ball mill, a bead mill, a roll mill, etc.
  • the orifice type shear generator is preferably made of metal from the viewpoint of durability.
  • the metal concentration derived from the device in the polymerizable composition (total concentration of cobalt (Co), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni)) is preferably 2 ppm or less. More preferably, it is 1.5 ppm or less.
  • the metal concentration derived from an apparatus is measured by the method as described in an Example.
  • the crosslinkable resin molded body (for example, prepreg) produced using a polymerizable composition having a metal concentration derived from the apparatus has a metal concentration of preferably 0.15 mg / m 2 or less, more preferably 0.
  • the metal concentration of a crosslinkable resin molding can be measured with the following method. First, a glass cloth # 2112 as a fibrous reinforcing material is impregnated with a polymerizable composition (weight per unit area of the polymerizable composition: 70 g / m 2 ). Subsequently, a crosslinkable resin molded body (prepreg) having a film thickness of 130 ⁇ m is obtained by heating at 120 ° C. for 3.5 minutes to cause a bulk polymerization reaction. This prepreg is pulverized and wet-decomposed, and the metal concentration (total concentration of Co, Cr, Fe, Mn and Ni) is measured using ICP-AES (apparatus: SPS-5100 (SII nanotechnology)).
  • Examples of the above-mentioned orifice type shear generating type disperser include “Damatori-kun” (nominal size: 1 / 2S) manufactured by Yoshida Kikai Kogyo Co., Ltd.
  • the polymerizable composition of the present invention contains (a) a liquid polymerizable monomer.
  • the liquid polymerizable monomer is not particularly limited as long as it is a polymerizable liquid monomer.
  • an alicyclic olefin monomer, a styrene monomer, an acrylate monomer, an epoxy monomer and the like can be mentioned.
  • (a1) an alicyclic olefin monomer and (a2) a styrene-based monomer are preferable, and (a1) an alicyclic olefin monomer is more preferable because a crosslinkable resin molded article having a low dielectric loss can be obtained.
  • Alicyclic olefin monomer (a1)
  • the alicyclic olefin monomer is not particularly limited as long as it is an olefin compound having an alicyclic structure.
  • Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and combinations of these (the same applies hereinafter).
  • the number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.
  • an ethylidene group having two or more double bonds in the alicyclic structure, and at least one containing double bonds not involved in ring-opening polymerization (hereinafter, And “an alicyclic olefin monomer (a1-2)”) and other alicyclic olefin monomers (hereinafter sometimes referred to as "alicyclic olefin monomer (a1-3)").
  • an alicyclic olefin monomer (a1-2) preferably an ethylidene group having two or more double bonds in the alicyclic structure, and at least one containing double bonds not involved in ring-opening polymerization
  • alicyclic olefin monomer (a1-2) alicyclic olefin monomer (a1-3)"
  • the alicyclic olefin monomer (a1-1) and the alicyclic olefin monomer (a1-2) are preferable, and the alicyclic olefin monomer (
  • Examples of the alicyclic olefin monomer (a1-1) include a monocyclic alicyclic olefin monomer having an ethyl group and / or an ethylidene group, a norbornene monomer having an ethyl group and / or an ethylidene group, and the like.
  • a norbornene-based monomer having an ethylidene group is more preferable.
  • alicyclic olefin monomer (a1-1) examples include 9-methylidenetetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-10-methyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-10-ethyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-10-isopropyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylidene-10-butyltetracyclo [6.2.1.1 3,6 .
  • tetracyclododecenes such as dodec-4-ene; 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, n-propylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5 , 6-diethylidene-2-norbornene and the like;
  • the content of the alicyclic olefin monomer (a1-1) in the polymerizable composition is preferably 5% by mass or more, more preferably 20% by mass, based on all monomers constituting the polymerizable composition. Or more, more preferably 35% by mass or more, and particularly preferably 70% by mass or more. If the content of the alicyclic olefin monomer (a1-1) is too small, the crack resistance of the resulting crosslinkable resin molded article may be lowered, which is not preferable.
  • the “double bond not involved in ring-opening polymerization” in the alicyclic olefin monomer (a1-2) means “crosslinkable carbon-carbon unsaturated bond”, and is not involved in ring-opening polymerization and is not crosslinked.
  • the crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction.
  • a radical crosslinking reaction or a metathesis crosslinking reaction is performed. In particular, it refers to a radical crosslinking reaction.
  • Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds excluding aromatic carbon-carbon unsaturated bonds, ie, aliphatic carbon-carbon double bonds or aliphatic carbon-carbon triple bonds. In the present invention, it usually means an aliphatic carbon-carbon double bond. In the alicyclic olefin monomer (a1-2) used in the present invention, all the carbon atoms constituting such a crosslinkable carbon-carbon unsaturated bond constitute a part of the alicyclic structure. It will be.
  • Examples of such alicyclic olefin monomers (a1-2) include monocyclic alicyclic olefin monomers having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure, and crosslinkable carbon- in the alicyclic structure. Examples thereof include a norbornene monomer having a carbon unsaturated bond, and a norbornene monomer having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure is preferable.
  • alicyclic olefin monomer (a1-2) examples include dicyclopentadiene, methyl-dicyclopentadiene, dimethyldicyclopentadiene, ethyldicyclopentadiene, 2,5-norbornadiene, 5-methyl-2,5- Examples thereof include compounds having two carbon-carbon unsaturated bonds in the alicyclic structure such as norbornadiene, 5-phenyl-2,5-norbornadiene, and 5,6-dimethyl-2,5-norbornadiene. These can be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable from the viewpoint that the effects of the present invention become more remarkable.
  • the content ratio of the alicyclic olefin monomer (a1-2) is preferably among all the monomers constituting the polymerizable composition. Is 95% by mass or less, more preferably 80% by mass or less, still more preferably 65% by mass or less, and particularly preferably 30% by mass or less.
