CN1761694A - Process for producing cycloolefin resin film and process for producing cycloolefin polymer sheet or film - Google Patents

Abstract

A process (1) for producing a cycloolefin resin film, characterized by conducting without delay the step (I) of mixing a cycloolefin monomer with a metathesis polymerization catalyst to prepare a polymerizable composition (A) and the step (II) of applying or infiltrating the polymerizable composition (A) to a substrate and by conducting the step (III) of polymerizing the polymerizable composition (A) by bulk polymerization; and a process (2) for producing a cycloolefin polymer sheet or film having a thickness of 1 mm or smaller which comprises polymerizing a liquid reaction mixture comprising a ruthenium complex catalyst having a heteroatom-containing carbene compound as a ligand and a cycloolefin monomer by ring-opening metathesis bulk polymerization, characterized by including a step in which the reaction mixture is heated to 100 DEG C or higher at a rate of 20 DEG C/min or higher to complete polymerization of the cycloolefin monomer. Thus, a cycloolefin resin film having excellent adhesion to other materials and a cycloolefin polymer sheet or film having a thickness of 1 mm or smaller can be efficiently produced.

Description

The method and the method for preparing cycloolefin polymer sheet or film that prepare cycloolefin resin film

Technical field

The present invention relates to prepare the method for cycloolefin resin film, comprise by hybrid ring alkene monomer and metathesis polymerization catalyzer (metathesis polymerization catalyst) preparation polymerisable compound, apply or dipping supporting mass and with this polymerisable compound by continuous bulk polymerization polymeric rings alkene monomer at once; And to relate to preparation thickness be 1 millimeter or the thinner polymer sheet or the method for film, comprises that polymerization contains the reactive solution of cyclenes monomer and ruthenium complex catalyst by the ring-opening metathesis mass polymerization.

Background technology

Because the cyclenes monomer, for example the polymkeric substance of norbornylene and Dicyclopentadiene (DCPD) has the mechanical property of low water absorption, low-dielectric, excellence etc., therefore is expected to utilize these advantages as the film that is applied in electronics or the electric field.

As the method for the film that obtains the cyclenes monomer-polymer, have in a large number about report from the film forming method of non-crosslinked cycloolefine polymer shape, described polymkeric substance can be dissolved in solvent and can pass through hot melt molding.

For example, the flat H6 of Japanese Patent Application Laid-Open (1994)-298956 has disclosed a kind of linear loop alkene polymer of thermoplastic shaping excellence and method of this polymkeric substance formed by stretching of preparing.Yet because this method requires the step at this polymkeric substance back draft linear polymer of preparation, from production efficiency, this method must not have advantage.

The flat H5 of Japanese Patent Application Laid-Open (1993)-70655, H5 (1993)-148413, H10 (1998)-101907 etc. have disclosed the method for dissolving linear loop alkene polymer and this polymers soln of curtain coating.The advantage of this method is to use existing membrane equipment and technology, but owing to has used a large amount of solvents need remove the step of desolvating after using the solution of linear polymer.In addition, when as electrically insulating material, understand because residual solvent have problems by the film of this method manufacturing, for example Copper Foil is peeled off, is produced bubble etc. because of generating gas.

The flat 2001-253934 of Japanese Patent Application Laid-Open has disclosed that polymerization comprises the liquid mixture of metathesis polymerization catalyzer and polymerizable cyclenes by metathesis polymerization on carrier, obtains the method for cross-linked resin film.Yet because the gained resin molding is the cross-linked resin film, fashionable when this film and other material layer, with this other material, for example the bond strength of tinsel, base material etc. is not enough sometimes.

Flat 2000-327756 of Japanese Patent Application Laid-Open and 2001-253934 have disclosed the method for preparing the norbornene resin film, comprise using ruthenium or osmium complex as the metathesis polymerization catalyzer ring-opening metathesis mass polymerization norbornene monomer.In the method, under specified temperature, contain the reactive solution of norbornene monomer and metathesis polymerization catalyzer by ring-opening metathesis mass polymerization polymerization after, this mixture is further heated, to finish polymerization and curing.Yet there is the bad problem of productivity in the method for describing in these documents because of needs control to heating rate below a certain fixed rate.

WO01/72870 has disclosed the method for the moulding product that obtains colourless norbornene resin, is included in ruthenium catalyst and exists mass polymerization down to contain the norbornene monomer of polymer modifiers.This patent specification points out that the conventional bulk polymerization in the presence of polymer modifiers produces phase separation structure in polymkeric substance, and this causes moulding product to bleach, and points out that this problem is caused by medium heating rate in the polymerization process.Heat energy is enough to remain on 20 ℃/second or higher with maximum heating speed to the ruthenium catalyst that this patent specification has been described some type because of sending out of producing in the polymerization process answered, and has prevented that thus moulding product from bleaching.

Summary of the invention

Consider that the above-mentioned situation of prior art finished the present invention.First purpose of the present invention provides with the method for high efficiency preparation with the cycloolefin resin film of adhesion excellence.

It is 1 millimeter or the polymer sheet of thinner cycloolefine polymer or the method for film that second purpose of the present invention provides effective preparation thickness, comprises by the mass polymerization polymerization and contains specific ruthenium complex catalyst and the monomeric reactive solution of cyclenes.

The present inventor has carried out further investigation to obtain above-mentioned purpose, and find that the cycloolefin resin film with excellent adhesiveness can effectively obtain by the preparation polymerisable compound, described preparation comprises hybrid ring alkene monomer and metathesis polymerization catalyzer, (at once) is coated to polymerisable compound on the supporting mass or with polymerisable compound and floods supporting mass immediately, and the heating supporting mass to specified temperature with by mass polymerization polymerization polymerisable compound.The inventor effectively prepares the sheet of cycloolefine polymer to containing the monomeric reactive solution of cyclenes by the ring-opening metathesis mass polymerization or the method for film has been carried out further further investigation.The result, the inventor finds to obtain sheet or the film that thickness is 1 millimeter or thinner cycloolefine polymer for the ring-opening metathesis mass polymerization by above-mentioned reactive solution, the method of using ruthenium complex catalyst that temperature of reaction is elevated to specialized range fast can be guaranteed high polymerisation conversion and effective required cycloolefin polymer sheet or the film of preparation, and wherein said catalyzer has and contains heteroatomic Cabbeen (carbene) compound as part.

According to the present invention, method (1)-(9) that prepare cycloolefin resin film below providing.

(1) prepare the method for cycloolefin resin film, may further comprise the steps: (I) hybrid ring alkene monomer and metathesis polymerization catalyzer are with the step of preparation polymerisable compound (A); (II) after step (I), use polymerisable compound (A) to apply or flood the step of supporting mass immediately; (III) step by mass polymerization polymerization polymerisable compound (A).

(2) according to the method for (1), wherein in the working life of polymerisable compound (A) (potlife), carry out step (II) in step (I) back.

(3) according to the method for (1) or (2), wherein step (I) is the step for preparing polymerisable compound (A) by hybrid ring alkene monomer, metathesis polymerization catalyzer and chain-transfer agent.

(4) each method in the basis (1) to (3), wherein step (I) is the step for preparing polymerisable compound (A) by hybrid ring alkene monomer, metathesis polymerization catalyzer and linking agent.

(5) each method in the basis (1) to (4), wherein step (III) is following steps: use warming mill, hot-plate or process furnace to apply or the supporting mass that floods be heated to specified temperature with polymerisable compound (A), with by mass polymerization polymerization polymerisable compound (A).

(6) each method in the basis (1) to (5), wherein norbornene monomer is as the cyclenes monomer.

(7) each method in the basis (1) to (6), wherein pass through with 20 ℃/min or higher heating rate, polymerisable compound (A) is heated to 100 ℃ of specified temperature or higher, use have contain heteroatomic carbene compound as the ruthenium complex of part as the metathesis polymerization catalyzer, carry out mass polymerization.

(8) each method in the basis (1) to (7), wherein tinsel is as supporting mass.

(9) each method in the basis (1) to (7), wherein filamentary material is as supporting mass.

According to second invention, provide the following method for preparing cycloolefin polymer sheet or film (10)-(14).

(10) preparation thickness is 1 millimeter or the thinner cycloolefin polymer sheet or the method for film, comprise by ring-opening metathesis mass polymerization polymerisation reactivity solution, this solution contains to have and contains ruthenium complex catalyst and the cyclenes monomer of heteroatomic carbene compound as part, wherein by with 20 ℃/min or higher heating rate, reactive solution is heated to 100 ℃ or higher and finish the monomeric polymerization of cyclenes.

(11) according to the method for (10), wherein reactive solution also comprises chain-transfer agent.

(12) according to the method for (10) or (11), wherein apply with reactive solution or the dipping supporting mass, this reactive solution carries out polymerization by the open loop mass polymerization.

(13) according to the method for (12), wherein supporting mass is made by electro-conductive material.

(14) according to the method for (12), wherein supporting mass is made by filamentary material.

Description of drawings

Fig. 1 is the sketch map that is presented at the apparatus for continous formation that uses among the embodiment 3, is used to form the laminated film of cycloolefin resin film and support membrane.

Fig. 2 is the sketch map that is presented at the apparatus for continous formation that uses among the embodiment 4, is used for cyclenes resin formation tinsel.

Fig. 3 is the sketch map that shows the apparatus for continous formation that uses among the embodiment 5, is used to form two-sided copper-clad layered product (double-sided copper-clad laminate).

Preferred forms

Describe the method that the present invention prepares the method for cycloolefin resin film and prepares cycloolefin polymer sheet or film now in detail.

1) prepares the method for cycloolefin resin film

The method for preparing cycloolefin resin film may further comprise the steps: step (I) hybrid ring alkene monomer and metathesis polymerization catalyzer, with preparation polymerisable compound (A); Step (II) uses polymerisable compound (A) to apply after step (I) or the dipping supporting mass immediately; And step (III) is by mass polymerization polymerization polymerisable compound (A).

Term among the present invention " immediately " refers to " carry out step (II) immediately behind the preparation polymerisable compound in step (I)." prepare in the preferred implementation of method of cycloolefin resin film in the present invention, also carry out step (III) at once continuously.

Each step is described now.

Step (I)

Step (I) is the step by hybrid ring alkene monomer and metathesis polymerization Preparation of Catalyst polymerisable compound (A).

Cyclenes monomer as using among the present invention can provide monocycle alkene monomer, norbornene monomer etc.These cyclenes monomers can use separately or being used in combination with two or more.When using two or more cyclenes monomers, might control the second-order transition temperature and the melt temperature of gained resin by regulating blending ratio.These cyclenes monomers can be substituted with alkyl, for example alkyl, alkenyl, alkylidene group or aryl or polar group.

Wherein, preferred especially in the present invention norborneol vinyl monomer (being called " norbornene monomer " in the specification sheets of the present invention).The amount of norbornene monomer is preferably the 60wt% or higher, the 80wt% or higher more preferably of cyclenes monomer total amount.Norbornene monomer can have two keys of the two keys that are different from the norbornylene ring.

As cycloolefin, can provide the cyclic monoolefins or the cyclic diene hydrocarbon that have 4-20 carbon atom and preferred 4-10 carbon atom usually.The specific examples of cyclic monoolefins comprises cyclobutene, cyclopentenes, methyl cyclopentene, tetrahydrobenzene, tetrahydrotoluene, suberene and cyclooctene.The specific examples of cyclic diene hydrocarbon comprises cyclohexadiene, methyl cyclohexadiene, cyclooctadiene, methyl cyclooctadiene and benzyl ring octadiene.

