Discharge method, method for manufacturing molded body, and discharge device

Abstract

To provide a discharge method and discharge device that can discharge and mold a one-component polymerizable composition with excellent stability over a long period of time.SOLUTION: Provided is a method for discharging a polymerizable composition containing cycloolefin monomers and a metathesis polymerization catalyst, wherein the polymerizable composition at a temperature [T1] of -30 to 10°C is discharged in increments of 0.0001 to 0.1 g. Also provided is a discharge device comprising: a discharge head for discharging a polymerizable composition containing cycloolefin monomers and a metathesis polymerization catalyst; a temperature control unit that controls the temperature [T1] of the polymerizable composition within the discharge head to be between -30 and 10°C; and a discharge control unit that controls the discharge amount of the polymerizable composition from the discharge head to be between 0.0001 and 0.1 g.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for discharging a one-component polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst. The present invention also relates to a discharging device for discharging the one-component polymerizable composition.

Background Art

[0002] Polymers obtained by polymerizing a cycloolefin monomer in the presence of a metathesis polymerization catalyst are excellent in electrical properties, mechanical properties, impact resistance, 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-based polymers are produced, for example, by the reaction injection molding method in which a reaction liquid 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 respect to the metathesis polymerization catalyst, in the reaction injection molding method, a monomer liquid containing the cycloolefin monomer and a catalyst liquid containing the metathesis polymerization catalyst are separately prepared, and a step of instantaneously mixing these plural liquids with a collision mixer or the like immediately before injecting them into the molding mold is required (for example, Patent Document 1). On the other hand, there is a demand for a molding method in which a one-component polymerizable composition in which a cycloolefin monomer and a metathesis polymerization catalyst are already sufficiently mixed is prepared in advance and used.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a discharge method and a discharge device capable of discharging a one-component polymerizable composition by long-term discharge molding with excellent stability.

Means for Solving the Problems

[0006] The present inventor conducted studies to achieve the above object, and found that the above problems can be solved by controlling the temperature and discharge amount of the polymerizable composition within a limited range, and thus completed the present invention.

[0007] That is, according to the present invention, the following discharge method and a method for manufacturing a molded article are provided. [1] A method for discharging a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, wherein the polymerizable composition having a temperature [T1] of -30 to 10°C is discharged in amounts of 0.0001 to 0.1 g each. [2] A step of storing the polymerizable composition cooled to a cooling temperature [T0] that is 5°C or more lower than the temperature [T1] in a storage means, and a step of discharging the polymerizable composition after heating the polymerizable composition from the cooling temperature [T0] to the temperature [T1]. The discharge method according to [1]. [3] The discharge method according to [1] or [2], wherein discharge is performed using an air pulse type dispenser. [4] The discharge method according to any one of [1] to [3], wherein the cycloolefin monomer contains a cycloolefin monomer having no polar group. [5] The discharge method according to any one of [1] to [4], wherein the cycloolefin monomer contains dicyclopentadienes. [6] The discharge method according to any one of [1] to [5], wherein the polymerizable composition further contains at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound. [7] A step of discharging a polymerizable composition by the discharge method according to any one of [1] to [6], and A method for manufacturing a molded article comprising a step of bulk polymerizing the discharged polymerizable composition.

[0008] Further, according to the present invention, the following discharge device is provided. [8] A discharge head that discharges a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, A temperature control unit that controls the temperature [T1] of the polymerizable composition in the discharge head to -30 to 10°C, A discharge device comprising a discharge control unit that controls the discharge amount of the polymerizable composition from the discharge head to 0.0001 to 0.1 g. [9] A tank for storing the polymerizable composition while cooling it to a cooling temperature [T0] that is 5°C or more lower than the temperature [T1], The discharge device according to [8], further comprising a transfer device that transfers the polymerizable composition from the tank to the discharge head.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a discharge method and a discharge device capable of discharging and molding a one-component polymerizable composition with excellent stability for a long time.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0011] <Discharge Method> The discharge method of the present disclosure is a method for discharging a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, and is a discharge method in which the polymerizable composition having a temperature [T1] of -30 to 10°C is discharged in amounts of 0.0001 to 0.1 g each.