  • the polymerizable composition contains other alicyclic olefin monomer (a1-3) in addition to the alicyclic olefin monomer (a1-1) and alicyclic olefin monomer (a1-2). Also good.
  • Examples of other alicyclic olefin monomers (a1-3) include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, and 5,6-dimethyl-2-norbornene.
  • the content ratio of the alicyclic olefin monomer (a1-3) is usually in the total monomers constituting the polymerizable composition. 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.
  • (A2) Styrene monomer (a2) The styrene monomer is a compound having an aromatic ring and a vinyl group or an isopropenyl group bonded to the aromatic ring.
  • (A2) Styrene monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylethylbenzene, vinylxylene, pt-butylstyrene, ⁇ -methyl-p- Examples include methyl styrene and vinyl naphthalene. Among them, styrene is preferable.
  • styrene monomer compounds having two or more vinyl groups or isopropenyl groups such as o-divinylbenzene, p-divinylbenzene and m-divinylbenzene can be used.
  • Use of such a compound is preferable because the crosslinking reactivity of the resulting crosslinkable resin molded article can be increased, and the crosslink density of the crosslinkable resin molded article can be increased.
  • these (a2) styrenic monomers can be used singly or in combination of two or more.
  • the content ratio of (a2) styrenic monomer in the polymerizable composition is preferably 15% by mass or less in all monomers constituting the polymerizable composition.
  • Inorganic compound particles can be used without particular limitation as long as they are generally used industrially. By blending the inorganic compound particles (b) in the polymerizable composition of the present invention, it is possible to improve the mechanical strength and heat resistance of the resulting crosslinkable resin molded article and the laminate.
  • inorganic compound particles include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, Metal oxide particles such as alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite and strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate and sodium hydrogen carbonate; calcium sulfate Inorganic sulfate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon, etc .; titanates such as calcium titanate, lead zirconate titanate, etc. Particles; antimony trioxide, etc. Chimon compounds; aluminum nitride, or the like silicon carbide particles and whiskers and the like.
  • metal oxide particles are preferable as the inorganic compound particles (b) from the viewpoint of mechanical strength and heat resistance.
  • the metal oxide particles preferably contain 50% by mass or more of silica particles, more preferably 50 to 100% by mass, and still more preferably 50 to 80% by mass.
  • silica particle you may use what performed the hydrophobization process on the surface. By performing the hydrophobization treatment, the affinity between the (a) liquid polymerizable monomer and the surface of the silica particles is improved, and the silica particles are more easily dispersed more uniformly in the (a) liquid polymerizable monomer.
  • the primary average particle diameter (D50) of the inorganic compound particles is preferably 3 ⁇ m or less, more preferably 0.1 to 3 ⁇ m.
  • Inorganic compound particles having a primary average particle diameter (D50) in the above range are likely to aggregate particularly when mixed with the liquid polymerizable monomer (a), and the dispersibility in the polymerizable composition may be reduced. .
  • the aggregate (secondary particles) of (b) inorganic compound particles can be sufficiently crushed, so that the primary average particle diameter (D50) is in the above range (b) inorganic compound It can be suitably used for particles.
  • the primary average particle diameter (D50) of the inorganic compound particles means that the inorganic compound particles are mixed with (a) the liquid polymerizable monomer before the laser diffraction particle size distribution measuring device. (B) 50% volume average particle diameter of the inorganic compound particles calculated and calculated.
  • the secondary average particle diameter (D50) before the dispersion step of the inorganic compound particles is preferably more than 10 ⁇ m and 200 ⁇ m or less, more preferably more than 10 ⁇ m and 100 ⁇ m or less. Even if the secondary average particle diameter (D50) is in the above range, according to the method for producing a polymerizable composition of the present invention, the time of dispersion step (average treatment time) is shortened or the number of dispersion steps (number of average treatments). ), The secondary particles can be easily crushed. Therefore, the productivity of the polymerizable composition is improved.
  • the secondary average particle diameter (D50) before the dispersion step of the inorganic compound particles is the value after (b) the inorganic compound particles are mixed with the (a) liquid polymerizable monomer.
  • the secondary average particle diameter (D50) after the dispersion step of the inorganic compound particles is preferably 10 ⁇ m or less, more preferably 0.1 ⁇ m to 8 ⁇ m, still more preferably 0.5 ⁇ m to 6 ⁇ m, and particularly preferably 1 ⁇ m. It is 4 ⁇ m or less.
  • Inorganic compound particles having a secondary average particle size (D50) in the above range after the dispersion step are excellent in dispersibility in the polymerizable composition. As a result, the bulk polymerization reaction of the polymerizable composition can be performed uniformly, and the residual of the unreacted (a) liquid polymerizable monomer is suppressed, and a crosslinkable resin molded article excellent in storage stability is obtained. Can do.
  • the secondary average particle size (D50) after the dispersion step of the inorganic compound particles is the laser diffraction type after the dispersion step is performed using an orifice type shear generating disperser.
  • B 50% volume average particle diameter of inorganic compound particles calculated and measured with a particle size distribution analyzer.
  • the blending amount of the inorganic compound particles (b) is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, still more preferably 50 to 200 parts per 100 parts by weight of the (a) liquid polymerizable monomer. Part by mass, particularly preferably 50 to 150 parts by mass.