As norbornene monomer, can provide replacement or unsubstituted, dicyclo, three rings or encircle norbornylene more.Specific examples as norbornene monomer, can provide the dicyclo norbornylene that can have functional group, norbornylene for example, norbornadiene, the methyl norbornylene, the dimethyl norbornylene, the ethyl norbornylene, the norbornylene that chlorine replaces, ethylidene norbornene, the chloromethyl norbornylene, the trimethyl silyl norbornylene, the phenyl norbornylene, the cyano group norbornylene, the dicyano norbornylene, the methoxycarbonyl norbornylene, the pyridyl norbornylene, nadic anhydride and 3, methylene radical 1 in the 6-, 2,3,6-tetrahydrophthalic acid imide; Three ring norbornylenes, for example Dicyclopentadiene (DCPD) or dihydro Dicyclopentadiene (DCPD), and the derivative that replaced by following group of these compounds: alkyl, alkenyl, alkylidene group, aryl, hydroxyl, anhydride group, carboxyl, alkoxy carbonyl etc.; Fourth Ring norbornylene, for example dimethano-hexahydro naphthalene (Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4, the 9-diene), dimethano-octahydro naphthalene (Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4-alkene) and 1,4-first bridge-1,4,4a, 9a-tetrahydrochysene-9H-fluorenes (Fourth Ring [9.2.1.0 ^2,10.0 ^3,8] 14-3,5,7, the 12-tetraene) and the derivative that replaced by following group of these compounds: alkyl, alkenyl, alkylidene group, aryl, hydroxyl, anhydride group, carboxyl, alkoxy carbonyl etc.; Five rings norbornylene, for example three cyclopentadiene; Six ring norbornylene, for example six cyclopentadiene; The compound that contains the norbornylene ring, for example derivative that replaced by alkyl or aryl etc. of the compound that connects by alkyl or ester group of two norbornylenes, two norbornylene rings and these compounds.

In the top monomer, when epoxy compounds was used as linking agent, because of effectively preparing cross-linked resin, the norbornene monomer that preferably has carboxyl or anhydride group was as norbornene monomer.The content of norbornene monomer in cyclenes monomer total amount with carboxyl or anhydride group is preferably 1mol% or higher, and 5mol% or higher more preferably.

The metathesis polymerization catalyzer that uses for the present invention is not particularly limited, as long as this catalyzer can be by transposition ring-opening polymerization polymeric rings alkene monomer.For example, can use the ring-opening metathesis catalysts of in Olefin Metathesis andMetathesis Polymerization (K.J.Ivin and J.C.Mol, Academic Press, San Diego, 1997), describing.

As operable metathesis polymerization catalyzer, can provide complex compound, it is by a plurality of ions, atom, polyatomic ion and/or the compound formation that are connected to as the transition metal atoms of central atom.As transition metal atoms, can use the atom in V, VI and the VIII family (the long period form of periodictable, down together).Although the atom that belongs to each family is not specifically limited, example comprises tantalum as V group atom, is the molybdenum and the tungsten of VI family atom, and is the ruthenium and the osmium of VIII family atom.

Wherein, the ruthenium of the preferred I of VII family metal and osmium are as the complex compound of metathesis polymerization catalyzer, and preferred especially ruthenium-carbene complex.Ruthenium-carbene complex demonstrates the high productivity of resin molding, and this is because it has excellent catalytic activity during mass polymerization.In addition, because this catalyzer is relatively stable, and is not easy to inactivation in aerial oxygen or the steam, use this catalyzer under atmospheric condition, to prepare thermoplastic resin.

Ruthenium-carbene complex is the compound by following formula (1) or (2) expression.

R wherein ¹And R ²Represent hydrogen atom, halogen atom independently or have the alkyl of 1-20 carbon atom, this alkyl can contain halogen atom, Sauerstoffatom, nitrogen-atoms, sulphur atom, phosphorus atom or Siliciumatom, X ¹And X ²Represent anion ligand independently, and L ¹And L ²Expression contains heteroatomic carbene compound or the neutral electron compound (neutral electron-donor compound) of giving independently.R ¹, R ², X ¹, X ², L ¹And L ²Group can any optional being connected form multiple tooth chelating ligand together.

Anion ligand X ¹And X ²It is the part that has negative charge during from the center metal separation.The example of this part comprises halogen atom, for example fluorine atom, chlorine atom, bromine atoms or iodine atom; Diketone acid esters group (diketonate group), cyclopentadienyl group, alkoxyl group, aryloxy or the carboxyl etc. that replace.Wherein, preferred halogen atom, more preferably chlorine atom.

Heteroatomic specific examples comprises N, O, P, S, As and Se.Wherein, preferred N, O, P, S etc., preferred especially N, this is because can obtain stable carbene compound.

What preferably have the both sides that are connected to the Cabbeen carbon atom heteroatomicly contains heteroatomic carbene compound, and preferred carbene compound has and comprises the Cabbeen carbon atom and at the heteroatomic heterocycle of Cabbeen carbon atom both sides.The heteroatoms of wishing contiguous Cabbeen carbon atom has big substituted radical.

As the described example that contains heteroatomic carbene compound, can provide compound by following formula (3) and (4) expression:

?

R wherein ³To R ⁶Represent hydrogen atom, halogen atom independently or have the alkyl of 1-20 carbon atom, this alkyl can contain halogen atom, Sauerstoffatom, nitrogen-atoms, sulphur atom, phosphorus atom or Siliciumatom.R ³To R ⁶Can be joined together to form ring with any optional combination.

The specific examples of the compound of formula (3) or (4) comprises 1,3-two basic imidazolidine-2-subunits, 1,3-two (1-adamantyl) imidazolidine-2-subunit, 1-cyclohexyl-3-base imidazolidine-2-subunit, 1,3-two basic octahydro benzimidazolyl-2 radicals-subunits, 1,3-di-isopropyl-4-tetrahydroglyoxaline-2-subunit, 1,3-two (1-styroyl)-4-tetrahydroglyoxaline-2-subunit and 1,3-two bases-2,3-dihydrobenzo imidazoles-2-subunit.

Except the compound of following formula (3) or (4) expression, can use other to contain heteroatomic carbene compound, for example 1,3,4-triphenyl-2,3,4,5-tetrahydrochysene-1H-1,2,4-triazole-5-subunit, 1,3-dicyclohexyl hexahydropyrimidine-2-subunit, N, N, N ', N '-tetra isopropyl carbonamidine subunit (N, N, N ', N '-tetraisopropylformamidinilidene), 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole-5-subunit and 3-(2, the 6-diisopropyl phenyl)-2,3-thiazoline-2-subunit.

In following formula (1) and (2), anion ligand X ¹And X ²It is the part that after the metal separation of center, has negative charge.The example of this part comprises halogen atom, for example fluorine atom, chlorine atom, bromine atoms and iodine atom; Cyclopentadienyl group, alkoxyl group, aryloxy and the carboxyl of diketone acid esters group, replacement.Wherein, preferred halogen atom, more preferably chlorine atom.

Neutral can be any part that is designated as electric neutrality (neutralcharge) after the metal separation of center to electron compound.Specific examples comprises carbonyl, amine, pyridine, ether, nitrile, ester, phosphine, thioether, aromatic substance, alkene, isocyanides and thiocyanate-(ester).Wherein preferred phosphine, ester and pyridine, more preferably trialkyl phosphine.

The example of the ruthenium complex of formula (1) comprises and wherein contains heteroatomic carbene compound and the neutral ruthenium complex compound that is connected to electron compound, for example benzylidene (1,3-two basic imidazolidine-2-subunits) (tricyclohexyl phosphine) ruthenous chloride, (1,3-two basic imidazolidine-2-subunits) (3-methyl-2-butene-1-subunit) (three cyclopentyl phosphines) ruthenous chloride, benzylidene (1,3-two bases-octahydro benzimidazolyl-2 radicals-subunit) (tricyclohexyl phosphine) ruthenous chloride, benzylidene [1,3-two (1-styroyl)-4-tetrahydroglyoxaline-2-subunit] (tricyclohexyl phosphine) ruthenous chloride, benzylidene (1,3-two bases-2,3-dihydrobenzo imidazoles-2-subunit) (tricyclohexyl phosphine) ruthenous chloride, benzylidene (tricyclohexyl phosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydrochysene-1H-1,2,4-triazole-5-subunit) ruthenous chloride, (1,3-di-isopropyl hexahydropyrimidine-2-subunit) (oxyethyl group methylene radical) (tricyclohexyl phosphine) ruthenous chloride, benzylidene (1,3-two basic imidazolidine-2-subunits) pyridine ruthenous chloride, (1,3-methylimidazole alkane-2-subunit) (2-phenyl ethylidene) (tricyclohexyl phosphine) ruthenous chloride and (1,3-two bases-4-tetrahydroglyoxaline-2-subunit) (2-phenyl ethylidene) (tricyclohexyl phosphine) ruthenous chloride; The wherein ruthenium compounds that connect to electron compound of two neutrality, for example benzylidene two (tricyclohexyl phosphine) ruthenous chloride and (3-methyl-2-butene-1-subunit) three (three cyclopentyl phosphines) ruthenous chloride; And wherein two contain the ruthenium complex compounds that heteroatomic carbene compound connects, for example two (1, the 3-dicyclohexyl imidazolidine-2-subunit) ruthenous chlorides of benzylidene and two (1, the 3-di-isopropyl-4-tetrahydroglyoxaline-2-subunit) ruthenous chlorides of benzylidene.

The example of the ruthenium complex of formula (2) comprises (1,3-two basic imidazolidine-2-subunits) (phenyl vinylidene) (tricyclohexyl phosphine) ruthenous chloride, (tertiary butyl vinylidene) (1,3-di-isopropyl-4-tetrahydroglyoxaline-2-subunit) (three cyclopentyl phosphines) ruthenous chloride and two (1,3-dicyclohexyl-4-tetrahydroglyoxaline-2-subunit) phenyl vinylidene chloride ruthenium.

These ruthenium complex catalysts can pass through for example Org.Lett., and 1999, Vol.1, p.953 with Tetrahedron Lett., 1999, Vol.40, the p.2247 middle method preparation of describing.

Mol ratio with atoms metal in the catalyzer and cyclenes is 1: 2,000 to 1: 2, and 000,000, preferred 1: 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1: 500,000 used the metathesis polymerization catalyzer.

If desired, the metathesis polymerization catalyzer can be dissolved in a small amount of inert solvent and use.The example of this solvent comprises acyclic aliphatic hydrocarbon, for example Skellysolve A, normal hexane and normal heptane, and alicyclic hydrocarbon, for example pentamethylene, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, trimethyl-cyclohexane, ethylcyclohexane, naphthane, norbornane, tristane, six hydrogen indenes and cyclooctane; Aromatic hydrocarbon, for example benzene, toluene and dimethylbenzene; Nitrogenous hydrocarbon, for example Nitromethane 99Min., oil of mirbane and acetonitrile; And ether, for example Anaesthetie Ether and tetrahydrofuran (THF).Wherein, the preferred use used industrial solvent, for example aromatic hydrocarbon, aliphatic hydrocarbon and alicyclic hydrocarbon always.In addition, under the degree that does not reduce the metathesis polymerization activity of such catalysts, can use liquid oxidation inhibitor, softening agent or elastomerics as solvent.

In the present invention, activator (promotor) can use with the metathesis polymerization catalyst combination, the active or increase polymerisation conversion with controlled polymerization.

As activator, can provide alkylate, halogenide, alkoxy compound, aryloxy compound of aluminium, scandium, tin, titanium or zirconium etc.

The specific examples of activator comprises tri-alkoxy aluminium, triple phenoxyl aluminium, dialkoxy aluminum alkyls, alkoxyl group aluminum dialkyl, trialkylaluminium, dialkoxy aluminum chloride, alkoxyalkyl aluminum chloride, dialkylaluminum chloride, tri-alkoxy scandium, four titan-alkoxides, four alkoxyl group tin and four zirconium alkoxides.

