Method for producing polymerizable oligomer composition and method for producing molded article

Abstract

To provide a production method that enables production of one-liquid type polymerizable composition having excellent storage stability and moldability.SOLUTION: A method for producing a polymerizable oligomer composition comprises: a polymerization step of obtaining a liquid oligomer composition derived from a cycloolefin monomer by adding a metathesis polymerization catalyst to a monomer liquid comprising the cycloolefin monomer and carrying out a polymerization rection of the cycloolefin monomer; and a cooling step of cooling the liquid oligomer composition to 0°C or less. The polymerization step is such that a polymerization reaction is conducted so that the viscosity [μ1] at 30°C of a liquid component in the liquid oligomer composition becomes larger by 3-150 cps than the viscosity [μ0] at 30°C of a liquid component in the monomer liquid, where the viscosities are values measured by using a B type viscometer at a number of revolution of 60 rpm.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a polymerizable oligomer composition and a method for producing a molded article.

Background Art

[0002] Cycloolefin polymers obtained by polymerizing cycloolefin monomers in the presence of a metathesis polymerization catalyst are excellent in electrical properties, mechanical properties, impact resistance properties, heat resistance, weather resistance, etc., and thus are used in a wide range of fields such as optical parts, electronic devices, medical instruments, and automotive parts.

[0003] Such cycloolefin polymers are produced, for example, by the reaction injection molding method in which a reaction solution containing a polymerizable monomer containing a cycloolefin monomer and a metathesis polymerization catalyst is injected into a mold and bulk polymerized. Here, since the cycloolefin monomer has high reactivity with the metathesis polymerization catalyst, in the reaction injection molding method, a monomer solution containing the cycloolefin monomer and a catalyst solution containing the metathesis polymerization catalyst are separately prepared, and a step of instantaneously mixing these plural solutions with a collision mixer or the like immediately before injecting them into the mold for molding is required. On the other hand, there is a demand for a molding method in which a one-component type polymerizable composition in which the cycloolefin monomer and the metathesis polymerization catalyst are already sufficiently mixed is prepared in advance and used.

[0004] For example, Patent Document 1 discloses a polymerizable composition obtained by cooling and solidifying a mixture containing a norbornene-based monomer and a metathesis polymerization catalyst.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a production method capable of producing a one-component polymerizable composition excellent in storage stability and moldability.

Means for Solving the Problems

[0007] The inventor of the present invention conducted studies to achieve the above object, and found that the above problems can be solved by a production method including a specific polymerization step and a cooling step, and thus completed the present invention.

[0008] That is, according to the present invention, there are provided a method for producing a polymerizable oligomer composition and a method for producing a molded article as follows. [1] A polymerization step of adding a metathesis polymerization catalyst to a monomer liquid containing a cycloolefin monomer and performing a polymerization reaction of the cycloolefin monomer to obtain an oligomer liquid composition containing an oligomer derived from the cycloolefin monomer, and A method for producing a polymerizable oligomer composition including a cooling step of cooling the oligomer liquid composition to 0°C or lower, wherein the polymerization step is a step of performing a polymerization reaction such that the viscosity [μ1] at 30°C of the liquid component in the oligomer liquid composition is 3 to 150 cps greater than the viscosity [μ0] at 30°C of the liquid component in the monomer liquid, The method for producing a polymerizable oligomer composition, wherein the viscosity is a value measured at a rotational speed of 60 rpm of a rotor using a B-type viscometer. [2] The method for producing a polymerizable oligomer composition according to [1], wherein the monomer liquid contains a cycloolefin monomer having no polar group as the cycloolefin monomer. [3] The method for producing a polymerizable oligomer composition according to [1] or [2], wherein the monomer liquid contains dicyclopentadienes and tricyclopentadiene as the cycloolefin monomer. [4] The production method of the polymerizable oligomer composition according to any one of [1] to [3], wherein the cooling step is a step of cooling and solidifying the oligomer liquid composition. [5] The production method of the polymerizable oligomer composition according to any one of [1] to [4], wherein the monomer liquid further contains a filler. [6] The production method of the polymerizable oligomer composition according to any one of [1] to [5], wherein the monomer liquid further contains a flame retardant. [7] The production method of the polymerizable oligomer composition according to any one of [1] to [6], wherein the monomer liquid further contains at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound. [8] A step of obtaining a polymerizable oligomer composition by the production method according to any one of [1] to [7], and A production method of a molded article comprising a polymerization step of bulk polymerizing the obtained polymerizable oligomer composition.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a production method capable of producing a one-component type polymerizable composition excellent in storage stability and moldability.

Embodiments for Carrying Out the Invention

[0010] The production method of the polymerizable oligomer composition of the present disclosure includes a multimerization step of adding a metathesis polymerization catalyst to a monomer liquid containing a cycloolefin monomer and performing a multimerization reaction of the cycloolefin monomer to obtain an oligomer liquid composition containing an oligomer derived from the cycloolefin monomer, and a cooling step of cooling the oligomer liquid composition to 0°C or lower. Here, the multimerization step is a step of performing a multimerization reaction such that the viscosity [μ1] at 30°C of the liquid component in the oligomer liquid composition is 3 to 150 cps greater than the viscosity [μ0] at 30°C of the liquid component in the monomer liquid.

[0011] By including such a multi - quantification step and a cooling step, the manufacturing method of the present disclosure can produce a one - component polymerizable composition excellent in storage stability and moldability. Specifically, the polymerizable oligomer composition obtained by the manufacturing method of the present disclosure is a one - component polymerizable composition in which a metathesis polymerization catalyst has been added in advance, and yet it is excellent in storage stability and can exhibit sufficient polymerizability even when stored for a long period. Further, the polymerizable oligomer composition obtained by the manufacturing method of the present disclosure is excellent in moldability and can be molded while ensuring uniformity.

[0012] <Multi - quantification step> In the multi - quantification step, a metathesis polymerization catalyst is added to a monomer liquid containing a cycloolefin monomer, and a multi - quantification reaction of the cycloolefin monomer is carried out to obtain an oligomer liquid composition containing an oligomer derived from the cycloolefin monomer.

[0013] The multi - quantification step is a step of carrying out a multi - quantification reaction such that the viscosity [μ1] of the liquid component at 30 ° C in the oligomer liquid composition is 3 - 150 cps greater than the viscosity [μ0] of the liquid component at 30 ° C in the monomer liquid. Here, the liquid component is a component that exhibits a liquid state in the monomer liquid and the oligomer liquid composition. Components present in a solid form in the monomer liquid and the oligomer liquid composition are not included in the above - mentioned liquid components. On the other hand, for example, a cycloolefin monomer and an oligomer derived from a cycloolefin monomer are usually included in the above - mentioned liquid components.