  • a polymerization catalyst in addition to the above components, if desired, as other additives, a polymerization catalyst, a crosslinking agent, a crosslinking assistant, a chain transfer agent, a flame retardant, a polymerization regulator, a polymerization reaction retarder, An anti-aging agent or other compounding agents can be further added. Any of these components can be used alone or in combination of two or more. The addition amount may be appropriately selected within a range that does not impair the effects of the present invention.
  • the polymerizable composition used in the present invention can contain a polymerization catalyst.
  • a metathesis polymerization catalyst is preferable.
  • the metathesis polymerization catalyst include transition metal complexes in which a plurality of ions, atoms, polyatomic ions, compounds, and the like are bonded with a transition metal atom as a central atom.
  • the transition metal atom include atoms of Group 5, Group 6, and Group 8 (according to the long-period periodic table; the same shall apply hereinafter).
  • 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.
  • the transition metal atom Group 8 ruthenium or osmium is preferable. That is, as the metathesis polymerization catalyst, a complex having ruthenium or osmium as a central atom is preferable, and a complex having ruthenium as a central atom is more preferable.
  • a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable.
  • the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the polymerizable composition is subjected to bulk polymerization to obtain a crosslinkable resin molded product, the resulting molded product has little odor derived from unreacted monomers. A high-quality molded product with good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.
  • ruthenium carbene complex examples include complexes represented by the following formula (V) or formula (VI).
  • R 11 and R 12 each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom.
  • X 1 and X 2 each independently represents an arbitrary anionic ligand.
  • L 1 and L 2 each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than a hetero atom-containing carbene compound.
  • R 11 and R 12 may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom.
  • R 11 , R 12 , X 1 , X 2 , L 1 and L 2 may be bonded together in any combination to form a multidentate chelating ligand.
  • a heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), a selenium atom (Se), etc. can be mentioned.
  • N, O, P, and S are preferable from the viewpoint of obtaining a stable carbene compound, and N is particularly preferable.
  • the mechanical strength and impact resistance of the resulting crosslinked resin molded product and laminate can be highly balanced, so that a carbene compound having a heterocyclic structure is coordinated as a heteroatom-containing carbene compound. What has at least 1 child is preferable.
  • a carbene compound having a heterocyclic structure is coordinated as a heteroatom-containing carbene compound. What has at least 1 child is preferable.
  • the heterocyclic structure an imidazoline ring structure or an imidazolidine ring structure is preferable.
  • Examples of the carbene compound having a heterocyclic structure include compounds represented by the following formula (VII) or formula (VIII).
  • R 13 to R 16 each independently contain a hydrogen atom; a halogen atom; or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom.
  • Examples of the compound represented by the formula (VII) or the formula (VIII) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1, 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenylethyl) ) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene and the like.
  • the anionic (anionic) ligands X 1 and X 2 are ligands having a negative charge when separated from the central atom.
  • halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, and carboxyl Examples include groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.
  • the neutral electron donating compound may be any ligand as long as it has a neutral charge when pulled away from the central atom.
  • Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates.
  • phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.
  • Examples of the ruthenium carbene complex represented by the formula (V) include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5- Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tricyclohexylphosphine) ) Ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl
  • a ruthenium carbene complex in which two neutral electron-donating compounds are bound such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride;
  • Examples of the ruthenium carbene complex represented by the formula (VI) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1, And 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride and bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride.
  • the metathesis polymerization catalyst can be used alone or in combination of two or more.
  • the content of the metathesis polymerization catalyst is preferably a molar ratio (metal atom in the metathesis polymerization catalyst: (a) liquid polymerizable monomer), preferably 1: 2,000 to 1: 2,000,000, more preferably The range is from 1: 5,000 to 1: 1,000,000, more preferably from 1: 10,000 to 1: 500,000.
  • the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent, if desired.
  • solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethyl Cycloaliphatic hydrocarbons such as cyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; nitrogen-
  • (C) Crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition of the present invention. Therefore, the obtained crosslinkable resin molding can be a postcrosslinkable thermoplastic resin.
  • “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin.
  • the crosslinkable resin molded product of the present invention is softened by heating to a glass transition temperature or higher, and can be molded into a desired shape by applying pressure in this state. Furthermore, when the used crosslinking agent (c) is heated to a temperature higher than the activity, the crosslinkable resin molded product undergoes a crosslinking reaction to obtain a crosslinked resin molded product.
  • the crosslinkable resin molded product undergoes a crosslinking reaction to obtain a crosslinked resin molded product.
  • the laminated body thus obtained is heated to a temperature at which the crosslinking agent is active (c), whereby the crosslinkable resin molded body undergoes a crosslinking reaction, so that the laminated body of the crosslinked resin molded body or the crosslinked resin is obtained.
  • a laminated body in which the molded body and an arbitrary member are integrated is obtained.
  • the laminated body should just be what the at least one part of each layer which comprises it mutually overlapped.