Mol ratio with atoms metal and activator in the metathesis polymerization catalyzer is 1: 0.05 to 1: 100, is preferably 1: 0.2 to 1: 20 and more preferably 1: 0.5 to 1: 10 and use activator.

When the complex compound of the transition metal atoms that uses V family or VI family during, need metathesis polymerization catalyzer and activator all to be dissolved in the monomer as the metathesis polymerization catalyzer.Yet, do not damaging substantially under the degree of products obtained therefrom character, can in a spot of solvent, dissolve or suspension metathesis polymerization catalyzer and activator.

Can pass through hybrid ring alkene monomer and metathesis polymerization Preparation of Catalyst polymerisable compound (A).In order to prepare thermoplasticity cyclenes resin of the present invention, preferably prepare polymerisable compound (A) by combination chain transfer agent and cyclenes monomer and metathesis polymerization catalyzer.

As chain-transfer agent, can use for example to have the alkene that can contain substituent chain structure.The specific examples of chain-transfer agent comprises aliphatic olefin, for example 1-hexene and 2-hexene; Atomatic olefins, for example vinylbenzene, Vinylstyrene and stilbene; Alicyclic olefin, for example vinyl cyclohexane; Vinyl ether, for example ethyl vinyl ether; Vinyl ketone, methyl vinyl ketone, 1 for example, 5-hexadiene-3-ketone, 2-methyl isophthalic acid, 5-hexadiene-3-ketone; By formula CH ₂The compound that=CH-Q represents, wherein Q is the group with at least one group, described at least one group is selected from methacryloyl, acryl, vinyl silyl, epoxy group(ing) and amino.These chain-transfer agents can use separately or two or more are used in combination.

Wherein, preferred formula CH ₂The compound that=CH-Q represents because group Q has introduced the terminal of polymkeric substance and helped back crosslinked (post-crosslinking) of polymkeric substance, increases cross-linking density thus.

As formula CH ₂The specific examples of the compound that=CH-Q represents, can provide wherein that Q is the compound with group of methacryloyl, for example methacrylic acid vinyl ester, allyl methacrylate(AMA), methacrylic acid 3-butene-1-ester, methacrylic acid 3-butene-2-ester and methacrylic acid styrene esters; Wherein Q is the compound with group of acryl, for example allyl acrylate, vinylformic acid 3-butene-1-ester, vinylformic acid 3-butene-2-ester, vinylformic acid 1-methyl-3-butene-2-ester, vinylformic acid styrene esters and ethylene glycol diacrylate; Wherein Q is the compound with group of vinyl silyl, for example allyl group trivinyl silane, allyl methyl divinyl silane and allyl dimethyl base vinyl silanes; Wherein Q is the compound with group of epoxy group(ing), for example glycidyl acrylate and allyl glycidyl ether; Wherein Q is the compound with amino group, for example allyl amine, 2-(diethylamino) ethanol vinyl ether, vinylformic acid 2-(divinyl amino) ethyl ester, 4-vinyl aniline etc.

The amount that chain-transfer agent adds is generally the 0.01-10 weight part and is preferably the 0.1-5 weight part based on the cyclenes monomer of 100 weight parts.But the amount of the chain-transfer agent in this scope has been guaranteed the high polymerisation conversion of post polymerization thermoplastic resin and effectively preparation.

Except cyclenes monomer and metathesis polymerization catalyzer, in preparation polymerisable compound (A), also can preferably add and mixed cross-linker.

Linking agent is the compound that can prepare cross-linked resin by the crosslinking reaction with the functional group of thermoplasticity cyclenes resin.As the example of functional group, can provide carbon-to-carbon double bond, hydroxy-acid group, anhydride group, hydroxyl, amino, reactive halogen atom, epoxy group(ing) etc.

As the example of operable linking agent, can provide free-radical generating agent, epoxy compounds, contain compound, the carboxylic compound of isocyanate groups, the compound that contains anhydride group, the compound that contains amino, Lewis acid etc.These linking agents can use separately or two or more are used in combination.Wherein preferred free-radical generating agent or epoxy compounds.

As the example of free-radical generating agent, can provide organo-peroxide and azo-compound.Organo-peroxide is not particularly limited.For example can provide ketone peroxide, for example methyl-ethyl-ketone peroxide, methyl-isobutyl ketone peroxide, pimelinketone superoxide, methyl cyclohexanone peroxide and 3,3,5-trimethyl hexanone peroxide; Acyl peroxide, for example acetyl peroxide, propionyl superoxide, isobutyl peroxide, sim peroxides, 3,5,5-trimethyl acetyl base decanoyl superoxide, lauroyl superoxide, benzoyl peroxide base, peroxidation 4-methyl benzoyl, peroxidation 4-chlorobenzoyl, peroxidation 2,4 dichloro benzene formyl and acetyl cyclohexane alkylsulfonyl (acetylcylohexanesulfonyl) superoxide; Hydroperoxide, for example t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, to methane hydroperoxide, 2,5-dimethylhexane-2,5-dihydro-peroxidase and 1,1,3,3-tetramethyl butyl hydroperoxide; Dialkyl peroxide, for example ditertiary butyl peroxide, tertiary butyl cumyl peroxide and dicumyl peroxide; Peroxy ketal, for example 1, two (t-butyl peroxy di-isopropyl) benzene, 1 of 1-, two (t-butyl peroxy)-3,5 of 1-, 5-trimethyl-cyclohexane and normal-butyl-4,4 '-two (t-butyl peroxy) butane; Alkyl super-acid ester, for example Peracetic Acid tertiary butyl ester, peroxide isopropylformic acid tertiary butyl ester, Peroxycaprylic acid tertiary butyl ester, peroxide PIVALIC ACID CRUDE (25) tertiary butyl ester, peroxide neodecanoic acid tertiary butyl ester, peroxide-3,5,5-tri-methyl hexanoic acid tertiary butyl ester, t-butyl-oxybenzoate, two power butyl peroxy phthalic esters, t-butyl peroxy isophthalic acid ester, t-butyl peroxy laurate, 2,5-dimethyl-2,5-dibenzoyl peroxide hexane; Peroxy carbonates, for example two-2-ethylhexyl peroxide, two carbonic ethers, diisopropyl peroxydicarbonate, di-secondary butyl peroxy carbonic ether, two-n-propyl peroxide, two carbonic ethers, dimethoxy sec.-propyl peroxide two carbonic ethers, two-3-methoxyl group butyl peroxy, two carbonic ethers, two-2-ethoxyethyl group peroxide, two carbonic ethers and two (4-tert-butylcyclohexyl) peroxide two carbonic ethers; Water-soluble peroxide, for example succinic acid peroxide; Alkyl silyl superoxide is as tertiary butyl trimethyl silyl superoxide etc.The example of azo-compound comprises 4,4 '-diazido benzylidene (4-methyl) pimelinketone, 4,4 '-two nitrine phenyl styryl ketone, 2, two (the 4 '-azido-benzylidene) pimelinketone, 2 of 6-, two (4 '-folded helium the benzylidene)-4-methylcyclohexanones, 4 of 6-, 4 '-diazido sulfobenzide, 4,4 '-diazido ditan, 2,2 '-diazido stilbene etc.Wherein, preferred dialkyl peroxide is because it hinders little to the transposition polyreaction.

As epoxy compounds, can be given in the compound that has two or more epoxy group(ing) in the molecule, for example linear phenolic aldehyde epoxy compounds, linear phenolic aldehyde (cresol novolak) epoxy compounds of cresols and cresols epoxy compounds; Glycidyl ether type epoxy compounds, for example bisphenol-A epoxy compound, Bisphenol F epoxy compounds, brominated bisphenol A epoxy compounds, brominated bisphenol F epoxy compounds and Hydrogenated Bisphenol A epoxy compounds; Multivalence epoxy compounds, for example alicyclic epoxide compound, glycidyl ester epoxy compounds, glycidyl group amine epoxy compounds and isocyanic ester epoxy compounds etc.

As the compound that contains isocyanate groups, can be given in the compound that contains two or more isocyanate groups in the molecule, for example to phenylene vulcabond.

As carboxylic compound, can be given in the compound that contains two or more carboxyls in the molecule, for example fumaric acid.

As the examples for compounds that contains anhydride group, can provide Tetra hydro Phthalic anhydride, pyromellitic anhydride etc.

As containing amino compound, can provide the compound that has two or more amino in the molecule, for example aliphatic diamine, aliphatic polyamines, aromatic diamine etc.

As Lewis acid, can provide silicon tetrachloride, hydrochloric acid, sulfuric acid, iron(ic) chloride, aluminum chloride, tin chloride, titanium tetrachloride etc.

In the present invention, can use different suitable linking agents according to the crosslinked position of thermoplasticity cyclenes resin.For example, can use free-radical generating agent when dividing the period of the day from 11 p.m. to 1 a.m at the carbon-to-carbon double bond cross-linked polymer.When having the thermoplastic resin of carboxyl or anhydride group, can use epoxy compounds when crosslinked.When having the thermoplastic resin of hydroxyl, can use compound when crosslinked with isocyanate groups.When having the thermoplastic resin of epoxy group(ing), can use compound when crosslinked with carboxyl or anhydride group.In addition, for cationic crosslinked molecule, also can use Lewis acid as linking agent.

Amount for linking agent is not particularly limited.This amount can suitably be determined according to the kind of used linking agent.When using free-radical generating agent as linking agent, based on the cyclenes monomer of 100 weight parts, the consumption of linking agent is generally the 0.1-10 weight part, and is preferably the 0.5-5 weight part.When epoxy compounds was used as linking agent, based on the cyclenes monomer of 100 weight parts, the consumption of linking agent was generally the 1-100 weight part, and is preferably the 5-50 weight part.

In the present invention, can be used in combination crosslinking activity auxiliary agent (crosslinking co-agent) to improve cross-linking effect.As the crosslinking activity auxiliary agent, can provide known crosslinking activity auxiliary agent, for example two oxime compounds, for example paraquinonedioxime; Methacrylate compound, for example methacrylic acid Lauryl Ester; Have two or more allylic compounds, for example fumaric acid diallyl ester, diallyl phthalate and triallyl cyanurate (triallyl cyanulate); Imide compound, for example maleimide etc.

Although be not particularly limited, the consumption of crosslinking activity auxiliary agent is generally the 0-100 weight part based on the cyclenes monomer of 100 weight parts, and is preferably the 0-50 weight part.

When free-radical generating agent is used as linking agent of the present invention, preferably add the stopper of radical crosslinking to polymerisable compound (A).The stopper of radical crosslinking is a kind of compound, and it has the free radical capture function usually and demonstrates the effect of the radical crosslinking reaction that delay causes by free-radical generating agent.Can improve the flowability of thermoplastic resin when laminated this resin and the package stability of thermoplastic resin by the stopper that adds radical crosslinking to polymerisable compound (A).

Example as the stopper of radical crosslinking can provide alkoxyl group phenol, for example 4-methoxyphenol, 4-thanatol, 4-Methoxy-2-t-Butylphenol, 4-methoxyl group-3-tert.-butyl phenol and 4-methoxyl group-2,6 di t butyl phenol; Hydroquinones, for example quinhydrones, 2-toluhydroquinone, 2,5-dimethyl hydroquinone, 2-tertiary butylated hydroquinone, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2, two (1, the 1-dimethylbutyl) quinhydrones and 2 of 5-, two (1,1,3, the 3-tetramethyl butyl) quinhydrones of 5-; Pyrocatechol, for example catechol, 4-tert-butyl catechol and 3,5-ditertiarybutyl catechol; And benzoquinones class, for example benzoquinones, naphthoquinones and methylbenzoquinone.Wherein, preferred alkoxy phenol, catechol and benzoquinones, preferred especially alkoxy phenol.

For the free-radical generating agent of 1mol, the amount of the stopper of radical crosslinking is generally 0.001-1mol, and is preferably 0.01-1mol.