[0012] The inventor focused on the extrusion molding method as a molding method capable of molding a minute molded body. When molding a minute molded body using the extrusion molding method, it is preferable to continuously use a small amount of a one-component polymerizable composition prepared in advance for a long time. In addition, when molding a minute molded body using the extrusion molding method, it is necessary to ensure a high level of moldability of the polymerizable composition so that the polymerizable composition can be extruded from a relatively thin nozzle.

[0013] However, since a one-component polymerizable composition has high polymerization reactivity and is likely to have reduced moldability, it has been difficult to perform extrusion molding of a one-component polymerizable composition for a long time with excellent stability by a conventional extrusion method. In contrast, the inventor has found that not only can extrusion molding be performed for a long time by an extrusion method in which the polymerizable composition is extruded in amounts of 0.0001 to 0.1 g at a temperature [T1] of -30 to 10°C, but also the stability of the extrusion molding can be improved.

[0014] In the extrusion method of the present disclosure, the temperature [T1] of the polymerizable composition is not particularly limited as long as it is within the range of -30 to 10°C, but it is preferably -20 to 5°C, and more preferably -10 to 0°C. When the temperature [T1] of the polymerizable composition is within the above range, the polymerizable composition can be extruded for a longer time with better stability.

[0015] In the extrusion method of the present disclosure, 0.0001 to 0.1 g of the polymerizable composition is extruded per extrusion. The extrusion amount per extrusion is not particularly limited as long as it is 0.0001 to 0.1 g, but it is preferably 0.001 to 0.05 g, and more preferably 0.005 to 0.02 g. When the extrusion amount is within the above range, the stability of the extrusion molding can be further enhanced.

[0016] In the extrusion method of the present disclosure, known extrusion means and known temperature control means can be used in combination. In the extrusion method of the present disclosure, as the extrusion means, it is preferable to perform extrusion using an air-type dispenser, and more preferably to perform extrusion using an air pulse type dispenser.

[0017] The discharging method of the present disclosure preferably includes a step of storing the polymerizable composition cooled to a cooling temperature [T0] that is 5°C or more lower than the temperature [T1], and a step of discharging the polymerizable composition after heating the polymerizable composition from the cooling temperature [T0] to the temperature [T1]. That is, in the discharging method of the present disclosure, it is preferable to cool the polymerizable composition to the cooling temperature [T0] in advance and then heat it to the temperature [T1]. By such a method, the polymerizable composition can be discharged and molded for a longer time with better stability.

[0018] The cooling temperature [T0] is preferably a temperature that is 5°C or more lower than the temperature [T1], more preferably a temperature that is 10°C or more lower than the temperature [T1], and even more preferably a temperature that is 20°C or more lower than the temperature [T1]. As a specific cooling temperature [T0], 0°C or lower is preferable, -5°C or lower is more preferable, and -10°C or lower is even more preferable. Note that the lower limit value of the cooling temperature [T0] is not particularly limited, but is usually -45°C or higher. When the cooling temperature [T0] is within the above range, the polymerizable composition can be discharged and molded for a longer time with better stability.

[0019] As the storage means for the polymerizable composition cooled to the cooling temperature [T0], known means can be used. Further, as the heating means for heating the polymerizable composition from the cooling temperature [T0] to the temperature [T1], known means can be used.

[0020] <Polymerizable composition> In the discharging method of the present disclosure, a one-component type polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst is used.

[0021] [Cycloolefin monomer] A 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, more preferably 5 to 15.

[0022] Examples of the cycloolefin monomer include monocyclic cycloolefin monomers and norbornene-based monomers, and norbornene-based monomers are preferred. A 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.

[0023] Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, cyclopentadiene, 1,5-cyclooctadiene, and the like.