  • a radical generator is preferably used as the cross-linking agent.
  • the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and (c1) organic peroxides are preferable.
  • organic peroxide examples include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, ⁇ , ⁇ ′-bis (T-butylperoxy-m-isopropyl) benzene, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5 Dialkyl peroxides such as di (t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane and 1,1-di (t-hexylperoxy) ) Cyclohexane, 1,1-di (t-butylperoxy)
  • diazo compound examples include 4,4'-bisazidobenzal (4-methyl) cyclohexanone and 2,6-bis (4'-azidobenzal) cyclohexanone.
  • Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.
  • the 1-minute half-life temperature of the radical generator is appropriately selected depending on the crosslinking conditions, but is preferably 100 to 300 ° C, more preferably 120 to 250 ° C. More preferably, it is in the range of 150 to 250 ° C, particularly preferably 160 to 230 ° C.
  • 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, NOF Corporation).
  • the crosslinking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent in the polymerizable composition used in the present invention is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid polymerizable monomer (a) in the polymerizable composition.
  • the range is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.
  • the temperature of the dispersion step using the orifice type shear generating disperser is preferably the polymerizable composition.
  • (C1) 1 minute half-life of organic peroxide, (c1) 1-minute half-life of organic peroxide The temperature is 120 ° C. or lower than the temperature, more preferably not lower than the melting point of the polymerizable composition and (c1) 150 ° C. or lower than the one minute half-life temperature of the organic peroxide. Further, when the temperature at which the viscosity value of the polymerizable composition is twice the viscosity value at 25 ° C.
  • the temperature of the dispersion step is “the temperature of the polymerizable composition at 25 ° C. More preferably, the temperature is a temperature at which the viscosity value is twice that of the viscosity value, and (c1) a temperature that is 100 ° C. lower than the one minute half-life temperature of the organic peroxide.
  • the polymerizable composition contains (c1) an organic peroxide, the start of the crosslinking reaction in the process can be suppressed by performing the dispersion process at the above temperature.
  • the crosslinked body is formed, the viscosity of the polymerizable composition increases, the orifice is clogged, and the dispersion treatment cannot be performed.
  • the melting point of the polymerizable composition is a value measured by raising the temperature at 5 ° C./min using a differential scanning calorimeter (DSC).
  • the “temperature at which the viscosity value of the polymerizable composition is twice the viscosity value at 25 ° C.” can be determined as follows. First, the viscosity value at 25 ° C. of the polymerizable composition is measured. Specifically, the viscosity value at 25 ° C. of the polymerizable composition can be measured using a high shear rate viscometer under the conditions of a cone plate having a diameter of 35 mm, a temperature of 25 ° C., and a rotation speed of 10 rpm.
  • the temperature (liquid temperature) of the polymerizable composition can be adjusted with a thermostat attached to the viscometer. When there is no thermostatic bath, it adjusts by immersing the container which put this polymeric composition in a 25 degreeC water tank for 10 minutes or more. Then, measurement is performed under the above conditions. The measurement time is 1 minute after the start of rotation, and the viscosity value at that time is read. Next, a double viscosity value is calculated from the obtained viscosity value. Similarly, the viscosity of the polymerizable composition adjusted to the temperature at which the dispersion step is performed is measured, and it is confirmed that the value is within twice the viscosity at 25 ° C.
  • the crosslinking aid is a polyfunctional compound that does not participate in the polymerization reaction but has two or more functional groups that can participate in the crosslinking reaction induced by the crosslinking agent and can constitute a part of the crosslinked structure.
  • a crosslinking aid By using a crosslinking aid, it is possible to obtain a crosslinked resin molded body or laminate having a high crosslinking density and more excellent heat resistance.
  • the functional group of the crosslinking aid include a vinylidene group.
  • the vinylidene group is preferably present as an isopropenyl group or a methacryloyl group, and more preferably as a methacryloyl group because of excellent crosslinking reactivity.
  • crosslinking aid examples include compounds having two or more isopropenyl groups such as p-diisopropenylbenzene, m-diisopropenylbenzene, o-diisopropenylbenzene; ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1 , 4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2'-bis (4- Compounds having two or more methacryloyl groups such as methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate; And the like.
  • isopropenyl groups such as p-diisopropeny
  • a compound having two or more methacryloyl groups is preferable, and a compound having three methacryloyl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate is more preferable.
  • the crosslinking aids can be used alone or in combination of two or more.
  • the content thereof is usually 0.1 to 100 parts by mass, preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the (a) liquid polymerizable monomer. .
  • the content of the crosslinking aid is within the above range, a crosslinked resin molded body or laminate having excellent heat resistance and a small dielectric loss tangent can be easily obtained.
  • the polymerizable composition of the present invention preferably contains a chain transfer agent.
  • a chain transfer agent When a chain transfer agent is blended in the polymerizable composition, the followability at the time of heating and melting can be further improved on the surface of the crosslinkable resin molded body obtained by bulk polymerization of the composition. Therefore, in a laminate obtained by laminating a crosslinkable resin molded article obtained by using a polymerizable composition containing a chain transfer agent, heating and melting, and crosslinking, the interlayer adhesion is further improved. This is preferable because the peel strength is further improved.