[0014] By the multi - quantification reaction of the cycloolefin monomer, an oligomer derived from the cycloolefin monomer is formed. The oligomer liquid composition may contain a cycloolefin monomer in addition to the oligomer derived from the cycloolefin monomer.

[0015] The value obtained by subtracting the viscosity [μ0] of the liquid component in the monomer liquid at a temperature of 30°C from the viscosity [μ1] of the liquid component in the oligomer liquid composition at a temperature of 30°C (μ1 - μ0; the increase in viscosity) is not particularly limited as long as it is 3 to 150 cps, preferably 5 to 100 cps, and more preferably 7 to 50 cps. Further, the value obtained by dividing the viscosity [μ1] of the liquid component in the oligomer liquid composition at a temperature of 30°C by the viscosity [μ0] of the liquid component in the monomer liquid at a temperature of 30°C (μ1 / μ0; the doubling rate of viscosity) is not particularly limited, but is preferably 2 to 50 times, more preferably 2.5 to 40 times, and even more preferably 3 to 30 times.

[0016] Note that the viscosity [μ0] of the liquid component in the monomer liquid at a temperature of 30°C is usually 1 to 6 cps, and the viscosity [μ1] of the liquid component in the oligomer liquid composition at a temperature of 30°C is usually 7 to 150 cps.

[0017] In the polymerization process, by increasing the viscosity of the liquid component within the above preferred range, the storage stability of the polymerizable oligomer composition can be further enhanced. Further, by increasing the viscosity of the liquid component within the above preferred range, the pot life when polymerizing the polymerizable oligomer composition can be extended, the fluidity can be improved, and the moldability can be further enhanced.

[0018] In the present disclosure, the viscosity is a value measured at a rotational speed of 60 rpm of the rotor using a B-type viscometer. Specifically, the viscosity can be measured by the method described in the examples.

[0019] The temperature of the polycondensation reaction is preferably 5 to 40°C, more preferably 10 to 35°C. The time of the polycondensation reaction is usually adjusted according to the temperature of the polycondensation reaction. For example, when the temperature of the polycondensation reaction is 25 to 35°C, the time of the polycondensation reaction is usually 30 to 150 seconds, preferably 40 to 120 seconds, and more preferably 50 to 100 seconds. When the time of the polycondensation reaction is within the above preferred range, it becomes easy to make the viscosity [μ0] at 30°C of the liquid component in the monomer solution within the above preferred range.

[0020] During the polycondensation reaction, the monomer solution and the metathesis polymerization catalyst may or may not be stirred and mixed. As the stirring and mixing method, a known method can be used.

[0021] <monomer solution> In the polycondensation step, a monomer solution containing a cycloolefin monomer is used.

[0022] [cycloolefin monomer] The cycloolefin monomer is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule. Examples of the alicyclic structure constituting the cycloolefin monomer include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combined polycyclic structures thereof. There is no particular limitation on the number of carbon atoms constituting the alicyclic structure, but it is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.

[0023] Examples of the cycloolefin monomer include monocyclic cycloolefin monomers and norbornene-based monomers, and norbornene-based monomers are preferred. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted by hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, aryl groups, and polar groups. Further, the norbornene-based monomer may have a double bond other than the double bond of the norbornene ring.

[0024] Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, 1,5-cyclooctadiene, and the like.

[0025] Specific examples of the norbornene-based monomer include dicyclopentadiene-based compounds such as dicyclopentadiene, methyldicyclopentadiene, and dicyclopentadiene monoepoxide; tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-4-ene, 9-ethylidene tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-4-ene, 9-phenyl tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-4-ene, tetracyclo[6.2.1.1 3,6 .0 2,7 dodeca-9-ene-4-carboxylic acid, tetracyclo[6.2.1.1 3,6 .0 2,7 tetracyclododecene-based compounds such as dodeca-9-ene-4,5-dicarboxylic anhydride; norbornene-based compounds such as 2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic anhydride; oxanorbornene-based compounds such as 7-oxa-2-norbornene and 5-ethylidene-7-oxa-2-norbornene; tetracyclo[9.2.1.0 2,10 .0 3,8 tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 pentadeca-4,10-diene, pentacyclo[9.2.1.0 2,10 .0 3,8Examples include polycyclic olefins with four or more rings such as pentadec-5,12-diene and tricyclopentadiene; etc.

[0026] Among these cycloolefin monomers, it is preferable to use a cycloolefin monomer having no polar group because a molded article with low water absorption can be obtained. Also, tetracyclo[9.2.1.0 2,10 .0 3,8 Using those having an aromatic condensed ring such as tetradeca-3,5,7,12-tetraene can further enhance the moldability of the polymerizable oligomer composition.

[0027] These cycloolefin monomers may be used alone or in combination of two or more. In addition, the monomer liquid may contain any monomer copolymerizable with the cycloolefin monomer as long as the effects of the present invention are not inhibited.

[0028] The monomer liquid preferably contains dicyclopentadienes as the cycloolefin monomer, and more preferably contains dicyclopentadienes and tricyclopentadiene. When the monomer liquid contains dicyclopentadienes and tricyclopentadiene, their content ratios are preferably in the ratio represented by [content of dicyclopentadienes: content of tricyclopentadiene] of 60:40 to 99:1, and more preferably 80:20 to 95:5. When the content ratio is within the above range, the moldability of the polymerizable oligomer composition can be further enhanced.

[0029] In the liquid component in the monomer liquid, the proportion occupied by the cycloolefin monomer is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass. When the proportion occupied by the cycloolefin monomer is within the above range, the mechanical properties of the molded article obtained from the polymerizable oligomer composition can be enhanced.

[0030] [(Meth)acrylate-based monomer] The monomer liquid may further contain a (meth)acrylate monomer in addition to the cycloolefin monomer as a monomer component.

[0031] The (meth)acrylate monomer may be a polyfunctional monomer having three or more (meth)acryloyl groups, but a monofunctional monomer having one (meth)acryloyl group or a difunctional monomer having two (meth)acryloyl groups is preferable, and a monofunctional monomer is more preferable. Further, as the (meth)acrylate monomer, a methacrylate monomer is preferable.

[0032] Since the (meth)acrylate monomer is excellent in expressing effects, it preferably has a hydrocarbon group having 6 or more carbon atoms. The number of carbon atoms of the hydrocarbon group is preferably 6 to 100, more preferably 8 to 50, and still more preferably 10 to 20.

[0033] Specific examples of the monofunctional monomer having one (meth)acryloyl group include benzyl methacrylate, hexyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, octenyl methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol methacrylate, phenoxyethylene glycol methacrylate, dicyclopentenyl oxyethyl methacrylate, dicyclopentanyl methacrylate, and the like.