[0024] Specific examples of the norbornene-based monomer include dicyclopentadienes 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-phenyltetracyclo[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 dodeca-9-ene-4,5-dicarboxylic anhydride and other tetracyclododecenes; Norbornenes 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, 5-norbornene-2,3-dicarboxylic anhydride; Oxanorbornenes such as 7-oxa-2-norbornene, 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 3,8 pentadeca-5,12-diene, and polycyclic olefins having four or more rings such as tricyclopentadiene; and the like.

[0025] 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, when using those having an aromatic condensed ring such as tetracyclo[9.2.1.0 2,10 .0 3,8 tetradeca-3,5,7,12-tetraene, the polymerizable composition can be extruded and molded for a longer time with even better stability.

[0026] These cycloolefin monomers may be used alone or in combination of two or more. In addition, the polymerizable composition may contain any monomer copolymerizable with the cycloolefin monomer as long as the expression of the effects of the present invention is not inhibited.

[0027] The polymerizable composition preferably contains dicyclopentadienes as the cycloolefin monomer, and more preferably contains dicyclopentadienes and tricyclopentadiene. When the polymerizable composition contains dicyclopentadienes and tricyclopentadiene, the content ratio thereof is 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 polymerizable composition can be extruded and molded for a longer time with better stability.

[0028] In the polymerizable composition, the proportion of the cycloolefin monomer is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. When the proportion of the cycloolefin monomer is within the above range, the mechanical properties of the obtained molded body can be improved.

[0029] [(Meth)acrylate monomer] The polymerizable composition may further contain a (meth)acrylate monomer as a monomer component in addition to the cycloolefin monomer.

[0030] 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 preferred, and a monofunctional monomer is more preferred. Further, as the (meth)acrylate monomer, a methacrylate monomer is preferred.

[0031] Since the (meth)acrylate monomer is excellent in expressing the effect, 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.

[0032] 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.

[0033] 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-methacryloxydiethoxyphenyl)propane, and the like.

[0034] Specific examples of the polyfunctional monomer having three or more (meth)acryloyl groups include trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like.

[0035] 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 and used in any ratio.

[0036] The content of the (meth)acrylate monomer in the coincidence composition is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and 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 can be enhanced.

[0037] [Metathesis polymerization catalyst] The polymerizable composition used in the discharge method of the present disclosure contains a metathesis polymerization catalyst in addition to the cycloolefin monomer.

[0038] The metathesis polymerization catalyst is not particularly limited as long as it can ring-opening polymerize the cycloolefin monomer, and known ones can be used.

[0039] 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 represented by (>C:). The ruthenium carbene complex is excellent in catalytic activity during bulk ring-opening polymerization, so that the resulting polymer has less 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.

[0040] Examples of the ruthenium carbene complex include those represented by the following general formula (1) or general formula (2).

Chemical formula

[0041] 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.

[0042] 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.

[0043] X 1 and X 2 each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand that 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.

[0044] L 1 and L 2 represents a heteroatom-containing carbene compound or a neutral electron-donating compound other than the heteroatom-containing carbene compound. The heteroatom-containing carbene compound and the neutral electron-donating compound other than the heteroatom-containing carbene compound are compounds having a neutral charge when separated from the central metal. From the viewpoint of improving catalytic activity, the heteroatom-containing carbene compound is preferred. The heteroatom means an atom of Group 15 and Group 16 of the periodic table, and specific examples thereof include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. 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.

[0045] 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

[0046] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 each independently represents 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). Further, R 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.

[0047] 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.

[0048] Examples of the neutral electron-donating compound include oxygen atom, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0049] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may each independently and / or in any combination bond to each other to form a polydentate chelating ligand.

[0050] 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.

[0051] The general formula (5) is shown below.

Chemical formula

[0052] 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, as Z, an oxygen atom is preferable.

[0053] 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 be independently and / or combined with each other in any combination to form a polydentate chelating ligand, provided that X 1 and L 1 do not form a polydentate chelating ligand, and R 1 and R 2 are preferably bonded 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).

[0054] 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 be bonded 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 preferably forms an aromatic ring, more preferably forms an aromatic ring having 6 to 20 carbon atoms, and even more preferably forms an aromatic ring having 6 to 10 carbon atoms.