  • the chain transfer agent may further have one or more crosslinkable carbon-carbon unsaturated bonds. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a vinyl group or vinylidene group.
  • chain transfer agent examples include hydrocarbon compounds having no hetero atom such as 1-hexene, 2-hexene, styrene, vinylcyclohexane, divinylbenzene; allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl Ketone, 2- (diethylamino) ethyl acrylate, 4-vinylaniline, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol diacrylate, allyltrivinylsilane, tetraallylsilane Hydrocarbon compounds having a heteroatom such as; These can be used alone or in combination of two or more. Among these, the hydrocarbon compound which does not have a hetero atom is preferable, and styrene is more preferable from the hydrocarbon
  • the blending amount of the chain transfer agent is preferably 0.01 to 10 mol, more preferably 0.02 to 1 mol, per 1 mol of the liquid polymerizable monomer (a).
  • the blending ratio of the chain transfer agent is too small, the laminate property of the resulting crosslinkable resin molded product tends to be lowered.
  • the peel strength of the obtained laminate tends to be lowered.
  • any flame retardant that can be used industrially can be used without any particular limitation.
  • Polymerization regulator The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate.
  • Examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like. These polymerization regulators can be used alone or in combination of two or more.
  • the polymerization regulator may not be used, but the blending amount of the polymerization regulator in the case of using the polymerization regulator as desired is preferably a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), preferably 1: 0. .05 to 1: 100, more preferably 1: 0.2 to 1:20, and even more preferably 1: 0.5 to 1:10.
  • a molar ratio metal atom in the metathesis polymerization catalyst: polymerization regulator
  • Polymerization reaction retarder The polymerization reaction retarder is used for the purpose of suppressing an increase in viscosity of the polymerizable composition and more uniformly impregnating the fibrous reinforcing material of the composition.
  • Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine And the like.
  • Anti- aging agents include, for example, phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, and sulfur-based anti-aging agents, and by blending these anti-aging agents It is preferable because the heat resistance of the obtained crosslinked resin molded product and laminate can be improved to a high degree without inhibiting the crosslinking reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable.
  • surfactants As other compounding agents , surfactants, solvents, colorants, light stabilizers, foaming agents, and the like can be used.
  • Surfactants include cationic surfactants, anionic surfactants, betaine surfactants, nonionic surfactants, and the like. Surfactant can be used individually by 1 type or in combination of 2 or more types.
  • a small amount of the solvent can be used to dissolve or disperse the polymerization catalyst as required.
  • a solvent is not particularly limited as long as it does not reduce the activity of the polymerization catalyst.
  • chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane; cyclopentane, cyclohexane, methylcyclohexane
  • Alicyclic hydrocarbons such as dimethylcyclohexane, hexahydroindene and cyclooctane
  • aromatic hydrocarbons such as benzene, toluene, xylene, indene and tetrahydronaphthalene
  • nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile
  • diethyl ether Oxygen-containing hydrocarbons such as tetrahydrofuran; and the like.
  • aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons that are excellent in solubility of the polymerization catalyst and are widely used industrially are preferable.
  • a liquid antioxidant, a liquid plasticizer, or a liquid modifier may be used as a solvent as long as it does not decrease the activity of the polymerization catalyst.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • colorant dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.
  • the polymerizable composition includes (a) a liquid polymerizable monomer, (b) inorganic compound particles, and the above-described other additives blended as necessary.
  • the method for producing the polymerizable composition of the present invention uses the above-described orifice-type shear generator and the maximum flow velocity at the orifice in the orifice-type shear generator is 1.8 m / s or more.
  • A) a dispersion step of dispersing (b) inorganic compound particles in the liquid polymerizable monomer;
  • the polymerizable composition obtained by the method for producing a polymerizable composition of the present invention can contain a polymerization catalyst in addition to (a) the liquid polymerizable monomer and (b) the inorganic compound particles.
  • the polymerization catalyst is preferably adjusted by adding it to the polymerizable composition in a state where it is appropriately dissolved or dispersed in a solvent (hereinafter sometimes referred to as “catalyst solution”) and stirring.
  • the filtration step is performed with a filtration filter.
  • the secondary particles are sufficiently crushed into primary particles, so that the solid content mass concentration of the aggregate captured by the filtration filter can be reduced. As a result, the lifetime of the filtration filter can be extended.
  • the addition of the soot catalyst solution is preferably performed immediately before the polymerization described below.
  • the addition of the catalyst solution is preferably performed in an inert gas atmosphere such as nitrogen.
  • the temperature of the polymerizable composition when the catalyst solution is added is usually ⁇ 10 to + 25 ° C., preferably ⁇ 5 to + 20 ° C., more preferably ⁇ 5 to + 15 ° C., and particularly preferably ⁇ 5 to + 10 ° C. . By being within this temperature range, it is possible to avoid an increase in the viscosity of the polymerizable composition by starting a polymerization reaction at the moment of mixing.
  • the temperature of the polymerizable composition from the addition of the catalyst solution to the start of polymerization is usually ⁇ 10 to + 25 ° C., preferably ⁇ 5 to + 20 ° C., more preferably ⁇ 5 to + 15 ° C., particularly preferably. -5 to + 10 ° C. By being within this temperature range, the polymerization reaction can be stably started without starting. In addition, freezing of the polymerizable composition can be prevented.
  • the order in which (b) inorganic compound particles and other additives added as necessary are added to (a) the liquid polymerizable monomer is not particularly limited.