[0034] Specific examples of the bifunctional monomer having two (meth)acryloyl groups include ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adamantyl dimethanol dimethacrylate, 2,2'-bis(4-methacryloxy diethoxyphenyl)propane and the like.

[0035] Specific examples of the polyfunctional monomer having three or more (meth)acryloyl groups include trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and the like.

[0036] The monofunctional monomer having one (meth)acryloyl group, the bifunctional monomer having two (meth)acryloyl groups and the polyfunctional monomer having three or more (meth)acryloyl groups may be arbitrarily combined in any ratio and used.

[0037] The content of the (meth)acrylate monomer in the monomer liquid is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of all the cycloolefin monomers used. By setting the content of the (meth)acrylate monomer within the above range, the mechanical properties of the molded body obtained from the polymerizable oligomer composition can be enhanced.

[0038] [Filler] The monomer liquid may further contain a filler. Examples of the filler include inorganic fillers and organic fillers.

[0039] Examples of the inorganic filler include metal oxides such as silica, alumina, titanium oxide, zinc oxide, and antimony oxide; metal hydrates such as aluminum hydrates like aluminum monohydrate, magnesium hydrate, calcium hydrate, nickel hydrate, iron hydrate, copper hydrate, zinc borate hydrate, and zinc stannate hydrate; metal nitrides such as silicon nitride and boron nitride; carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate; calcium hydroxide; aluminum hydroxide; magnesium hydroxide; calcium silicate; calcium sulfate; barium titanate; red phosphorus; various metal powders; clay; various ferrites; hydrotalcite; glass; carbon-based materials such as carbon black, graphite, and fullerene; etc. The inorganic filler may be used alone or in combination of two or more kinds.

[0040] As the filler, at least one selected from metal oxides, metal hydrates, metal nitrides, and glass is preferable, at least one selected from silica, aluminum monohydrate, and glass is more preferable, and at least one selected from silica and glass is even more preferable.

[0041] The shape of the filler is not particularly limited and may be, for example, flaky particles or spherical particles.

[0042] The filler may be one having its surface hydrophobized. By using a hydrophobized filler, aggregation and sedimentation of the filler in the polymerizable oligomer composition can be suppressed, and the moldability of the polymerizable oligomer composition can be further enhanced. Examples of the treatment agent used for the hydrophobization treatment include silane coupling agents such as vinyltrimethoxysilane, titanate-based coupling agents, aluminate-based coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc. Note that the hydrophobization treatment of the filler is also possible by mixing the treatment agent simultaneously with the filler when preparing the monomer liquid.

[0043] When the monomer liquid contains a filler, the content of the filler is not particularly limited, but is preferably 10 to 1000 parts by mass, more preferably 30 to 750 parts by mass, and still more preferably 100 to 500 parts by mass with respect to 100 parts by mass of all the cycloolefin monomers used. By setting the content of the flame retardant within the above range, the mechanical properties of the molded body obtained from the polymerizable oligomer composition can be enhanced.

[0044] [Flame retardant] The monomer liquid may further contain a flame retardant. As the flame retardant, any of solids, liquids, and combinations thereof can be used.

[0045] Examples of the flame retardant include phosphorus-based flame retardants, nitrogen / phosphorus-based flame retardants, nitrogen-based flame retardants, etc. Note that as the flame retardant, it is preferable to use a non-halogen-based flame retardant that does not generate halogen-containing harmful substances during incineration. The monomer liquid preferably does not contain a halogen-based flame retardant that generates halogen-containing harmful substances during incineration.

[0046] The phosphorus-based flame retardant is a flame retardant having a phosphorus atom and no nitrogen atom. Examples of the phosphorus-based flame retardant include organic phosphorus-based flame retardants and inorganic phosphorus-based flame retardants. Examples of the organic phosphorus-based flame retardant include phosphate esters such as triphenyl phosphate; organic phosphonic acid compounds such as diphenyl methanephosphonate and diethyl phenylphosphonate; organic phosphinic acid compounds such as methyl phosphinate; phosphine oxides such as triphenylphosphine oxide and tricresylphosphine oxide; etc. Examples of the inorganic phosphorus-based flame retardant include red phosphorus; orthophosphoric acid; phosphorous acid; hypophosphorous acid; polyphosphoric acids such as metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid; polyphosphorous acids such as metaphosphorous acid and pyrophosphorous acid; non-condensed (meta)phosphates; condensed (meta)phosphates; etc. Among these, phosphine oxide is preferable.

[0047] Nitrogen / phosphorus-based flame retardants are flame retardants having phosphorus atoms and nitrogen atoms. Examples of nitrogen / phosphorus-based flame retardants include melamine phosphate compounds such as melamine polyphosphate, melamine orthophosphate, and melamine pyrophosphate; piperazine phosphate compounds such as piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate; phosphonitrile compounds such as phenyl phosphonitrilate and (poly)phenoxyphosphazene; phosphate ester amides; phosphate amides; ammonium phosphates such as ammonium monophosphate, ammonium diphosphate, ammonium triphosphate, and ammonium polyphosphate; etc. Among these, melamine polyphosphate, melamine polyphosphate, and phenyl phosphonitrilate are preferred.

[0048] Nitrogen-based flame retardants are flame retardants having nitrogen atoms without having phosphorus atoms. Examples of nitrogen-based flame retardants include guanidine compounds, melamine compounds, and triazine compounds. Among these, melamine compounds are preferred, and melamine cyanurate is more preferred.

[0049] When the monomer liquid contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and still more preferably 30 to 100 parts by mass with respect to 100 parts by mass of all cycloolefin monomers used. By setting the content of the flame retardant within the above range, the flame retardancy and mechanical properties of the molded body obtained from the polymerizable oligomer composition can be enhanced.

[0050] The monomer liquid may optionally contain at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

[0051] The coupling agent is not particularly limited, but examples thereof include silane coupling agents having at least one hydrocarbon group having a norbornene structure (norbornene skeleton). Specific examples of such silane coupling agents include bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, bicycloheptenylhexyltriethoxysilane, etc. Among them, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane are preferred, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, and bicycloheptenylhexyltrimethoxysilane are more preferred, and bicycloheptenylethyltrimethoxysilane is even more preferred.

[0052] In addition, the monomer solution may contain a silane coupling agent having no hydrocarbon group having a norbornene structure, a thiol coupling agent, an aluminate coupling agent, a titanate coupling agent, or a coupling agent other than a silane coupling agent such as fatty acid esters.

[0053] The content of the coupling agent in the monomer solution is not particularly limited, but is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass with respect to 100 parts by mass of all the cycloolefin monomers used.