According to using and application target, can add various additives to polymerisable compound (A).Be used to improve film character, film with function be provided, improve formability etc.These additives comprise for example filler, improvement material (reforming materials), defoamer, whipping agent, tinting material, uv-absorbing agent, photostabilizer, oxidation inhibitor, fire retardant etc.These additives can dissolve in advance or be dispersed in the solution or dispersion liquid of cyclenes monomer (hereinafter being called " monomer solution " sometimes) or metathesis polymerization catalyzer (hereinafter being called " catalyst solution " sometimes).

For the cyclenes monomer of 100 weight parts, the amount of these additives is generally the 0.001-500 weight part.

In addition, the reaction stopper can add and prevents in the polymerisable compound (A) that before polymerization viscosity increases.

As operable reaction stopper, can provide and have 1,3-diene structure or 1,3, the linearity or the ring compound of 5-triolefin structure.Wherein, ring compound can be the monomer that is used to react, and serves as the reaction stopper simultaneously.In addition, Lewis base, for example phosphine, aniline etc. can be as the reaction stoppers.

The add-on of reaction stopper is generally the 0.001-5 weight part based on the cyclenes monomer of 100 weight parts, and is preferably the 0.002-2 weight part.If the amount of reaction stopper can not demonstrate the reaction polymerization inhibition effect less than 0.001 weight part.On the other hand, if should measure,, can damage the character of polymkeric substance because the reaction stopper remains in the polymkeric substance greater than 5 weight parts.Also can not fully carry out polyreaction.

Although the method for preparing polymerisable compound (A) is not particularly limited, can provides following method: for example prepare monomer solution and catalyst solution separately and before reaction, mix them.Chain-transfer agent, linking agent, crosslinked stopper and other additive can join monomer solution or catalyst solution.Perhaps, these compositions can join in the polymerisable compound (A) that obtains by mixed monomer solution and catalyst solution.

Monomer solution and catalyst solution are usually at 0-50 ℃ and preferably mix under 10-30 ℃ temperature.

In order to ensure high efficiency and stable product quality, wish in the present invention by continuous mixed monomer solution and catalyst solution and prepare polymerisable compound (A) continuously.In order to prepare polymerisable compound (A) continuously, monomer solution and catalyst solution use volume pump to be fed in the mixing tank respectively.

This pump volume pump is not particularly limited, as long as can be measured the amount of feed.Toothed gear pump, surge pump, pipe pump (tube pump), rotary pump, axial plunger pump (axial plunger pump), post pump (cylinderpump) etc. can be used as example and provide.Be not particularly limited for mixing tank.For example can use static mixer, dynamic mixer, collision type mixing tank (impingement mixer) etc.Conventional agitator also can be used as mixing tank.Wherein, preferred collision type mixing tank is because the productivity height of polymerisable compound (A).When using the collision type mixing tank, preferably mix the method for three kinds or more kinds of liquid.Particularly, monomer solution is divided into two portions, and this causes clashing into each other, produces Impact energy thus.Use the Impact energy mixed monomer solution and the catalyst solution that produce.

Step (II)

Step (II) is with polymerisable compound (A) the coating supporting mass of step (I) preparation or the step of flooding supporting mass with this polymerisable compound (A).

In the present invention, after step (I), carry out step (II) immediately continuously.Particularly, the polymerisable compound (A) of preparation (does not cause polymerisable compound to be detained after preparation) from the mixing tank supply continuously and immediately in the step (I), is used for applying or the dipping supporting mass.After preparation, be detained (for example, in the batch system reactor) if cause polymerisable compound (A), then can polymerization reaction take place change the viscosity of polymerisable compound (A).As a result, existence can not obtain the situation of homogeneous cycloolefin resin film.

Begin during from mixed monomer solution mixing tank and catalyst solution to apply at supporting mass or during the dipping polymerisable compound during t ₁Usually less than the working life of polymerisable compound (A), be also referred to as storage period this working life, and expression from beginning mixed monomer solution and catalyst solution when mixture gel and the lost flowability during.Time t ₁Be preferably working life 60% or still less, more preferably 10% or still less, also be preferably 1% or still less, and be preferably 0.1% or still less especially.

Working life can be according to JIS K6901, and the method for 4.8 joints determines that condition is that the measurement temperature is the temperature of the polymerisable compound (A) in the step (I).Time t ₁Short more, the precision of film thickness is high more, and dipping effect is good more when with polymerisable compound (A) dipping supporting mass.Polymkeric substance can adhere on the wall surface of the pipeline that polymerisable compound (A) flows through.Adhesive capacity along with during t ₁Shortening and reduce.

Because the method according to this invention, can use continuously to have mobile polymerisable compound (A) and applies continuously or flood supporting mass, so can obtain with the resin molding of supporting mass adhesive power excellence or evenly flooded the cyclenes resin of the filamentary material of form membrane.

As operable supporting mass, can provide tinsel, resin support film, filamentary material, metal drum, steel band, fluoridize (fluorin) resin strip etc.Wherein, preferable alloy paper tinsel, resin support film and filamentary material.

As the specific examples of tinsel, can provide Copper Foil, aluminium foil, nickel foil, lead foil, goldleaf, silver foil etc.Wherein, preferred Copper Foil.Type to Copper Foil is not specifically limited, as long as this Copper Foil can be used as the copper-clad layered product.Can suitably select thickness and roughness.

Silane coupling agent, mercaptan coupling agent (thiol coupling agent), processing such as titanate coupling agent (titanate coupling agent), various tackiness agents can be used in the surface of tinsel.Wherein, preferably use formula (5), the silane coupling agent of RSiXYZ or formula (6), the tinsel of the mercaptan coupling agent treatment of T (SH) n.

In the silane coupling agent of formula (5), R is illustrated in end and has two keys, sulfydryl key or amino group, and X and Y represent hydrolysable group, hydroxyl or alkyl independently, and Z represents hydrolysable group or hydroxyl.

The specific examples of the silane coupling agent of formula (5) can provide allyltrimethoxysilanis, styryl Trimethoxy silane, N-β-(N-(vinyl benzyl) amino-ethyl)-γ-An Bingjisanjiayangjiguiwan and salt thereof, vinyl three (2-methoxy ethoxy) silane, δ-methacryloxy butyl trimethoxy silane, γ-Qiu Jibingjisanjiayangjiguiwan, N-β-(amino-ethyl)-γ-An Bingjisanjiayangjiguiwan etc.

In the mercaptan coupling agent shown in the formula (6), T represents aromatic ring, alicyclic ring, heterocycle or aliphatic chain, and n is the integer more than 2 or 2.

The example of the mercaptan coupling agent of formula (6) can provide 2,4,6-tri-thiol-1,3,5-triazines, 2,4-dimercapto-6-dibutylamino-1,3,5-triazines, 2,4-dimercapto-6-anilino-1,3,5-triazines etc.

As the specific examples of resin support film, can provide polyethylene terephthalate film, polypropylene screen, polyethylene film, polycarbonate membrane, PEN film, polyene propyl ester film (polyallylatefilm), nylon membrane, poly tetrafluoroethylene etc.

Although the thickness to these tinsels and resin support film is not specifically limited, from considerations such as processibilities, thickness is generally 1-150 μ m, is preferably 2-100 μ m, and 3-75 μ m more preferably.

As filamentary material, can use any known filamentary material, comprise organic and/or inorganic fibre, and be not particularly limited.As the specific examples of filamentary material, can provide glass fibre, carbon fiber, Kevlar, pet fiber, vinylon fiber, trevira, nylon, steel fiber, ceramic fiber etc.These filamentary materials can use separately, or two or more are used in combination.As the form of filamentary material, can provide pad, cloth, nonwoven fabric etc.

Be not specifically limited for method with polymerisable compound (A) coating or dipping supporting mass.Can use known coating method, for example spraying method, dip coating, rolling method, curtain are coated with method, mouthful pattern coating method, slot coated method and use hyperacoustic atomizing coating method (atomizing method).These methods can obtain to have the level and smooth film of precise thickness.

Can use any conventional known devices of the enough polymerisable compounds of energy (A) coating supporting mass, and without any concrete restriction.The coating unit that can be given in description among the flat H1 of Japanese Patent Application Laid-Open (1989)-198639, No.H8 (1996)-134235 and the No.H8 (1996)-174549 is as specific examples.

When filamentary material is used as supporting mass; can use polymerisable compound (A) dipping supporting mass, comprise that the polymerisable compound (A) with specified amount is administered on the filamentary material, as required laminated protective membrane on filamentary material; and the material that closes with neutralizing layers such as cylinders.

For applying or the amount of the polymerisable compound (A) of dipping supporting mass is not specifically limited.Can suitably select this amount according to required thickness of resin film.The coating of polymerisable compound (A) or dipping temperature are generally 0-80 ℃.If coating or dipping temperature are too high, owing to meeting polymerization reaction take place during coating or dip operation, polymerisable compound (A) can not evenly be coated with.

Step (III)

Step (III) is by being heated to specified temperature and the step of mass polymerization polymerisable compound (A) with the supporting mass of polymerisable compound (A) coating or dipping.In the present invention, step (III) is preferably carried out continuously and after step (II) immediately.

Although the method for heating with the supporting mass of polymerisable compound (A) coating or dipping is not specifically limited, preferably uses the method for warming mill, hot-plate or process furnace.Use the method for these heating installations to guarantee effectively and continuously to prepare cycloolefin resin film with excellent smoothness and precise thickness by the mass polymerization of polymerisable compound (A).

The method of using warming mill particularly including as required apply with polymerisable compound (A) or the surface of the supporting mass of dipping on laminated protective membrane and use warming mill hot pressing laminate.The hot pressing of use warming mill has guaranteed that the mass polymerization of polymerisable compound (A) is with preparation cyclenes resin.

As protective membrane, can use any film, and be not specifically limited with rippability from the cyclenes resin.For example, can provide polyethylene terephthalate film, polypropylene screen, polyethylene film, polycarbonate membrane, PEN film, polyene propyl ester film, nylon membrane, poly tetrafluoroethylene etc.

Using the method for hot-plate specifically to comprise will apply with polymerisable compound (A) or the supporting mass of dipping is placed on the plate, and heats this plate with the mass polymerization acquisition cyclenes resin by polymerisable compound (A).

Using the method for process furnace specifically to comprise will apply with polymerisable compound (A) or the supporting mass of dipping is placed in the process furnace, and in process furnace the whole supporting mass of heating with mass polymerization acquisition cyclenes resin by polymerisable compound (A).

By using the long support body anyly to prepare the long film of cyclenes resin continuously with supporting mass with aforesaid method.Can reel, store and the cycloolefin resin film that gets of transport point with long support body.

Polymeric reaction temperature is generally 100-300 ℃, is preferably 100-250 ℃, more preferably 120-250 ℃ and 140-250 ℃ the most.If maximum temperature of reaction is set De Genggao, can obtain the cross-linked resin film, this is because not only carried out polyreaction, has also carried out crosslinking reaction.

For obtaining the cross-linked resin film, preferably do not adding polymerization polymerisable compound (A) under the chain-transfer agent, this is because when not having chain-transfer agent, can obtain to have the cross-linked resin film than high crosslink density.Use filamentary material and tinsel as supporting mass for obtaining cross-linked resin film preferably combination, to guarantee good productivity, this is to need not to prepare prepreg (prepreg) because preparing the layered product that belongs to covered with gold leaf.

On the other hand, can the crosslinked thermoplastic resin film in back in order to prepare, preferably must be lower than 200 ℃ by control body polymeric maximum temperature.Herein, " can be back crosslinked " refers to prepare by heating and fusion cross-linked resin film the state of cross-linked resin.At this moment, when free-radical generating agent when the linking agent, preferably the maximum temperature of mass polymerization is controlled to one minute half life temperature (one-minutehalf-life temperature) of free-radical generating agent or lower.Herein, " one minute half life temperature " is the temperature that a half of initial amount is decomposed and reduced to free-radical generating agent after a minute.For example, one minute half life temperature of ditertiary butyl peroxide is 186 ℃ and 2,5-dimethyl-2, and the temperature of two (the t-butyl peroxy)-3-hexins of 5-is 194 ℃.