  • the upper limit of the viscosity of the polymerizable composition is preferably 5 Pa ⁇ s, more preferably 3 Pa ⁇ s, still more preferably 2 Pa ⁇ s, and particularly preferably 1 Pa ⁇ s.
  • the lower limit of the viscosity is preferably 0.01 Pa ⁇ s, more preferably 0.1 Pa ⁇ s.
  • the viscosity of the polymerizable composition is a value measured immediately after addition of the polymerization catalyst at 25 ° C. using a high shear rate viscometer and measuring for 1 minute at 10 rpm with a cone plate having a diameter of 35 mm.
  • the viscosity of the soot polymerizable composition tends to increase, for example, when the amount of (b) inorganic compound particles increases, and tends to decrease as the amount of surfactant increases.
  • crosslinkable resin molded body The polymerizable composition obtained by the production method of the present invention is a precursor of a crosslinkable resin molded body, and the crosslinkable resin molded body is obtained by bulk polymerization of the polymerizable composition. It is done. In bulk polymerization, polymerization is carried out substantially without using a solvent.
  • the application in the method (i) can be carried out smoothly, and the injection in the method (ii) can be quickly spread without causing foaming even in a space having a complicated shape.
  • the fibrous reinforcing material can be impregnated quickly and uniformly.
  • a crosslinkable resin molded product such as a film or plate
  • the thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less.
  • the support include films and plates made of resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver, and the like.
  • films and plates made of metal materials are Especially, use of metal foil or a resin film is preferable.
  • the thickness of the metal foil or resin film is usually 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 3 to 75 ⁇ m from the viewpoint of workability and the like.
  • Examples of the method for applying the polymerizable composition on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.
  • the polymerizable composition coated on the support is dried as necessary, and then bulk polymerized.
  • the polymerizable composition is heated for bulk polymerization.
  • a heating method a method of placing and heating the polymerizable composition applied to a support on a heating plate, a method of heating while applying pressure using a press (hot pressing), a method of pressing a heated roller, Examples include a method using a heating furnace.
  • the shape of the crosslinkable resin molded product obtained by the method (ii) can be arbitrarily set by a molding die.
  • a film shape, a column shape, other arbitrary three-dimensional shapes, etc. are mentioned.
  • the shape, material, size, etc. of the mold are not particularly limited.
  • a conventionally known mold for example, a split mold structure, that is, a mold having a core mold and a cavity mold; a mold having a spacer between two plates; and the like can be used.
  • the pressure (injection pressure) for injecting the polymerizable composition into the space (cavity) of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the injection pressure is too low, the filling may be insufficient and the transfer surface formed on the inner surface of the cavity may not be transferred well.If the injection pressure is too high, the mold may have high rigidity. Needed and not economical.
  • the mold clamping pressure is usually in the range of 0.01 to 10 MPa.
  • Bulk polymerization can be performed by heating the polymerizable composition filled in the heel space.
  • Examples of a method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in a mold, and a method for heating the mold in an electric furnace.
  • Examples of the crosslinkable resin molded article obtained by the method (iii) include a prepreg formed by filling a bulk polymer with a gap between fibrous reinforcing materials.
  • fibrous reinforcing material inorganic and / or organic fibers can be used, such as glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, Examples include known liquid crystal fibers such as polyarylate. These can be used alone or in combination of two or more. Examples of the shape of the fibrous reinforcing material include mats, cloths, and nonwoven fabrics. Said prepreg is used for a printed wiring board.
  • the metal concentration in the prepreg is preferably 0.1 mg / m 2 or less.
  • the metal concentration is within the above range, adverse effects such as defective insulation can be effectively prevented when the prepreg is used for a printed wiring board.
  • the above prepreg is suitably used for printed wiring boards.
  • a predetermined amount of the polymerizable composition is poured onto a fibrous reinforcing material cloth, mat or the like, and if necessary, protected thereon. It can be carried out by stacking films and pressing them with a roller or the like from above.
  • a prepreg impregnated with a resin can be obtained by impregnating the fibrous composition with the polymerizable composition and then heating to a predetermined temperature to bulk polymerize the impregnated material.
  • a heating method for example, an impregnated material is placed on a support and heated as in the above method (i), a fibrous reinforcing material is set in advance in a mold, and a polymerizable composition is prepared. After the impregnation, a method of heating as in the method (ii) is used.
  • the heating temperature for bulk polymerization of the polymerizable composition is usually 30 to 250 ° C.
  • the temperature is preferably 50 to 200 ° C.
  • the polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes or less.
  • the bulk polymerization reaction is started by heating the polymerizable composition to a predetermined temperature.
  • the temperature of the polymerizable composition rapidly increases due to the heat of reaction, and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). Further, the bulk polymerization reaction proceeds, but the polymerization reaction gradually stops and the temperature decreases. It is preferable to control the peak temperature so as to be equal to or higher than the glass transition temperature of the polymer constituting the molded product obtained by this polymerization reaction, since the polymerization proceeds completely.
  • the peak temperature can be controlled by the heating temperature.
  • the weight average molecular weight (Mw) of the resin constituting the crosslinkable resin molded product is 10,000 to 100,000 as measured by gel permeation chromatography (polystyrene conversion) with toluene as the eluent. It is 10,000 to 50,000, more preferably 15,000 to 40,000, still more preferably 20,000 to 35,000.