[0054] The radical generator has the action of generating radicals by heating, thereby inducing a crosslinking reaction in the molded body obtained from the polymerizable oligomer composition. The site where the radical generator induces the crosslinking reaction is mainly the carbon-carbon double bond contained in the polymer component in the obtained molded body, but crosslinking may also occur at the saturated bond portion.

[0055] Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. Examples of the organic peroxides include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and t-butyl cumyl peroxide; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; peroxyketals such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, and 1,3-di(t-butylperoxyisopropyl)benzene; peroxy esters such as t-butyl peroxyacetate and t-butyl peroxybenzoate; peroxy carbonates such as t-butyl peroxyisopropyl carbonate and di(isopropylperoxy)dicarbonate; and alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide. Among them, dialkyl peroxides are particularly preferred in that they cause less hindrance to the metathesis polymerization reaction in bulk polymerization.

[0056] Examples of the diazo compounds include 4,4'-bisazidobenzal(4-methyl)cyclohexanone, 4,4'-diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone, 4,4'-diazidodiphenyl sulfone, 4,4'-diazidodiphenylmethane, and 2,2'-diazidostilbene.

[0057] Examples of the non-polar radical generator include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

[0058] The amount of the radical generator in the monomer solution is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of all the cycloolefin monomers used.

[0059] Examples of the diisocyanate compounds include aromatic diisocyanate compounds such as 4,4'-methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate dibenzyl; aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanate compounds such as 4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI, and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols or polyamines so that the terminals become isocyanate. Further, those having polyfunctional isocyanate groups in the form of isocyanurate, biuret, adduct, or polymeric forms of these compounds, which are known and have been conventionally used, can be used without particular limitation. Examples of such compounds include dimers of 2,4-tolylene diisocyanate, triphenylmethane triisocyanate, tris-(p-isocyanate phenyl) thiophosphite, polyfunctional aromatic isocyanate compounds, polyfunctional aromatic aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid-modified polyfunctional aliphatic isocyanate compounds, polyfunctional blocked-type isocyanate compounds such as blocked polyfunctional aliphatic isocyanate compounds, and polyisocyanate prepolymers.Among these, aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional non-blocked isocyanate compounds, are preferably used because of their excellent availability and ease of handling. These compounds can be used alone or in combination of two or more thereof.

[0060] The polyfunctional blocked isocyanate compound is one in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound to be inactivated at normal temperature. The isocyanate compound generally has a structure in which the isocyanate groups are masked by a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. The polyfunctional blocked isocyanate compound generally does not react at normal temperature and thus has excellent storage stability, but the isocyanate groups are usually regenerated by heating at 140 to 200 °C and can exhibit excellent reactivity.

[0061] The diisocyanate compounds may be used alone or in combination of two or more thereof. The blending amount of the diisocyanate compound in the monomer liquid is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of all the cycloolefin monomers.

[0062] By using the polyfunctional (meth)acrylate compound together with the diisocyanate compound, it is presumed that the function as an adhesion improver or an adhesion imparting agent of the diisocyanate compound is synergistically enhanced. Preferred examples of the polyfunctional (meth)acrylate compound include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.

[0063] The polyfunctional (meth)acrylate compound may be used alone or in combination of two or more thereof. The blending amount of the polyfunctional (meth)acrylate compound in the monomer liquid is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of all the cycloolefin monomers used.

[0064] The monomer liquid may contain, as other optional components, an activator, an activity regulator, an elastomer, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like.

[0065] The activator acts as a co-catalyst for the metathesis polymerization catalyst and is a compound that improves the polymerization activity of the catalyst. Examples of the activator include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides in which a part of the alkyl group of these alkylaluminum halides is substituted with an alkoxy group; and organotin compounds. The amount of the activator used is not particularly limited, but is preferably 0.1 to 100 moles, more preferably 1 to 10 moles, per 1 mole of all the metathesis polymerization catalysts used in the polycondensation step.

[0066] The activity regulator can be selected according to the type of the metathesis polymerization catalyst. Examples of the activity regulator when using a compound of a transition metal of Group 5 or Group 6 of the periodic table as the metathesis polymerization catalyst include compounds having an action of reducing the metathesis polymerization catalyst, and alcohols, haloalcohols, esters, ethers, nitriles, etc. can be used. Among them, alcohols and haloalcohols are preferred, and haloalcohols are more preferred.

[0067] Specific examples of the alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, t-butyl alcohol and the like. Specific examples of the haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, 1-chlorobutanol and the like.

[0068] As a metathesis polymerization catalyst, especially when using a ruthenium carbene complex, examples of the activity regulator include Lewis base compounds. Examples of the Lewis base compounds include Lewis base compounds containing a phosphorus atom such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenyl phosphite, n-butylphosphine; Lewis base compounds containing a nitrogen atom such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, imidazole, and the like. Further, norbornenes substituted with an alkenyl group such as vinylnorbornene, propenylnorbornene, and isopropenylnorbornene are both the above-mentioned cycloolefin monomers and also act as activity regulators. The amount of these activity regulators used may be appropriately adjusted depending on the compound used.

[0069] Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and their hydrogenated products. By dissolving the elastomer in the monomer solution and using it, the viscosity can be adjusted. Further, by adding the elastomer, the impact resistance of the molded body obtained from the polymerizable oligomer composition can be improved. The amount of the elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of all the cycloolefin monomers used.

[0070] Examples of the antioxidant include various antioxidants for plastics and rubbers such as phenolic, phosphorus-based, and amine-based antioxidants.

[0071] As the monomer liquid, it is preferable that the resulting polymerizable oligomer composition can be bulk polymerized to obtain a solid bulk polymer. In the liquid component of the monomer liquid, the proportion of the monomer component containing the cycloolefin monomer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 98 to 100% by mass. When the proportion of the monomer component is within the above range, the mechanical properties of the molded body obtained from the polymerizable oligomer composition can be enhanced.

[0072] The monomer liquid is prepared by appropriately mixing the above components according to a known method.

[0073] <Metathesis polymerization catalyst> In the multimerization step, a metathesis polymerization catalyst is added to the monomer liquid containing the cycloolefin monomer.

[0074] The metathesis polymerization catalyst is not particularly limited as long as it can ring-open polymerize the cycloolefin monomer, and known ones can be used.