In the present invention, when use contains heteroatomic carbene compound as the ruthenium complex compound of part during as the metathesis polymerization catalyzer, preferably by under 20 ℃/minute or higher heating rate, and under preferred 50 ℃/minute or the higher heating rate, be heated to 100 ℃ or higher, by mass polymerization polymerization polymerisable compound (A).This ruthenium complex compound has high catalytic activity and demonstrate tangible temperature dependency in the metathesis polymerization reaction.Therefore, if, in the very short time, can obtain high polymerisation conversion by under high heating rate, polymerisable compound (A) being heated to 100 ℃ or highlyer carry out mass polymerization.

Because mass polymerization almost completely in resin, the gained resin molding only contains very small amount of residual monomer.High polymerisation conversion obtains not having the resin of the smell that residual monomer produces, and has therefore guaranteed good working environment.In addition, owing to do not proceed mass polymerization (transposition ring-opening polymerization) between the shelf lives, product has excellent stability in storage.

The dissolving of resin in solvent of mass polymerization preparation confirms that this resin is a thermoplastic resin.Particularly, if tree liposoluble then is thermoplastic resin in solvent, if be insoluble in the solvent then be cross-linked resin.As the example of solvent, can provide aromatic hydrocarbon, for example benzene and toluene; Ether, for example Anaesthetie Ether and tetrahydrofuran (THF); And halohydrocarbon, for example methylene dichloride and chloroform.

Can be by being dissolved in thermoplastic resin in the toluene and using known analytical procedure, gas chromatographic analysis gained solution and determine the polymerisation conversion of thermoplastic resin for example.The polymerisation conversion of gained thermoplastic resin is generally 80% or higher, and more preferably 90% or higher, and most preferably be 95% or higher.The gained thermoplastic resin film may not be fully can the back crosslinked, but the surf zone of thermoplastic resin film is can the back crosslinked just enough at least.

It is 2mm or thinner that preparation method of the present invention goes for preparing its thickness, is preferably 1mm or thinner, more preferably 0.5mm or thinner and most preferably be 0.1mm or thinner cycloolefin resin film.

When the cycloolefin resin film that obtains by method of the present invention is thermoplastic resin film, resin flow and adhesive power excellence.Therefore, if this thermoplastic resin and substrate layer merging are crosslinked, can obtain the cross-linked resin matrix material of planeness excellence, this matrix material is made of the cross-linked resin that is tightly adhered on the base material.

When the supporting resin molding was used as supporting mass, separating the thermoplastic resin film that obtains from the supporting resin molding can be laminated with base material.Base material as use herein can provide tinsel, conductive polymer membrane, other thermoplastic resin film and plate etc.

When tinsel, when being used for the outer field gold filled that belongs to layered product or be used for internal layer covered with gold leaf and belonging to layered product as base material, can be between stainless steel plate (stainless plate) laminated these base materials and thermoplastic resin film, and can the laminated material of hot pressing, obtain the base material of cross-linked resin-gold filled genus layered product or cross-linked resin-mutually combine with cross-linked thermoplastic resin part.

When tinsel when the supporting mass, cross-linked resin-gold filled genus layered product can partly obtain by the thermoplastic resin that crosslinked gained has a tinsel of resin.

For example, when Copper Foil was used as matrix, gained cross-linked resin-copper-clad layered product was made of the crosslinked cyclenes resin of secure adhesion to matrix.This is as electronic material, for example the ideal material of printed circuit board.The stripping strength of the Copper Foil of measuring according to JIS C6481 is preferably 0.8kN/m or higher, and 1.2kN/m or higher more preferably.

The temperature of cross-linked thermoplastic resin is generally 170-250 ℃ and be preferably 180-220 ℃.Although be not particularly limited, the time of cross-linked resin was generally several minutes to several hours.

2) prepare the method for cycloolefin polymer sheet or film

It is 1 millimeter or the thinner cycloolefin polymer sheet or the method for film that second invention provides preparation thickness, comprise by ring-opening metathesis mass polymerization polymerization and contain ruthenium complex catalyst and the monomeric reactive solution of cyclenes, described catalyzer has as containing of part of heteroatomic carbene compound, wherein finishes the monomeric polymerization of cyclenes by with 20 ℃/minute or higher heating rate reactive solution being heated to 100 ℃ or higher temperature.

Ruthenium complex catalyst

Being used for ruthenium complex catalyst of the present invention is to have to contain the ruthenium complex compound of heteroatomic carbene compound as part.This ruthenium complex catalyst is the catalytic activity excellence in mass polymerization.Therefore, this catalyzer demonstrates the excellent cycloolefin polymer sheet or the productivity of film.Resulting polymers sheet or film also demonstrate excellent productivity, and do not come from the monomeric smell of unreacted cyclenes.

Have contain heteroatomic carbene compound as the ruthenium complex catalyst (hereinafter being called " ruthenium complex catalyst " sometimes) of part be a kind of have ruthenium as central metal with contain the ruthenium complex that heteroatomic carbene compound is connected.Therefore this catalyzer has the structure that the ruthenium atoms metal directly is connected with the Cabbeen carbon atom.

The compound that above-mentioned formula (1) or (2) show can provide the specific examples as the ruthenium complex compound.In above-mentioned formula (1) and (2), L ¹And L ²In at least one for containing heteroatomic carbene compound.

With ruthenium atom in the catalyzer and the monomeric mol ratio of cyclenes is 1: 2,000 to 1: 2, and 000,000, be preferably 1: 5,000 to 1: 1,000,000 and more preferably 1: 10,000 to 1: 500,000 ratio was used ruthenium complex catalyst.

If desired, ruthenium complex catalyst can be dissolved in a small amount of inert solvent and using.As described solvent, can provide and the above-mentioned solvent phase solvent together that is used to dissolve the metathesis polymerization catalyzer.

Activator (promotor) can be used in combination with ruthenium complex catalyst, the active or increase polymerisation conversion with controlled polymerization.As activator, can provide alkylate, halogenide, alkoxy compound, aryloxy compound of aluminium, scandium, tin, titanium or zirconium etc.Activator is 1: 0.05 to 1: 100 with the mol ratio of ruthenium atom in the catalyzer and activator, is preferably 1: 0.2 to 1: 20, and more preferably 1: 0.5 to 1: 10 ratio is used.

The cyclenes monomer

As being used for cyclenes monomer of the present invention, can provide monocycle alkene monomer, norbornene monomer etc.These cyclenes monomers can use separately or being used in combination with two or more.When using two or more cyclenes monomers, can control the second-order transition temperature and the melt temperature of gained resin by regulating blending ratio.These cyclenes monomers can be by alkyl, and for example alkyl, alkenyl, alkylidene group or aryl or polar group replace.

In these, norborneol vinyl monomer (being called " norbornene monomer " in specification sheets) is preferred especially in the present invention.The amount of norbornene monomer is preferably the monomeric 60wt% of cyclenes or higher, more preferably 80wt% or higher.Norbornene monomer can have the two keys that are different from the two keys of norbornylene ring.

As monocycle cyclenes monomer and norbornene monomer, can be given in the monomer of mentioning among the preparation method of cycloolefin resin film in first invention.

In the aforementioned monomer, when epoxy compounds was used as linking agent, the preferred norbornene monomer with carboxyl or anhydride group that uses was as norbornene monomer, because be easy to prepare cross-linked resin.The content of norbornene monomer in cyclenes monomer total amount with carboxyl or anhydride group is preferably 1mol% or higher, and 5mol% or higher more preferably.

Reactive solution

Being used for reactive solution of the present invention is to contain above-mentioned ruthenium complex catalyst and the monomeric solution of cyclenes.

Although the method to preparation feedback solution is not particularly limited, but can provide following method as an example: prepare cycloolefin monomers liquid solution and catalyst solution separately, and before polymerization begins mixed monomer solution and catalyst solution immediately, ruthenium complex catalyst is dissolved in or is dispersed in the solvent in this catalyst solution.

Monomer solution and catalyst solution be usually at-20 ℃ to+50 ℃, and preferably mix under 0 ℃ to 30 ℃ temperature.

In the present invention, when needs prepare thermoplasticity cycloolefine polymer (thermoplastic resin), preferably chain-transfer agent is added in the above-mentioned reactive solution.

As chain-transfer agent, can be given in those that mention in the method for preparing cycloolefin resin film in first invention.

The add-on of chain-transfer agent is generally the 0.01-10 weight part and is preferably the 0.1-5 weight part based on 100 weight part cyclenes monomers.Chain transfer dosage in this scope has been guaranteed high polymerisation conversion and has effectively been prepared thermoplastic resin.

Linking agent also can add reactive solution.Linking agent can prepare cross-linked resin by the functional group's crosslinking reaction with thermoplasticity cyclenes resin.

As the example of functional group, can provide carbon-to-carbon double bond, hydroxy-acid group, anhydride group, hydroxyl, amino, reactive halogen atom, epoxy group(ing) etc.

As the example of spendable linking agent, can provide free-radical generating agent, epoxy compounds, contain compound, the carboxylic compound of isocyanate groups, the compound that contains anhydride group, the compound that contains amino, Lewis acid etc.As specific examples, can be given in those that mention in the method for preparing cycloolefin resin film in first invention.These linking agents can use separately or two or more are used in combination.

Amount for linking agent is not particularly limited.This amount can suitably be determined according to the kind of used linking agent.When free-radical generating agent was used as linking agent, based on the cyclenes monomer of 100 weight parts, the amount of used linking agent was generally the 0.1-10 weight part and is preferably the 0.5-5 weight part.When epoxy compounds was used as linking agent, based on the cyclenes monomer of 100 weight parts, the amount of used linking agent was generally the 1-100 weight part and is preferably the 5-50 weight part.

When using linking agent, can use to improve the effect of linking agent with the crosslinking activity auxiliary agent.As the crosslinking activity auxiliary agent, can be given in those that mention in the method for preparing cycloolefin resin film in first invention.

Although be not particularly limited, the consumption of crosslinking activity auxiliary agent is generally the 0-100 weight part based on the cyclenes monomer of 100 weight parts, and is preferably the 0-50 weight part.

Preferably the stopper with radical crosslinking joins in the reactive solution.The stopper of this radical crosslinking is generally the compound with free radical capture function, and demonstrates the effect that the delayed free base produces the radical crosslinking reaction that agent causes.Can join the flowability of thermoplastic resin when improving laminated resin in the reactive solution and the stability in storage of thermoplastic resin by stopper with radical crosslinking.

As the stopper of radical crosslinking, can be given in those that mention in the method for preparing cycloolefin resin film in first invention.

The amount of the stopper of radical crosslinking is generally 0.001-1mol based on the free-radical generating agent of 1mol, and is preferably 0.01-1mol.

To react stopper joins and can prevent in the reactive solution that before polymerisation reactivity solution viscosity increases.

As the reaction stopper, can be given in those that mention in the method for preparing cycloolefin resin film in first invention.

The add-on of reaction stopper is generally the 0.0001-5 weight part based on the cyclenes monomer of 100 weight parts, and is preferably the 0.001-2 weight part.If the amount of reaction stopper less than 0.0001 weight part, can not demonstrate reaction and hinder effect.On the other hand, if should measure greater than 5 weight parts, the character of product can suffer damage because of the reaction stopper that remains in the polymkeric substance.Polyreaction also may be carried out insufficient.

According to the purpose of using and using, various additives can join in the reactive solution, to improve the character of sheet and film, function are provided, improve formability etc. for sheet or film.