  • a resin molded body containing a resin having a weight average molecular weight in such a range is excellent in the balance between the resin fluidity during heat melting and the strength of the molded body.
  • the polymerizable composition used for the production of the crosslinkable resin molded article is excellent in the dispersibility of the inorganic compound particles (b). Therefore, a bulk polymerization reaction can be carried out uniformly, a residue of unreacted polymerizable monomer is suppressed, and a crosslinkable resin molded article having excellent storage stability can be obtained.
  • ⁇ Maximum flow velocity (maximum linear velocity)> Polymerization when each component used for the preparation of the polymerizable composition is dispersed using each disperser (orifice-type shear-generating disperser, high-speed rotating rotor / stator disperser, planetary triaxial agitator / emulsifier) The maximum flow rate (maximum linear velocity) of the sex composition was measured. The maximum flow velocity in the orifice-type shear generator was calculated from the flow rate of the polymerizable composition passing through the most downstream orifice and the cross-sectional area of the orifice (flow velocity flow rate / cross-sectional area of the orifice).
  • the maximum flow velocity in the high-speed rotating rotor / stator type disperser was calculated from the fact that the rotation speed of the outer edge of the rotor is equal to the flow velocity of the liquid when the liquid contacts the rotor.
  • the maximum flow rate in the planetary triaxial agitator / emulsifier was calculated because it was equal to the rotation speed of the homomixer.
  • the residue was weighed in a beaker, wet-decomposed with sulfuric acid and nitric acid, and then adjusted to a volume of 10 mL. Then, the supernatant was measured by ICP-AES (apparatus: SPS-5100 (SII nanotechnology), calibration curve: internal standard calibration curve method), and the metal concentration derived from the disperser (Co, Cr, Fe, Mn, Ni) Total concentration).
  • ICP-AES Appatus: SPS-5100 (SII nanotechnology), calibration curve: internal standard calibration curve method
  • the metal concentration derived from the disperser Co, Cr, Fe, Mn, Ni
  • Example 1 Preparation of Polymerizable Composition 9-Ethylidenetetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene (ETD) 100 parts and a mixture containing 2,6-bis (1,1-dimethylethyl) -4-methylphenol 0.3 part as an antioxidant Put in a glass container, where 100 parts of silica (volume average particle diameter (primary average particle diameter (D50)): 0.5 ⁇ m, secondary average particle diameter (D50): 62.5 ⁇ m) as inorganic compound particles, crosslinking aid 30 parts of trimethylolpropane trimethacrylate as an agent and 60 parts of aluminum dimethylphosphinate as a flame retardant were mixed uniformly.
  • silica volume average particle diameter (primary average particle diameter (D50)): 0.5 ⁇ m
  • secondary average particle diameter (D50): 62.5 ⁇ m) as inorganic compound particles
  • distribution process was performed 10 times so that the volume average particle diameter (secondary average particle diameter (D50)) of the inorganic compound particle
  • Table 1 shows the time per unit volume per one dispersion step and the number of circulations of the dispersion step as “average processing time” and “average number of processing times ( ⁇ )”.
  • distribution process was 25 degreeC.
  • Preparation of Prepreg The above metathesis catalyst solution was added in total to the polymerizable composition and stirred to obtain a catalyst-containing polymerizable composition.
  • the obtained catalyst-containing polymerizable composition was applied to glass cloth # 2112 at a basis weight of 70 g / m 2 and subjected to a polymerization reaction at a temperature of 120 ° C. and a gauge pressure of 0 kPa for 3.5 minutes to obtain a film thickness of 130 ⁇ m.
  • a prepreg was prepared. About the obtained prepreg, the metal concentration derived from a disperser was measured. The results are shown in Table 1.
  • Example 2 Comparative Examples 1 to 4
  • a monomer liquid was obtained in the same manner as in Example 1 except that the dispersion step shown in Table 1 was used and the dispersion step was performed at the maximum flow rate and average number of treatments ( ⁇ ) shown in Table 1. Adjusted. However, about the comparative example 4, it processed with the capacity
  • Example 1 the dispersion of silica as inorganic compound particles was carried out using an orifice type shear generating disperser under the condition that the maximum flow velocity at the orifice in the orifice type shear generating disperser was 1.8 m / s or more.
  • Example 1 and Example 2 performed, the proportion of inorganic compound particles having a volume average particle diameter of 10 ⁇ m or more is suppressed to a low level, the solid content mass concentration captured by the filter is suppressed to a low level, and the concentration of metal derived from the apparatus The result was low.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Le problème décrit par la présente invention est de pourvoir à un procédé destiné à la production d'une composition polymérisable et permettant, lorsqu'un monomère liquide polymérisable (a) et des particules (b) de composé inorganique sont mélangés, de broyer de manière appropriée les agrégats (particules secondaires) des particules (b) de composé inorganique et de réduire la concentration en métal provenant d'un dispositif. La solution selon l'invention porte sur un procédé de production d'une composition polymérisable qui est un procédé destiné à produire une composition polymérisable comprenant un monomère liquide polymérisable (a) et des particules (b) de composé inorganique. Le procédé comprend une étape de dispersion permettant d'utiliser un dispositif de dispersion de type orifice, générant un cisaillement, pour disperser les particules (b) de composé inorganique dans le monomère liquide polymérisable (a) dans des conditions dans lesquelles le débit maximum au niveau de l'orifice à l'intérieur du dispositif de dispersion de type orifice, générant un cisaillement, est supérieur ou égal à 1,8 m/s.
PCT/JP2014/083254 2013-12-26 2014-12-16 Procédé de production de composition polymérisable Ceased WO2015098620A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015554766A JPWO2015098620A1 (ja) 2013-12-26 2014-12-16 重合性組成物の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-268420 2013-12-26
JP2013268420 2013-12-26