[0075] The metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions, and / or compounds with a transition metal atom as the central atom. As the transition metal atom, atoms of Groups 5, 6, and 8 (long-period type periodic table, the same applies hereinafter) are used. The atoms of each group are not particularly limited. Examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include ruthenium and osmium. Among these transition metal atoms, ruthenium and osmium of Group 8 are preferred. That is, as the metathesis polymerization catalyst, a complex having ruthenium or osmium as the central atom is preferred, and a complex having ruthenium as the central atom is more preferred. As the complex having ruthenium as the central atom, a ruthenium carbene complex formed by coordinating a carbene compound to ruthenium is preferred. Here, the "carbene compound" is a general term for compounds having a methylene free radical and refers to a compound having a divalent carbon atom (carbene carbon) without charge as represented by (>C:). The ruthenium carbene complex is excellent in catalytic activity during bulk ring-opening polymerization, so the resulting polymer has little odor derived from unreacted monomers, and a high-quality polymer can be obtained with good productivity. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so it can be used even under the atmosphere. The metathesis polymerization catalyst may be used alone or in combination of a plurality of types.

[0076] Examples of the ruthenium carbene complex include those represented by the following general formula (1) or general formula (2).

Chemical formula

[0077] In the above general formulas (1) and (2), R 1 and R 2is, independently of each other, a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have substituents and may also be bonded to each other to form a ring. R 1 and R 2 Examples of the case where and are bonded to each other to form a ring include indenylidene groups which may have substituents, such as phenylindenylidene groups.

[0078] Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an alkylsulfinyl group having 1 to 20 carbon atoms, an alkylsulfonic acid group having 1 to 20 carbon atoms, an arylsulfonic acid group having 6 to 20 carbon atoms, a phosphonic acid group, an arylphosphonic acid group having 6 to 20 carbon atoms, an alkylammonium group having 1 to 20 carbon atoms, and an arylammonium group having 6 to 20 carbon atoms, etc. These organic groups having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom may have substituents. Examples of the substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, etc.

[0079] X 1 and X 2 each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand which has a negative charge when separated from the central metal atom, and examples thereof include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, a carboxyl group, etc.

[0080] L 1 and L 2 represents a heteroatom-containing carbene compound or a neutral electron-donating compound other than a heteroatom-containing carbene compound. A heteroatom-containing carbene compound and a neutral electron-donating compound other than a heteroatom-containing carbene compound are compounds that have a neutral charge when separated from the central metal. From the viewpoint of improving catalytic activity, a heteroatom-containing carbene compound is preferred. A heteroatom means an atom of Group 15 and Group 16 of the periodic table, and specific examples include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom, etc. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferred, and a nitrogen atom is more preferred.

[0081] As the heteroatom-containing carbene compound, a compound represented by the following general formula (3) or (4) is preferred, and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferred.

Chemical formula

[0082] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulas (1) and (2). Also, R 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.

[0083] In addition, since the effects of the present invention become even more remarkable, R 5 and R 6 are preferably hydrogen atoms. Also, R 3 and R 4 are preferably aryl groups which may have substituents, more preferably phenyl groups having an alkyl group with 1 to 10 carbon atoms as a substituent, and even more preferably mesityl groups.

[0084] Examples of the neutral electron-donating compound include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0085] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may each be bonded to each other alone and / or in any combination to form a polydentate chelating ligand.

[0086] Among the compounds represented by the above general formula (1) or (2), the ruthenium carbene complex is preferably a compound represented by the above general formula (1) from the viewpoint that the effects of the present invention become more remarkable. Among them, a compound represented by the following general formula (5) or general formula (6) is even more preferable.

[0087] The general formula (5) is shown below.

Chemical formula

[0088] In the above general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, NR 12 , PR 12 or AsR 12 , and R 12is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; however, since the effects of the present invention become more remarkable, an oxygen atom is preferable as Z.

[0089] In addition, R 1 and R 2 and X 1 and L 1 are the same as in the cases of the above general formulas (1) and (2), and may each independently and / or in any combination bond to each other to form a polydentate chelating ligand. However, X 1 and L 1 do not form a polydentate chelating ligand, and it is preferable that R 1 and R 2 bond to each other to form a ring, more preferably an indenylidene group which may have a substituent, and even more preferably a phenylindenylidene group. Further, specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as in the cases of the above general formulas (1) and (2).

[0090] In the above general formula (5), R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms, and these groups may have a substituent and may also bond to each other to form a ring. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. The ring formed when forming a ring may be any of an aromatic ring, an alicyclic ring and a heterocyclic ring, but it is preferable to form an aromatic ring, more preferably to form an aromatic ring having 6 to 20 carbon atoms, and even more preferably to form an aromatic ring having 6 to 10 carbon atoms.

[0091] In the above general formula (5), R 9 and R 10 and R 11is, independently of each other, a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; these groups may have substituents and may be bonded to each other to form a ring. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the case of the above general formulas (1) and (2). R 9 , R 10 and R 11 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0092] Specific examples of the compound represented by the above general formula (5) and its production method include, for example, those described in International Publication No. 03 / 062253 (Japanese Patent Application Laid-Open No. 2005-515260).

[0093] The general formula (6) is shown below.

Chemical formula

[0094] In the above general formula (6), m is 0 or 1. m is preferably 1, and in that case, Q is an oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, an ethylene group or a carbonyl group, preferably a methylene group.

[0095] In the above general formula (6),

Chemical formula

[0096] R 1 , X 1 , X 2 and L 1is the same as in the case of the above general formulas (1) and (2), and may be combined with each other alone and / or in any combination to form a multidentate chelating ligand, but X 1 and X 2 and L 1 do not form a multidentate chelating ligand, and R 1 is preferably a hydrogen atom.

[0097] R 13 to R 21 are a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; and these groups may have substituents and may be bonded to each other to form a ring. Further, specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as in the case of the above general formulas (1) and (2). R 13 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, R 14 to R 17 are preferably hydrogen atoms, and R 18 to R 21 are preferably hydrogen atoms or halogen atoms.

[0098] In addition, specific examples of the compound represented by the above general formula (6) and its production method include, for example, those described in International Publication No. 11 / 079799 (Special Table 2013-516392).

[0099] In addition, as the compound represented by the above general formula (1), in addition to the compounds represented by the above general formula (5) or general formula (6), the following compound (7) can also be preferably used. In compound (7), PCy3 represents tricyclohexylphosphine, and Mes represents a mesityl group.

Chemical formula

[0100] The content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and still more preferably 0.015 to 20 mmol, per 1 mol of all the cycloolefin monomers used in the reaction.

[0101] In the multimerization step, when adding the metathesis polymerization catalyst to the monomer liquid containing the cycloolefin monomer, a solution or dispersion of the metathesis polymerization catalyst in a small amount of an inert solvent can be used. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; diethyl ether, dichloromethane, dimethyl sulfoxide, ethyl acetate, etc. Among them, aromatic hydrocarbons are preferred, and toluene is more preferred.