These additives comprise, for example filler, improvement material, defoamer, whipping agent, tinting material, uv-absorbing agent, photostabilizer, oxidation inhibitor, fire retardant etc.

The amount of these additives is generally the 0.001-500 weight part based on the cyclenes monomer of 100 weight parts.

Chain-transfer agent, linking agent, crosslinked stopper and other additive can join monomer solution or join catalyst solution.Perhaps, these compositions can join in the reactive solution that obtains by mixed monomer solution and catalyst solution.

The open loop mass polymerization

Zhi Bei reactive solution is heated to specified temperature (curing) with by open loop mass polymerization polymerisation reactivity solution in the above described manner, obtains cycloolefin polymer sheet or film thus.Solidification value is generally 100-300 ℃, and is preferably 100-250 ℃.

The present invention has with 20 ℃/minute or higher, is preferably 50 ℃/minute or higher heating rate reactive solution is heated to more than 100 ℃ or 100 ℃, to finish cyclenes monomer step of polymerization.If it is 1 millimeter or thinner sheet or film that heating rate less than 20 ℃/minute, is difficult to prepare thickness,, cause catalytic activity and polymerisation conversion to reduce because heat of polymerization is lost because of thermodiffusion.Can by use have contain heteroatomic carbene compound as the ruthenium complex catalyst of part as the position polymerizing catalyst, and rapid heating reaction system, and improve catalytic activity and obtain high polymerisation conversion.The method according to this invention by the catalytic activity of abundant increase ruthenium complex catalyst, can prepare cycloolefin polymer sheet or film effectively with high polymerisation conversion.

In the present invention, preferably after preparation, apply with reactive solution immediately or the dipping supporting mass.From preparation feedback solution to reactive solution is fed to mould or with reactive solution apply or during the dipping supporting mass during preferred in the working life of reactive solution, more preferably 60% of working life or still less.

Open loop mass polymerization by reactive solution is obtained sheet that thickness is 1mm or thinner moulding or the method for film is not particularly limited.For example can provide (i) packs into reactive solution and is heated to the mould of specified temperature, with by open loop mass polymerization polymeric method, (ii) apply or the dipping supporting mass, and be heated to specified temperature with by open loop mass polymerization polymeric method etc. with reactive solution.Wherein, be 1mm or the thinner polymer sheet or the ability of film owing to can effectively prepare thickness, more preferably method is (ii).

The mould that uses in method (i) is not particularly limited.Can use the conventional mould that is used to form sheet, this mould can prepare the sheet or the membranaceous product of moulding.For example, the mould that is used to form sheet can comprise two stainless steel plates being clamped by U type spacer (spacer) and be administered to panel heater (face-plate heaters) on the stainless steel plate.

When the temperature of the mould of filling reactive solution is generally-20 ℃ to+80 ℃.Then with 20 ℃/minute or higher, and be preferably 50 ℃/minute or higher heating rate, by being provided in panel heater in the mould with mold heated to 100 ℃ or higher, be preferably 150 ℃ or higher, to finish the open loop mass polymerization of reactive solution, obtain required cycloolefin polymer sheet or film thus.

Example as the supporting mass that uses in (ii) in method can provide electro-conductive material; Filamentary material; Resin support film, for example polyethylene terephthalate film, polypropylene screen, polyethylene film, polycarbonate membrane, PEN film, polyene propyl ester film, nylon membrane, poly tetrafluoroethylene; The fluorine resin band; Deng.Wherein, when cycloolefin polymer sheet of the present invention or film preferred conductive material and filamentary material during as electronic material.

As electro-conductive material, can provide metal, for example alloy of two or more in copper, nickel, aluminium, iron, tin, chromium, silver, gold, platinum, tungsten and these metals, and conductive polymers.More preferably metal.

Form to metallic substance is not particularly limited.Can use the liquid and the solid metal of drum, band or film (tinsel) form.Wherein, preferable alloy paper tinsel, for example Copper Foil, aluminium foil, nickel foil, lead foil, goldleaf, silver foil etc.Type for tinsel is not particularly limited, as long as this tinsel can be as the layered product that belongs to covered with gold leaf.Can suitably select thickness and roughness.Although the thickness to electro-conductive material is not particularly limited, consider processibility etc., thickness is generally 1-150 μ m, is preferably 2-100 μ m, more preferably 3-75 μ m.When electro-conductive material is used as supporting mass, can obtain to have the cycloolefin polymer sheet or the film of conductive layer.For example when tinsel is used as electro-conductive material, can obtain tinsel with resin.

Processing such as silane coupling agent, mercaptan coupling agent, titanate coupling agent, various tackiness agents can be used in the surface that is used as the tinsel of electro-conductive material.Especially preferably use the tinsel of the mercaptan coupling agent treatment of the silane coupling agent of following formula (5) or following formula (6).

As filamentary material, can use organic fibrous material or inorganic fibers, and without any special restriction.As the specific examples of filamentary material, can provide glass fibre, carbon fiber, Kevlar, pet fiber, vinylon fiber, trevira, nylon, steel fiber, ceramic fiber etc.These filamentary materials can use separately or two or more are used in combination.As the form of filamentary material, can provide pad, cloth, nonwoven fabric etc.When filamentary material is used as supporting mass, can obtain fibre-reinforced prepreg.

Be not particularly limited for the method that applies supporting mass with reactive solution.Can be given in first invention and prepare the same procedure that the method for cycloolefin resin film is partly described.

When filamentary material is used as supporting mass; can apply supporting mass with reactive solution, comprise and use above-mentioned coating method, the reactive solution of specified amount is administered on the filamentary material; laminated protective membrane and with neutralizing layer condensation materials such as rollers on filamentary material as required.

To applying or the amount of the reactive solution of dipping supporting mass is not particularly limited.This amount can suitably be determined according to the thickness of required polymer sheet or film.The coating or the dipping temperature of reactive solution is generally-20 ℃ to+80 ℃.If coating or dipping temperature are too high, reactive solution can not evenly be coated with, and this is because can polymerization reaction take place during coating or dip operation.

Although to passing through with 20 ℃/minute or higher heating rate, reactive solution is heated to 100 ℃ or higher and finish the polymeric method and be not particularly limited, but, preferably use the method for warming mill, hot-plate or process furnace for the reactive solution of heating coating or dipping supporting mass.Heating by these methods can apply or the identical mode of heating means of the supporting mass of dipping is carried out with polymerisable compound (A) with above-mentioned.These methods have been guaranteed the mass polymerization by reactive solution, also prepare cycloolefin polymer sheet or film continuously effectively.

Can be with any aforesaid method, by using the long support body, preparation has the long cycloolefin polymer sheet or the film of supporting mass continuously.Gained has the cycloolefin polymer sheet or the film of long support body and can reel, stores or transport.

The polymerisation conversion of cycloolefine polymer of the present invention is generally 80% or higher, and more preferably 90% or higher, even more preferably 95% or higher.Because mass polymerization is almost carried out in the cycloolefine polymer diaphragm fully, the gained resin molding only contains very small amount of residual monomer.In other words, because the polymerisation conversion height, polymer sheet or film can be owing to from monomeric smells and aggravating working environment.In addition, polymer sheet or film stability in storage excellence, this is because can not carry out mass polymerization in storage process.And, the excellent heat resistance of polymer sheet or film, this is because when not having residual monomer, and the second-order transition temperature of polymkeric substance can not take place to reduce by plasticising.

Can prepare wherein that cycloolefine polymer is the polymer sheet or the film of thermoplastic resin by method of the present invention, or wherein cycloolefine polymer is the polymer sheet or the film of cross-linked resin.Particularly, wherein cycloolefine polymer is that the polymer sheet of thermoplastic resin or film can prepare by the reactive solution that mass polymerization contains chain-transfer agent, and wherein cycloolefine polymer is that the polymer sheet of cross-linked resin or film can prepare by the reactive solution that mass polymerization contains linking agent.

And, if by the mass polymerization polymerization, can obtain can crosslinked thermoplasticity cycloolefin polymer sheet or the film in back for the reactive solution that contains linking agent and chain-transfer agent.Can determine the thermoplasticity of this cycloolefine polymer by this cycloolefin polymer sheet of dissolving or film in solvent.

Can crosslinked thermal plasticity slice or the film in back in order to prepare, be necessary that control body polymeric top temperature is preferably less than 200 ℃.When free-radical generating agent was used as linking agent, the top temperature of mass polymerization preferably controlled to one minute half life temperature or lower of free-radical generating agent.

When cycloolefin polymer sheet or film were thermoplastic resin sheet or film, this sheet or film demonstrated excellent flowability and binding property.By this sheet or film and base layer are merged the cross-linked thermoplastic resin, can obtain planeness excellent and also with the cross-linked resin matrix material of matrix secure adhesion.

Usually at 170-250 ℃, and preferably 180-220 ℃ crosslinked can crosslinked thermoplasticity cycloolefin polymer sheet or the film in back.Although be not particularly limited, crosslinking time was generally several minutes to several hours.

The support membrane of making when metal sheet or resin can be laminated with matrix by separate the cycloolefin polymer sheet or the film that obtain with supporting mass during as supporting mass.Matrix as use herein can provide full genus paper tinsel, conductive polymer membrane and other thermoplastic resin film and plate.

When tinsel, when being used for the outer field gold filled that belongs to layered product or be used for internal layer covered with gold leaf and belonging to layered product as matrix, can be between stainless steel plate laminated these matrixes and thermoplastic resin film, and laminate can hot pressing, with cross-linked thermoplastic resin part, thereby obtain the base material of cross-linked resin-gold filled genus layered product or cross-linked resin-mutually combine.

When tinsel when the supporting mass, cross-linked resin-gold filled genus layered product can partly obtain by the thermoplastic resin that crosslinked gained has a tinsel of resin.For example, when Copper Foil was used as matrix, gained cross-linked resin-copper-clad layered product was made of the crosslinked cyclenes resin of secure adhesion to matrix.This is as electronic material, for example the ideal material of printed circuit board.The stripping strength of the Copper Foil of measuring according to JIS C6481 is preferably 0.8kN/m or higher, more preferably 1.2kN/m or higher.In addition, because gained cross-linked resin-copper-clad layered product only contains micro residue solvent and monomer, so this product does not for example have the blistered problem owing to produce gas.

Embodiment

By embodiment and Comparative Examples the present invention is described in more detail.Yet the following examples should not be construed as limiting the invention.Monomeric kind of catalyzer and cyclenes and quantity can freely change, and do not deviate from essence of the present invention.

Measure working life in the following manner: during when mixing 15ml monomer solution and 0.12ml catalyst solution and measuring when beginning to mix to mixture gelling and lost flowability.In nitrogen atmosphere, carry out sequence of operations, and at 25 ℃ of mixed monomer solutions and catalyst solution.

Use differential scanning calorimeter, after with 10 ℃/minute heating rate heating, measure the second-order transition temperature (Tg) of mold compound.Add thermal residue with residue weight percentage ratio mensuration, it uses thermobalance to measure after sample is heated to 400 ℃ from room temperature.

＜the present invention is used to solve the embodiment and the Comparative Examples of first purpose 〉

Embodiment 1

The 100ml glass flask is equipped with 1.1 gram benzylidene (1,3-two basic imidazolidine-2-subunits) (tricyclohexyl phosphine) ruthenous chlorides and 1.6 gram triphenylphosphines.Add 44 gram toluene dissolving mixts, thereby obtain catalyst solution 1, and the concentration of ruthenium is 0.025mol/l.

With 1.8 gram 4-methoxyl group-2,6 di t butyl phenols, 450 gram Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4-alkene, 150 gram 2-norbornylenes, 15ml allyl methacrylate(AMA) and the 8.6ml ditertiary butyl peroxide 1 liter of eggplant shape flask of packing into, obtain monomer solution 1.Use monomer solution 1 and catalyst solution 1 to determine that be 6 minutes working life.