Publications (1)

Publication Number Publication Date
WO2015098620A1 true WO2015098620A1 (fr) 2015-07-02

Family

ID=53478484

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/083254 Ceased WO2015098620A1 (fr) 2013-12-26 2014-12-16 Procédé de production de composition polymérisable

Country Status (3)

Country Link
JP (1) JPWO2015098620A1 (fr)
TW (1) TW201529610A (fr)
WO (1) WO2015098620A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61159409A (ja) * 1984-11-16 1986-07-19 ハ−キユリ−ズ・インコ−ポレ−テツド シクロオレフイン類の遅延ゲル化による重合方法，そのための組成物，および重合生成物
JPH04348122A (ja) * 1991-05-24 1992-12-03 Nippon Zeon Co Ltd 成形品の製造方法および反応成形用金型
JPH07137069A (ja) * 1993-11-12 1995-05-30 Nippon Zeon Co Ltd 反応射出成形方法と金型装置
JPH07268082A (ja) * 1982-01-25 1995-10-17 Teijin Meton Kk 架橋したジシクロペンタジエンポリマーからなる成形物の製造法
JP2006056196A (ja) * 2004-08-23 2006-03-02 Oji Paper Co Ltd 分散液中の無機微粒子の微細分散方法、インク受容層用塗工液及びインクジェット記録体
JP2006249276A (ja) * 2005-03-11 2006-09-21 Tokyo Electric Power Co Inc:The ポリマー系ナノコンポジットの製造方法
WO2007058249A1 (fr) * 2005-11-18 2007-05-24 Rimtec Corporation Moulages en resine de norbornene et leur procede de fabrication
JP2009013227A (ja) * 2007-07-02 2009-01-22 Tokyo Electric Power Co Inc:The 電気絶縁材料用の樹脂組成物及びその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07268082A (ja) * 1982-01-25 1995-10-17 Teijin Meton Kk 架橋したジシクロペンタジエンポリマーからなる成形物の製造法
JPS61159409A (ja) * 1984-11-16 1986-07-19 ハ−キユリ−ズ・インコ−ポレ−テツド シクロオレフイン類の遅延ゲル化による重合方法，そのための組成物，および重合生成物
JPH04348122A (ja) * 1991-05-24 1992-12-03 Nippon Zeon Co Ltd 成形品の製造方法および反応成形用金型
JPH07137069A (ja) * 1993-11-12 1995-05-30 Nippon Zeon Co Ltd 反応射出成形方法と金型装置
JP2006056196A (ja) * 2004-08-23 2006-03-02 Oji Paper Co Ltd 分散液中の無機微粒子の微細分散方法、インク受容層用塗工液及びインクジェット記録体
JP2006249276A (ja) * 2005-03-11 2006-09-21 Tokyo Electric Power Co Inc:The ポリマー系ナノコンポジットの製造方法
WO2007058249A1 (fr) * 2005-11-18 2007-05-24 Rimtec Corporation Moulages en resine de norbornene et leur procede de fabrication
JP2009013227A (ja) * 2007-07-02 2009-01-22 Tokyo Electric Power Co Inc:The 電気絶縁材料用の樹脂組成物及びその製造方法

Also Published As

Publication number Publication date
TW201529610A (zh) 2015-08-01
JPWO2015098620A1 (ja) 2017-03-23

Similar Documents

Publication Publication Date Title
WO2013146660A1 (fr) Composition polymérisable, corps moulé en résine réticulable, corps moulé de résine réticulée et stratifié
JP5625304B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP5644501B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP5994843B2 (ja) 重合性組成物、樹脂成形体、及び樹脂複合成形体
JP2016190988A (ja) 架橋性樹脂成形体、架橋樹脂成形体、及び積層体
JP5434442B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP5617373B2 (ja) プリプレグの製造方法
JP5278305B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP5278306B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP4936016B2 (ja) 多価アルコール含有重合性組成物、プリプレグ、及び積層体
WO2015098620A1 (fr) Procédé de production de composition polymérisable
JP5212635B2 (ja) 高誘電フィラー含有重合性組成物、プリプレグ、積層体、及び誘電体デバイス
JP5187110B2 (ja) 層状複水酸化物含有重合性組成物、プリプレグ、及び積層体
JP2010084043A (ja) 重合性組成物、プリプレグ、及び積層体
JP2013076015A (ja) 重合性組成物、樹脂成形体、および積層体
EP2653501B1 (fr) Corps moulés de résine pouvant être réticulée, et stratifié
WO2016035716A1 (fr) Procédé d'évaluation de liquide catalyseur de polymérisation par métathèse, et procédé de production de polymère de cyclo-oléfine
JP5742218B2 (ja) 重合性組成物、樹脂成形体、及び積層体
JP2010168487A (ja) 重合性組成物、架橋体および架橋樹脂複合体
WO2016031766A1 (fr) Corps moulé en résine réticulable, corps moulé en résine réticulé, et stratifié
JP2012097166A (ja) 重合性組成物、樹脂成形体、及び積層体
JP2016190987A (ja) 架橋性樹脂成形体、架橋樹脂成形体、及び積層体
WO2016031765A1 (fr) Corps moulé en résine réticulable, corps moulé en résine réticulée et stratifié
JP2010106217A (ja) アルミナ一水和物含有重合性組成物、プリプレグ、及び積層体
JP2010168488A (ja) 重合性組成物、架橋体および架橋樹脂複合体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14875080

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015554766

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14875080

Country of ref document: EP

Kind code of ref document: A1