[0102] <Cooling step> The production method of the present disclosure further includes a cooling step of cooling the oligomer liquid composition obtained in the above multimerization step to 0 °C or lower. In the cooling step, the oligomer liquid composition whose viscosity [μ1] at a temperature of 30 °C is adjusted within the above range is used.

[0103] The cooling temperature in the cooling step is not particularly limited as long as it is 0 °C or lower, but -20 °C or lower is preferred, -30 °C or lower is more preferred, -40 °C or lower is still more preferred, -45 °C or lower is particularly preferred, and -50 °C or lower is most preferred. When the cooling temperature is within the above preferred range, the storage stability of the polymerizable oligomer composition can be further enhanced, and sufficient polymerizability can be exhibited even when stored for an extremely long period. Also, when the cooling temperature is within the above preferred range, the pot life when polymerizing the polymerizable oligomer composition can be extended, the fluidity can be improved, and the moldability can be further enhanced. The lower limit value of the cooling temperature is not particularly limited, but is usually -196 °C or higher.

[0104] In the cooling step, it is preferable to cool the oligomer liquid composition to solidify it into a freeze-solidified body. That is, the cooling temperature in the cooling step is preferably equal to or lower than the solidification temperature of the oligomer liquid composition. Specifically, the cooling temperature in the cooling step is preferably 5°C or more lower than the solidification temperature of the oligomer liquid composition, more preferably 10°C or more lower, and even more preferably 15°C or more lower.

[0105] The polymerizable oligomer composition obtained in the cooling step may be stored for a long period of time. The polymerizable oligomer composition obtained by the production method of the present disclosure has excellent storage stability and can exhibit sufficient polymerizability even when stored for a long period of time. The storage period is not particularly limited and can be, for example, from several days to several months.

[0106] The cooling method in the cooling step is not particularly limited, and a known method can be adopted.

[0107] <Method for manufacturing a molded body> A molded body can be manufactured by a production method including a polymerization step of bulk polymerizing the polymerizable oligomer composition obtained in the above cooling step. The present disclosure also relates to such a method for manufacturing a molded body.

[0108] When manufacturing a molded body, usually, after injecting the polymerizable oligomer composition into a mold, the polymerizable oligomer composition is bulk polymerized. When the polymerizable oligomer composition is a freeze-solidified body, it may be heated and melted and then injected into the mold. As the mold, one having a desired shape can be used.

[0109] In addition, a molding method for a minute molded body, such as an extrusion molding method, can be applied to the polymerizable oligomer composition. The polymerizable oligomer composition is excellent in storage stability and moldability, and moreover, since it is a one-component type polymerizable composition in which a monomer liquid containing a cycloolefin monomer and a metathesis polymerization catalyst are already mixed, it can be suitably used for manufacturing a minute molded body.

[0110] <Coincidence process> In the coincidence process, the polymerizable oligomer composition is bulk polymerized. The bulk polymerization is usually carried out by heating the polymerizable oligomer composition cooled in the cooling process.

[0111] The heating temperature (initial temperature) in the coincidence process is preferably 0 °C or higher, more preferably 10 °C or higher, from the viewpoint of productivity. Usually, the bulk polymerization is an exothermic reaction, and as the bulk polymerization proceeds, the temperature inside the system becomes higher than the initial temperature. The bulk polymerization time can be determined according to the temperature inside the system and the composition of the polymerizable oligomer composition. For example, when the heating temperature (initial temperature) in the coincidence process is 20 to 40 °C, the bulk polymerization time can be 5 minutes to 5 hours.

[0112] The bulk polymerization may be carried out in two stages if necessary. For example, in the first stage, the bulk polymerization is carried out to such an extent that the polymerizable oligomer composition loses its fluidity to obtain a solid or gel-like primary cured product, and in the second stage, the primary cured product is heated to further proceed with the bulk polymerization to obtain a secondary cured product.

[0113] In this case, the heating temperature (initial temperature) in the first stage is preferably 5 °C or higher, more preferably 10 °C or higher, and even more preferably 20 to 40 °C. Also, the reaction time in the first stage can be determined according to the temperature inside the system. For example, when the heating temperature (initial temperature) in the first stage is 20 to 40 °C, the reaction time in the first stage is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour.

[0114] The heating temperature (initial temperature) in the second stage is preferably 60 to 300 °C, more preferably 100 to 180 °C. The reaction time in the second stage is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour.

[0115] The molded article obtained by the production method of the present disclosure has characteristics such as heat resistance, low water absorption, and low dielectric constant, and is preferably used as various members that require these characteristics. In particular, it is preferably used as a sealing material for protecting components in electrical and electronic applications.

Examples

[0116] Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples. In addition, "parts" and "%" are based on mass unless otherwise specified. Further, various tests and evaluations were conducted according to the following methods.

[0117] (Viscosity) The viscosity was measured using a B-type viscometer (trade name "TVB-25L", rotor type "M1", manufactured by Toki Sangyo Co., Ltd.) at a rotor rotation speed of 60 rpm.

[0118] (Homogeneity of the secondary cured product) The homogeneity of the secondary cured product of the polymerizable composition was visually confirmed. When uncured sites were unevenly distributed and when thickness unevenness was confirmed, it was judged that the homogeneity was poor. Also, in the examples and comparative examples using a filler, when the filler was unevenly distributed, it was judged that the homogeneity was poor. On the other hand, when these problems were not confirmed, it was judged that the homogeneity was excellent.

[0119] (Presence or absence of voids in the secondary cured product) The presence or absence of voids in the secondary cured product of the polymerizable composition was visually confirmed.

[0120] (Adhesion of the secondary cured product) An attempt was made to peel the secondary cured product of the polymerizable composition from the Si dummy wafer. When peeling was difficult, it was judged that the adhesion was excellent, and when peeling was easy, it was judged that the adhesion was poor.

[0121] <Example 1> (Preparation of the monomer solution) 95.3 parts of RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenyl ethyltrimethoxysilane, and 0.8 part of phenoxyethylene glycol methacrylate were mixed to prepare a monomer solution. The composition of the above RIM monomer consists of about 90% by mass of dicyclopentadiene and about 10% by mass of tricyclopentadiene.

[0122] (Polymerization process, cooling process, and polymerization process) The temperature of the monomer solution obtained above was adjusted to 30°C. To the monomer solution at 30°C, 0.04 part of the compound (7) was added as a metathesis polymerization catalyst, and after stirring the whole for a short time, it was allowed to stand at 30°C for 60 seconds to carry out a polymerization reaction. The amount of the metathesis polymerization catalyst used was 0.055 mmol per 1 mol of the total cycloolefin monomer. At the time when 60 seconds had elapsed after the addition of the metathesis polymerization catalyst, the obtained oligomer liquid composition was rapidly cooled to -85°C to obtain a frozen solid (the polymerizable oligomer composition of Example 1). The obtained frozen solid was allowed to stand at -85°C for 14 days. When the frozen solid after standing for 14 days was allowed to stand in a room at 25°C, bulk polymerization proceeded and a hardened molded body was obtained.