Woven fiber glass enhanced teflon resin film (hereinafter be called " woven fiber glass enhanced PTFE resin molding ", thickness is 0.08mm, by the Product#5310 of Saint-Gobain KK manufacturing) is cut into 150mm * 4100mm fragment (sections).(Asahi Schwebel Co., the Product#2116/AS891AW that Ltd. makes) is placed on the woven fiber glass enhanced PTFE resin molding with three sheet glass cloth, and each sheet is of a size of 100mm * 4000mm and thickness is 0.092mm.

Then, the tubule pump is connected to every kind of solution, respectively with the speed of 15ml/ minute and 0.12ml/ minute with described solution be fed to little static mixer (spiral, element (element) length: 3.18mm, number of elements: 24).The mixing solutions that flows out static mixer is fed to the end (starting end) of woven fiber glass, and is transported to the other end (end) with 400mm/ minute transport velocity.Above-mentioned woven fiber glass enhanced PTFE resin molding is covered the woven fiber glass part that is supplied with mixing solutions, and use roller to suppress, so that the mixed solution impregnation of woven fiber glass from the top.

Beginning to supply mixing solutions after three minutes, with hot-plate (being heated to 200mm * 200mm aluminium sheet of 150 ℃) be placed on woven fiber glass enhanced PTFE resin molding below, and make and to contact with it from starting end, heat and solidify this mixture.Then, hot-plate is moved to end with 400mm/ minute speed from the starting end of woven fiber glass.

Beginning to supply mixing solutions after 10 minutes, finished dipping at the end of woven fiber glass, finished mixing solutions supply operation thus.In addition, after 13 minutes, hot-plate arrives the end of woven fiber glass, has finished heating/curing operation thus at the supply mixing solutions.Afterwards, remove woven fiber glass enhanced PTFE resin molding in both sides, obtain prepreg.

The part prepreg is put into platinum crucible, and burning-off resin part in the electronic heating stove is determined glass content according to the remaining glass weight in burning back.The discovery glass content is 57wt%.The part prepreg is immersed in the toluene, with the molten resin part of going.Determine the residual monomer amount by vapor-phase chromatography.From residual monomer amount and glass content calculating polymerisation conversion is 97%.

Two acetate are added in the 60 gram distilled water.Then 0.18 gram vinyl three (2-methoxy ethoxy) silane (Ltd. makes for trade name: A-172, Nippon Unicar Co.) is joined in this aqueous solution, this mixture was stirred 10 minutes, with hydrolysis and dissolves silicon hydride compounds.Solution of silane is absorbed in the absorbent cotton, is administered to the Copper Foil (handle uneven surface with GTS, thickness: 0.018mm, Furukawa Circuit Foil Co., Ltd. makes) of galvanic deposit, and in nitrogen atmosphere 130 ℃ of dryings one hour.

It is 90mm * 90mm (thickness: in square framework 1mm) (square frame) that four above-mentioned prepregs (each sheet is cut into 87mm * 87mm fragment) are placed into interior dimensions, and clamp from both sides with the Copper Foil (being cut into 115mm * 115mm fragment) of above-mentioned silane treatment, so that coarse side is to the preimpregnation side.Should sandwich material hot pressing 15 minutes 4.1MPa and 200 ℃.Then, when exerting pressure, cool off this material.Be 100 ℃ or shift out sample when lower in temperature, thereby obtain two-sided copper-clad layered product.

The Copper Foil peeling force of the two-sided copper-clad layered product of gained is measured according to the method for JIS C6481, and the discovery peeling force is 1.6kN/m.The thermotolerance of this scolder of test continues 20 seconds in 260 ℃ scolders (solder) groove, confirms not bubble.Use fiber-reinforced resin part (thickness: 1.5mm) peeling off the laggard line bend test of Copper Foil, confirming that elastic bending modulus (bending modulus of elasticity) is that 12GPa and flexural strength are 386MPa.Use electric impedance analyzer (E4991, Agilent Corp. manufacturing) specific inductivity and tangent of the dielectric loss angle have been measured, confirmed that specific inductivity (moldlectric constant) and tangent of the dielectric loss angle are respectively 3.5 and 0.0013 under 100MHz, be respectively 3.5 and 0.0022 at 1GHz.

Embodiment 2

The 100ml glass flask is equipped with 4.1 gram benzylidenes, two-tricyclohexyl phosphine) ruthenous chloride and 5.2 gram triphenylphosphines.Add 35 gram toluene and dissolve this mixture, obtain catalyst solution 2 thus, the concentration of ruthenium is 0.10mol/l (ruthenium complex catalyst, it does not contain as containing of part of heteroatomic carbene compound).Use monomer solution 1 and catalyst solution 2 to determine that be 3 minutes 50 seconds working life.

Prepare prepreg according to the mode identical with embodiment 1, difference is to use catalyst solution 2 to replace catalyst solutions 1.Obtained to be of a size of the long prepreg of 4000mm * 100mm continuously as embodiment 1.

Comparative Examples 1

Prepare ten sheet glass cloth enhanced PTFE resin moldings (with use among the embodiment 1 identical, be cut into 150mm * 500mm fragment).Three sheet glass cloth (identical with the woven fiber glass that uses among the embodiment 1, as to be cut into 100mm * 400mm fragment) are placed on each sheet glass cloth enhanced PTFE resin molding.

The catalyst solution 2 of preparation among monomer solution 1 that the 150ml embodiment 1 that packs in the 200ml beaker prepares and the 1.2ml embodiment 2, and the acquisition mixing solutions that stirs the mixture.In syringe, measure the 15ml mixing solutions, and be added on the woven fiber glass of the first woven fiber glass enhanced PTFE resin molding.Use another sheet glass cloth enhanced PTFE resin molding (identical) to cover this woven fiber glass enhanced PTFE resin molding then, it is suppressed so that mixing solutions floods this woven fiber glass with roller with first type.Then, product being placed on hot-plate (200mm * 200mm aluminium sheet is heated to 150 ℃) goes up and heated cured resin one minute.Remove woven fiber glass enhanced PTFE resin molding, obtain prepreg.

Use identical mixing solutions to repeat top same operation, with preimpregnation of each minute preparation.As a result, the viscosity of confirmation mixing solutions increases in time.In the process of the 4th prepreg of preparation, be difficult to use the mixing solutions impregnated glass-fiber cloth.Therefore, finish the preparation of prepreg.Three prepregs have been obtained.

Embodiment 3

The apparatus for continous formation that in embodiment 3, uses Fig. 1 to show.12 gram pyrolytic silicon dioxides (AEROSIL 200, and Japan Aerosil Co. makes), 450 gram Fourth Ring [6.2.1.1 pack in monomer solution jar 1 ^3,6.0 ^2,7] 12-4-alkene, 150 restrains the 2-norbornylenes, 10 gram methacrylic acid styrene esters and 8.6 restrain 1,3-two (2-t-butyl peroxy sec.-propyl) benzene (one minute half life temperature: 175 ℃).Stir the mixture and obtain monomer solution 2.The catalyst solution 1 that the embodiment 1 that packs in catalyst solution jar 2 prepares.Use monomer solution 2 and catalyst solution 1 to determine that be 5 minutes and 40 seconds working life.

Tubule pump 3 and 4 is connected respectively to monomer solution jar 1 and catalyst solution jar 2, with 0.12ml/ minute flow solution was fed to little static mixer 5 (identical with the agitator that uses among the embodiment 1) with 15ml/ minute respectively, obtain mixing solutions, mixing solutions is fed to coated portion 6.

Thickness is that 75 μ m and width are that the PEN film of 100mm is delivered to coated portion 6 from support membrane transmitting portions 7 forward with the transmission speed of 50mm/s, this continuously coating this support membrane to coat-thickness be 50 μ m.The support membrane that will be coated with is delivered to process furnace 9 continuously.In process furnace 9, by heating for 30 seconds at 150 ℃, polymerization and curing monomer mixture obtain the film on the support membrane.The film that is attached on the support membrane is wound up on the axle of volume membrane portions 10.

The part of this film is taken out from support membrane, and immerse in the toluene with dissolving resin.Send out the amount of measuring residual monomer in the solution by gas-chromatography.Based on the residual monomer amount of gained, calculating polymerisation conversion is 97%.

On the other hand, film is adhered to the two-sided copper-clad layered product (thickness: 1mm of glass epoxide, be cut into the both sides of 80mm * 80mm), this layered product has used surperficial roughening instrument (surface roughener) CZ-8100 (MEC Co., Ltd.) microetch, and 5.2MPa and 200 ℃ of following hot pressings 15 minutes.When exerting pressure, be cooled to 100 ℃ or lower after, this sample is shifted out, obtain two-sided copper-clad layered product, and cross-linked resin adheres on its surface.Carry out cross-hatching sticking power test (cross-cutadhesion test) according to JIS K5400, with the sticking power between test resin layer and the inner copper-clad.As a result, there is not overburden (peel-off).

Embodiment 4

In embodiment 4, use the apparatus for continous formation shown in Fig. 2.12 gram pyrolytic silicon dioxides (AEROSIL 200), 252 gram Fourth Ring [6.2.1.1 pack in monomer solution jar 11 ^3.6.0 ^2.7] 12-4-alkene, 108 gram 2-norbornylenes, 240 gram Dicyclopentadiene (DCPD), 5.0ml vinylbenzene and 8.6 ditertiary butyl peroxides (one minute half life temperature: 186 ℃).Stir the mixture and obtain monomer solution 3.Catalyst solution jar 12 1.1 gram benzylidene (1,3-two bases-4-tetrahydroglyoxaline-2-subunit) (tricyclohexyl phosphine) ruthenous chloride and the 1.6g triphenylphosphines of packing into.Add 44 gram toluene with dissolving mixt, obtain catalyst solution 3 thus.Use monomer solution 3 and catalyst solution 3 to determine that be 23 minutes working life.

Tubule pump 13 and 14 is connected respectively to monomer solution jar 11 and catalyst solution jar 12, with 15ml/ minute flow solution is fed in the little static mixer 15 (identical with the agitator that uses among the embodiment 1) respectively with 0.12ml/ minute, obtain mixing solutions, this mixing solutions is fed to coated portion 16.

Width be the continuous extension of 100mm electro-deposition copper foil 18 (with use among the embodiment 1 identical) from the speed transmission of Copper Foil transmitting portions 17 with 50mm/sec so that in coated portion 16 continuously coating uneven surface to coat-thickness be 50 μ m.Then, transmitting thickness is that 75 μ m and width are that the banded PEN film 20 of successive of 100mm is from protective membrane transmitting portions 19 and be laminated on the coated side of Copper Foil.Make the light face of Copper Foil contact 15 seconds, finish polymerization with warming mill 21 160 ℃ of heating.Gained bonded resin Copper Foil is wound on the Copper Foil winding part 22 of protective membrane around binding resin.

Remove the Copper Foil of part binding resin from support membrane, and immerse dissolving resin part in the toluene.Measure the amount of residual monomer in the solution by the gas chromatographic analysis of solution.According to the residual quantity of gained residual monomer amount and copper, the calculating polymerisation conversion is 96wt%.

The Copper Foil of binding resin is attached to the two sides of the two-sided copper-clad layered product of glass epoxide (with the identical materials of using among the embodiment 2), and the resin face is in the inboard, and the gained material was 5.2MPa and 200 ℃ of following hot pressings 15 minutes.When exerting pressure, be cooled to 100 ℃ or lower after, shift out sample and obtain multilayer copper-clad layered product.