[0123] (Measurement of viscosity in the polymerization process) A monomer solution was prepared in the same manner as above and the temperature was adjusted to 30°C. When the viscosity of the monomer solution at 30°C was measured by setting it in a B-type viscometer, it was 3 mPa·s. Also, to the monomer solution at 30°C prepared in the same manner, 0.04 part of the compound (7) was added as a metathesis polymerization catalyst, and after stirring the whole for a short time, it was allowed to stand at 30°C for 60 seconds to carry out a polymerization reaction. At the time when 60 seconds had elapsed after the addition of the metathesis polymerization catalyst, the obtained oligomer liquid composition was set in a B-type viscometer and the viscosity was quickly measured. The viscosity was 10 mPa·s.

[0124] (Measurement of viscosity in the polymerization process) In the same manner as above, a frozen solid (the polymerizable oligomer composition of Example 1) was obtained and allowed to stand at a temperature of -85°C for 14 days, and then allowed to stand in a room at 25°C. When the temperature of the frozen solid rose from -85°C to about -35°C, the solid content disappeared and a liquid polymerizable composition was obtained. When the solid content disappeared, the liquid polymerizable composition was immediately set in a B-type viscometer to measure the viscosity. The viscosity was 13.9 mPa·s. Further, the liquid polymerizable composition was allowed to stand in a room at 25°C, and the viscosity at the time when 1800 seconds had elapsed after the disappearance of the solid content was measured in the same manner, and the viscosity was 30.0 mPa·s.

[0125] <Example 2> (Polymerization process, cooling process, and polymerization process) A frozen solid (the polymerizable oligomer composition of Example 2) was obtained in the same manner as in Example 1, except that the polymerization reaction time was changed from 60 seconds to 90 seconds. The obtained frozen solid was allowed to stand at a temperature of -85°C for 14 days, and then allowed to stand in a room at 25°C. As a result, bulk polymerization proceeded and a hardened molded body was obtained.

[0126] (Measurement of viscosity in the polymerization process) The viscosity of the oligomer liquid composition at the time when 90 seconds had elapsed after the addition of the metathesis polymerization catalyst was measured in the same manner as in Example 1. The viscosity was 50 mPa·s.

[0127] (Measurement of viscosity in the polymerization process) In the same manner as described above, a frozen solid (the polymerizable oligomer composition of Example 2) was obtained and allowed to stand at a temperature of -85°C for 14 days, and then allowed to stand in a room at 25°C. When the temperature of the frozen solid rose from -85°C to about -35°C, the solid content disappeared, and a liquid polymerizable composition was obtained. At the time when the solid content disappeared, the liquid polymerizable composition was quickly set in a B-type viscometer to measure the viscosity. The viscosity was 49.8 mPa·s. Further, the liquid polymerizable composition was allowed to stand in a room at 25°C, and the viscosity at the time when 900 seconds had elapsed after the solid content disappeared was measured in the same manner. As a result, the viscosity was 74.9 mPa·s. Similarly, when the liquid polymerizable composition was allowed to stand in a room at 25°C, the curing of the polymerizable composition was confirmed at the time when 3600 seconds had elapsed after the solid content disappeared.

[0128] <Example 3> (Polymerization process, cooling process, and polymerization process) A frozen solid (the polymerizable oligomer composition of Example 3) was obtained in the same manner as in Example 1, except that the polymerization reaction time was changed from 60 seconds to 120 seconds. The obtained frozen solid was allowed to stand at a temperature of -85°C for 14 days, and then allowed to stand in a room at 25°C. As a result, bulk polymerization proceeded, and a cured molded body was obtained.

[0129] (Measurement of viscosity in the polymerization process) The viscosity of the oligomer liquid composition at the time when 120 seconds had elapsed after the addition of the metathesis polymerization catalyst was measured in the same manner as in Example 1. The viscosity was 100 mPa·s.

[0130] <Example 4> (Polymerization process, cooling process, and polymerization process) In the same manner as in Example 1, a frozen solid (the polymerizable oligomer composition of Example 1 and Example 4) was obtained, allowed to stand at a temperature of -85°C for 7 days, and then allowed to stand in a room at 25°C. Thereafter, the solid content of the frozen solid disappeared, and a liquid polymerizable composition was obtained. The obtained liquid polymerizable composition was supplied to a molding apparatus, and coating molding of a 12-inch Si dummy wafer was performed. Then, by performing primary curing and secondary curing of the polymerizable composition, a molded body in which the Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained. The detailed conditions are shown below.

[0131] (Coating conditions) Molding apparatus: Trade name "CPM1080", a molding apparatus for wafer-level packaging, manufactured by TOWA Coating thickness of the polymerizable composition: 0.5 mm (Primary curing conditions) Press pressure: 8 MPa Curing temperature: 35°C Curing time: 30 minutes (Secondary curing conditions) Curing apparatus: Hot plate Curing temperature: 175°C Curing time: 40 minutes

[0132] The coating thickness of the secondary cured body of the polymerizable composition in the obtained molded body was 0.49 to 0.51 mm. Also, when the uniformity, presence or absence of voids, and adhesiveness were evaluated according to the above method, the secondary cured body of the polymerizable composition was excellent in uniformity, had no voids, and was excellent in adhesiveness.

[0133] <Example 5> (Preparation of monomer solution) 95.3 parts of RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenyl ethyltrimethoxysilane, 0.8 part of phenoxyethylene glycol methacrylate, 50 parts of a phosphorus-based flame retardant (phosphine oxide, trade name "PQ60", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 15 parts of a nitrogen-based flame retardant (melamine cyanurate, trade name "MC4000", manufactured by Nissan Chemical Industries, Ltd.), and 330 parts of silica (spherical silica, trade name "MLR1114", manufactured by Tatsumori Co., Ltd., volume average particle diameter 10 μm) were mixed to prepare a monomer solution.

[0134] (Polymerization process, cooling process, and polymerization process) A frozen solid (the polymerizable oligomer composition of Example 5) was obtained in the same manner as in Example 1 except that the obtained monomer solution was used, and a molded article in which a Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained in the same manner as in Example 4. The coating thickness of the secondary cured body of the polymerizable composition in the obtained molded article was 0.50 to 0.52 mm. Further, when the uniformity, presence or absence of voids, and adhesiveness were evaluated according to the above method, the secondary cured body of the polymerizable composition was excellent in uniformity, had no voids, and was excellent in adhesiveness.