Embodiment 5

The apparatus for continous formation that in embodiment 5, uses Fig. 3 to show.600 gram Fourth Ring [6.2.1.13,6.02, the 7] 12-4-alkene of packing in the monomer solution jar 23 are used as monomer solution 4.Catalyst solution jar 24 is equipped with 1.1 gram benzylidene (1,3-two basic tetrahydroglyoxaline-4-subunits) (tricyclohexyl phosphine) ruthenous chloride and 1.6g triphenylphosphines.Add 44 gram toluene dissolving mixts, obtain catalyst solution 4 thus.Use monomer solution 4 and catalyst solution 4 to determine that be 5 minutes 30 seconds working life.

Tubule pump 25 and 26 is connected respectively to monomer solution jar 23 and catalyst solution jar 24, with 25ml/ minute flow velocity solution is fed in the little static mixer 27 (identical with the agitator that uses among the embodiment 1) respectively with 0.20ml/ minute, obtain mixing solutions, this mixing solutions is fed to coated portion 28.

Width be the electro-deposition copper foil 30 (identical) of the continuous extension of 100mm with the material that uses among the embodiment 1 from Copper Foil transmitting portions 29 with the speed of 50mm/sec to front transfer, so that the coating uneven surface.Simultaneously, width be the woven fiber glass 32 (with materials used among the embodiment 1 identical) of the continuous extension of 100mm from filamentary material transmitting portions 31 with the speed of 50mm/sec to front transfer, so that laminated glass cloth, and at continuous coating of coated portion 28 usefulness mixing solutionss and dipping.

Then, width be the continuous extension electro-deposition copper foil 34 (identical) of 100mm with top 30 material from Copper Foil transmitting portions 33 to front transfer, and be laminated on the glass cloth surface, uneven surface contacts with the glass cloth cover.Make the wet look of Copper Foil contact 15 seconds with hot-plate 35 220 ℃ of heating, and with press roller 37 compactings to finish polymerization.The two-sided copper-clad layered product of gained is reeled around two-sided copper-clad layered product winding part 36.The thermotolerance of the scolder of testing two-sided copper-clad layered product 260 ℃ of heating 20 seconds, confirms not occur bubbling in scolder is bathed.

＜the present invention solves the embodiment and the Comparative Examples of second purpose 〉

Embodiment 6

In the oval flask of 20ml, pack into 4.2mg benzylidene (1,3-two basic imidazolidine-2-subunits) (tricyclohexyl phosphine) ruthenous chloride and 6.6mg triphenylphosphine.Add 0.05ml toluene dissolving mixt.Add 8.1ml Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4-alkene (styrene content: 1mol%) in solution, stir simultaneously with the preparation feedback solution 1 (concentration of ruthenium: 0.6mmol/l).As compact dimensions is the mould of the plate of 0.5mm * 80mm * 80mm, has used the stainless steel plate that panel heater is of a size of 0.25mm * 100mm * 100mm for two and has been clamped by U type spacer (thickness 0.5mm).Reactive solution 1 is fed to mould (aforesaid operations carries out in room temperature (25 ℃)), and mould is heated to 220 ℃ with 80 ℃/minute heating rate.After the cooling, take out the flake products of moulding, and carry out hot analysis to measure.The Tg of matrix band is 201 ℃, and to add thermal residue be 97.5%.

From the result of embodiment 6 as can be seen, when heating rate height (80 ℃/minute), polymerisation conversion height (promptly adding thermal residue increases).

Embodiment 7

Have benzylidene (1,3-two basic imidazolidine-2-subunits) (tricyclohexyl phosphine) ruthenous chloride and 2.2mg triphenylphosphine that 1.4mg is housed in the glass flask of stirring rod.Add 0.03ml toluene, dissolving mixt obtains catalyst solution thus.With 8.1ml Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4-alkene (styrene content: 1mol%) join in the catalyst solution, stir simultaneously with the preparation feedback solution 2 (concentration of ruthenium: 0.2mmol/l).Reactive solution 2 is applied to the stainless steel plate that is heated to 220 ℃ to harden immediately with affirmation solution.Solid is removed fast, and obtaining thickness is the polymeric film of 0.1mm.The Tg of polymeric film is 205 ℃ and to add thermal residue be 98.8%.

Embodiment 8

Same way as with embodiment 7 prepares catalyst solution, and difference is not add triphenylphosphine.The mixing solutions of 8.0ml Dicyclopentadiene (DCPD) and cyclopentadiene tripolymer 9: 1 (weight ratio) is added catalyst solution, stir simultaneously with the preparation feedback solution 3 (concentration of ruthenium: 0.2mmol/l).

Reactive solution 3 is applied on the stainless steel plate that is heated to 180 ℃, to confirm that solution hardens immediately.Solid is removed fast, and obtaining thickness is the polymeric film of 0.1mm.The Tg of polymeric film is 165 ℃, and to add thermal residue be 98.5%.

Can find out from the result of embodiment 7 and 8, when heating immediately, can obtain desired product with high polymerization rate even catalytic amount reduces also.

Comparative Examples 2

Being of a size of the mould of the sheet of 0.5mm * 80mm * 80mm as formation, is that the aluminium sheet of 10mm * 100mm * 100mm is clamped by U type spacer (thickness 0.5mm) with two chip sizes of having used panel heater.Prepare sheet material in embodiment 6 identical modes, but heating rate is 12 ℃/minute.

The Tg of matrix band is 164 ℃, and to add thermal residue be 93.0%.

Comparative Examples 3

Prepare sheet material in Comparative Examples 2 identical modes, difference is to use reactive solution 3.It is 93.5% with adding thermal residue that the Tg of this sheet is 105 ℃.

From the result of Comparative Examples 2 and 3 as can be seen, when heating rate little (12 ℃/minute), polymerisation conversion low (promptly adding thermal residue reduces).

Reference example 1

Prepare sheet in Comparative Examples 3 identical modes, difference is to use by two aluminium sheets of the using board heating apparatus (mould of 10mm * 100mm * 100mm) form (3mm * 80mm * 80mm), this aluminium sheet is clamped by U type spacer (thickness 3mm), with the identical mode preparation feedback solution of reactive solution 1, difference is to use the component in the reactive solution 1 of 6 times of amounts.When die temperature reaches 61 ℃, because reaction heat and cigarette is emerged from the top of mould.

It is 98.5% with adding thermal residue that the Tg of gained sheet is 202 ℃.From the test-results of reference example 1 as can be seen, when the thickness thick (3mm) of mould, because reaction heat, temperature raises fast.Therefore, even when die temperature slowly raises, also can obtain desired product with high polymerization rate.

Comparative Examples 4

Reactive solution 3 is applied to the stainless steel plate that is heated to 80 ℃, and reacted 10 minutes, obtaining thickness is the polymeric film of 0.5mm.The Tg of polymeric film is 80 ℃, and to add thermal residue be 88.5%.

As can be seen, when preparation thickness is the die temperature of 1mm or thinner film when being 80 ℃, reaction heat is absorbed by mould, so this mould can not be used for abundant cured resin, causes the oligomerization transformation efficiency.

Comparative Examples 5

Same way as with embodiment 6 prepares flake products, and difference is to use two (tricyclohexyl phosphine) ruthenous chlorides of 4.1mg benzylidene to replace 4.2mg benzylidene (1,3 two basic imidazolidine-2-subunit) (tricyclohexyl phosphine) ruthenous chloride.The Tg of gained sheet is 145 ℃ and to add thermal residue be 91.5%.

Embodiment 9

Prepare catalyst solution in embodiment 7 identical modes, difference is to use the 2.7mg triphenylphosphine.With 7.0ml Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12-4-alkene (vinylbenzene that contains 1mol%), 3.4ml 5-ethene-2-norbornylene and 0.079ml vinylbenzene adds in this catalyst solution, and stir the mixture and obtain reactive solution 4.

Copper Foil (Furukawa Circuit Foil Co., Ltd. makes for TYPE GTS, thickness: 0.018mm) is placed on the plate, uneven surface upwards, and with nonwoven polyamide fabric sheet (" Kepler ", DuPontde Nemous ﹠amp; Co. make) cover.Behind dipping reactive solution 4, with teflon plate (thickness: 0.08mm) cover on the nonwoven polyamide fabric.

The gained layered product is taken out from plate, and be placed on the chromium plating iron plate of 150 ℃ of heating, Copper Foil is downward, then uses the hand roller (using handy roll) (aluminium bar of 80mm diameter is made) 150 ℃ of heating to suppress with cured resin immediately.Obtained to comprise the complex body of tynex and Copper Foil enhanced resin.

The industry practicality

According to first invention, flowability in the time of can or heating by continuously shaped effective acquisition storage stability With the excellent cycloolefin resin film of laminated property (lamination).

When the cycloolefin resin film that obtains by preparation method of the present invention is thermoplastic resin film, can lead to Cross laminated thermoplastic resin film and matrix, and heating and melting thermoplasticity resin part is with crosslinked, and effectively Preparation and matrix adhere to the crosslinked resin composite materials of property excellence. The crosslinked resin that obtains by this way is multiple Condensation material is made of cyclenes resin and the secure adhesion matrix to the cyclenes resin, and this cyclenes resin is at electric insulation The aspect excellences such as property, mechanical intensity, heat resistance, adhesion, dielectric properties, and be suitable for use as the electronics material Material, for example printed circuit board.

According to second invention, can be by in heating, ring-opening metathesis bulk polymerization solution Effectively preparation thickness is polymer sheet or the film of 1 millimeter or thinner cyclenes polymer, this reactive solution Contain ruthenium complex catalyst and cyclenes monomer, this catalyst has as containing of part of heteroatomic Cabbeen Compound.

Claims (14)

1. method for preparing cycloolefin resin film, it may further comprise the steps: step (I) hybrid ring alkene monomer and metathesis polymerization catalyzer are with preparation polymerisable compound (A); Step (II) uses polymerisable compound (A) to apply after step (I) or the dipping supporting mass immediately; And step (III) is by mass polymerization polymerization polymerisable compound (A).

2. according to the process of claim 1 wherein that step (II) is to carry out in the working life of polymerisable compound (A) in step (I) back.

3. according to the method for claim 1 or 2, wherein step (I) comprising: prepare polymerisable compound (A) by hybrid ring alkene monomer, metathesis polymerization catalyzer and chain-transfer agent.

4. according to each method among the claim 1-3, wherein step (I) comprises by hybrid ring alkene monomer, metathesis polymerization catalyzer and linking agent and prepares polymerisable compound (A).

5. according to each method among the claim 1-4, wherein step (III) comprising: use warming mill, hot-plate or process furnace to apply or the supporting mass that floods be heated to specified temperature with polymerisable compound (A), with by mass polymerization polymerization polymerisable compound (A).

6. according to each method among the claim 1-5, wherein the cyclenes monomer is a norbornene monomer.

7. according to each method among the claim 1-6, wherein mass polymerization is carried out in the following manner: use ruthenium complex as the metathesis polymerization catalyzer, with 20 ℃/minute or higher heating rate polymerisable compound (A) is heated to specified temperature more than 100 ℃, this complex compound has and contains heteroatomic carbene compound as part.

8. according to each method among the claim 1-7, wherein supporting mass is a tinsel.

9. according to each method among the claim 1-7, wherein supporting mass is made by filamentary material.

One kind to prepare thickness be 1 millimeter or the thinner cycloolefin polymer sheet or the method for film, it comprises: by ring-opening metathesis mass polymerization polymerisation reactivity solution, this reactive solution contains ruthenium complex catalyst and cyclenes monomer, described catalyzer has and contains heteroatomic carbene compound as part, wherein by with 20 ℃/minute or higher heating rate reactive solution being heated to 100 ℃ or highlyer finish the monomeric polymerization of cyclenes.

11. according to the method for claim 10, wherein reactive solution also comprises chain-transfer agent.

12. according to the method for claim 10 or 11, wherein with the polymeric reactive solution applies or the dipping supporting mass by the open loop mass polymerization.

13. according to the method for claim 12, wherein supporting mass is made by electro-conductive material.

14. according to the method for claim 12, wherein supporting mass is made by filamentary material.

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