[0135] <Example 6> (Preparation of monomer solution) 95.3 parts of RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenyl ethyltrimethoxysilane, 0.8 part of phenoxyethylene glycol methacrylate, 50 parts of a phosphorus-based flame retardant (organic phosphorus-based compound, trade name "FCX-210", manufactured by Teijin Chemicals Ltd.), 15 parts of a nitrogen-based flame retardant (melamine cyanurate, trade name "MC4000", manufactured by Nissan Chemical Industries, Ltd.), and 330 parts of silica (spherical silica, trade name "MLR1114", manufactured by Tatsumori Co., Ltd., volume average particle diameter 10 μm) were mixed to prepare a monomer solution.

[0136] A frozen solid (the polymerizable oligomer composition of Example 6) was obtained in the same manner as in Example 1, except that the obtained monomer solution was used. A molded body in which a Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained in the same manner as in Example 4. The coating thickness of the secondary cured body of the polymerizable composition in the obtained molded body was 0.47 to 0.49 mm. Further, when the uniformity, the presence or absence of voids, and the adhesiveness were evaluated according to the above method, the secondary cured body of the polymerizable composition was excellent in uniformity, had no voids, and was excellent in adhesiveness.

[0137] <Example 7> (Preparation of monomer solution) 95.3 parts of a RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenyl ethyltrimethoxysilane, 0.8 part of phenoxyethylene glycol methacrylate, 65 parts of a phosphorus-nitrogen composite flame retardant (metal phosphinate, trade name "OP-1312", manufactured by Clariant Corporation), and 330 parts of silica (spherical silica, trade name "MLR1114", manufactured by Tatsumori Co., Ltd., volume average particle diameter 10 μm) were mixed to prepare a monomer solution.

[0138] A frozen solid (the polymerizable oligomer composition of Example 7) was obtained in the same manner as in Example 1, except that the obtained monomer solution was used. A molded body in which a Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained in the same manner as in Example 4. The coating thickness of the secondary cured body of the polymerizable composition in the obtained molded body was 0.50 to 0.52 mm. Further, when the uniformity, the presence or absence of voids, and the adhesiveness were evaluated according to the above method, the secondary cured body of the polymerizable composition was excellent in uniformity, had no voids, and was excellent in adhesiveness.

[0139] <Example 8> 95.3 parts of RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts of dicyclopentadiene monoepoxide (DCPME), 1.7 parts of bicycloheptenyl ethyltrimethoxysilane, 0.8 part of phenoxyethylene glycol methacrylate, 75 parts of a phosphorus-nitrogen composite flame retardant (metal phosphinate, trade name "OP-1312", manufactured by Clariant), and 75 parts of glass flakes (trade name "GF001", manufactured by Glassflake, average diameter (D50) measured by a laser diffraction particle size analyzer (Malvern Mastersizer 2000) of 27 to 32 μm, standard thickness of 1.0 to 1.3 μm) were mixed to prepare a monomer solution.

[0140] A frozen solid (the polymerizable oligomer composition of Example 8) was obtained in the same manner as in Example 1 except that the obtained monomer solution was used, and a molded body in which a Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained in the same manner as in Example 4. The coating thickness of the secondary cured body of the polymerizable composition in the obtained molded body was 0.47 to 0.49 mm. Further, when the uniformity, presence or absence of voids, and adhesiveness were evaluated according to the above method, the secondary cured body of the polymerizable composition was excellent in uniformity, had no voids, and was excellent in adhesiveness.

[0141] <Comparative Example 1> A monomer solution was prepared in the same manner as in Example 8, and the temperature of the obtained monomer solution was adjusted to 30°C. 0.04 part of the compound (7) was added to the monomer solution at 30°C as a metathesis polymerization catalyst, and the whole was stirred for a short time to prepare a polymerizable composition. The obtained polymerizable composition was promptly supplied to a molding apparatus to perform coating molding of a 12-inch Si dummy wafer. Then, by performing primary curing and secondary curing of the polymerizable composition, a molded body in which a Si dummy wafer was coated with a secondary cured body of the polymerizable composition was obtained. The detailed conditions for molding and curing were the same as in Example 4.

[0142] The coating thickness of the secondary cured product of the polymerizable composition in the obtained molded body was 0.47 to 0.49 mm. When the presence or absence of voids and the adhesiveness were evaluated according to the above method, the secondary cured product of the polymerizable composition had no voids and was excellent in adhesiveness. On the other hand, when the secondary cured product of the polymerizable composition was visually confirmed, the glass flakes were unevenly distributed only in the central portion of the Si dummy wafer and hardly existed in the outer peripheral portion. That is, the secondary cured product of the monomer solution was inferior in uniformity.

Claims

1. A method for producing a polymerizable oligomer composition, comprising: a polymerization step of adding a metathesis polymerization catalyst to a monomer solution containing a cycloolefin monomer and performing a polymerization reaction of the cycloolefin monomer to obtain an oligomer liquid composition containing an oligomer derived from the cycloolefin monomer; and a cooling step of cooling the oligomer liquid composition to 0 °C or lower. The method for producing a polymerizable oligomer composition is characterized in that The polycondensation step is such that the viscosity [μ ０ at a temperature of 30°C of the liquid component in the monomer liquid is such that the viscosity [μ １ at a temperature of 30°C of the liquid component in the oligomer liquid composition is increased by 3 to 150 cps, and the polycondensation reaction is carried out in this step, the viscosity is a value measured at a rotational speed of 60 rpm of the rotor using a B-type viscometer.

2. The method for producing a polymerizable oligomer composition according to claim 1, wherein the monomer solution contains a cycloolefin monomer having no polar group as the cycloolefin monomer.

3. The method for producing a polymerizable oligomer composition according to claim 1 or 2, wherein the monomer solution contains dicyclopentadienes as the cycloolefin monomer.

4. The method for producing a polymerizable oligomer composition according to claim 1 or 2, wherein the cooling step is a step of cooling and solidifying the oligomer liquid composition.

5. The method for producing a polymerizable oligomer composition according to claim 1 or 2, wherein the monomer solution further contains a filler.

6. The method for producing a polymerizable oligomer composition according to claim 1 or 2, wherein the monomer solution further contains a flame retardant.

7. The method for producing a polymerizable oligomer composition according to claim 1 or 2, wherein the monomer solution further contains at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

8. A method for producing a molded article, comprising: a step of obtaining a polymerizable oligomer composition by the production method according to claim 1 or 2; and a polymerization step of bulk polymerizing the obtained polymerizable oligomer composition.

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