[0055] In the above general formula (5), R 9 and R 10 and R 11is, independently of one another, 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, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0056] 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).

[0057] The general formula (6) is shown below.

Chemical formula

[0058] 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.

[0059] In the above general formula (6),

Chemical formula

[0060] R 1 , X 1 , X 2 and L 1is the same as in the cases of the above general formulas (1) and (2), and they may combine with each other individually and / or in any combination to form a multidentate chelating ligand, provided that X 1 and X 2 and L 1 do not form a multidentate chelating ligand, and R 1 is preferably a hydrogen atom.

[0061] 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 a substituent and may combine with 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 cases 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 a hydrogen atom, and R 18 to R 21 are preferably a hydrogen atom or a halogen atom.

[0062] 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).

[0063] In addition, as the compound represented by the above general formula (1), in addition to the compound 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

[0064] The content of the metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and even more preferably 0.015 to 20 mmol, based on 1 mol of all the cycloolefin monomers used in the reaction.

[0065] The polymerizable composition may optionally contain at least one selected from a coupling agent, a radical generator, a diisocyanate compound, and a polyfunctional (meth)acrylate compound.

[0066] The coupling agent is not particularly limited, and 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 and bicycloheptenylethyltriethoxysilane are more preferred, and bicycloheptenylethyltrimethoxysilane is even more preferred.

[0067] In addition, 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 may be used.

[0068] The content of the coupling agent in the polymerizable composition 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, based on 100 parts by mass of all the cycloolefin monomers used.

[0069] The radical generator has the function of generating radicals by heating, thereby inducing a crosslinking reaction in the resulting molded article. The site where the radical generator induces the crosslinking reaction is mainly the carbon-carbon double bond contained in the polymer component in the resulting molded article, but crosslinking may also occur at the saturated bond portion.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] The amount of the radical generator in the polymerizable composition 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.

[0074] 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 isocyanates. Further, known ones having polyfunctional isocyanate groups in the form of isocyanurate, biuret, adduct, or polymeric forms of these compounds 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 individually or in combination of two or more.

[0075] The polyfunctional blocked isocyanate compound is obtained by reacting at least two isocyanate groups in the molecule with an active hydrogen-containing compound to make it inactive at room temperature. The isocyanate compound generally has a structure in which the isocyanate groups are masked with a blocking agent such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. The polyfunctional blocked isocyanate compound generally does not react at room 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.

[0076] The diisocyanate compounds may be used individually or in combination of two or more. The blending amount of the diisocyanate compound in the polymerizable composition 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 the total cycloolefin monomer.

[0077] By using a polyfunctional (meth)acrylate compound together with the diisocyanate compound, it is presumed that the function as an adhesion improver or 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.

[0078] 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 polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, still more preferably 2 to 10 parts by mass, based on 100 parts by mass of all the cycloolefin monomers used.

[0079] The polymerizable composition may contain, as other optional components, a filler, a flame retardant, an activator, an activity regulator, an elastomer, an antioxidant, an ultraviolet absorber, a light stabilizer, and the like.

[0080] 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 reaction.

[0081] The activity regulator can be selected according to the type of the metathesis polymerization catalyst. Examples of the activity regulator when a compound of a transition metal of Group 5 or Group 6 of the periodic table is used 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.

[0082] 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.

[0083] As a metathesis polymerization catalyst, particularly as an activity regulator when using a ruthenium carbene complex, Lewis base compounds can be mentioned. Examples of 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, etc. Also, norbornenes substituted with an alkenyl group such as vinyl norbornene, propenyl norbornene, and isopropenyl norbornene are simultaneously the above-mentioned cycloolefin monomers and also act as activity regulators. The usage amount of these activity regulators may be appropriately adjusted according to the compound used.

[0084] Examples of elastomers 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, etc. By dissolving the elastomer in the polymerizable composition and using it, the viscosity can be adjusted. Also, by adding the elastomer, the impact resistance of the obtained molded article can be improved. The usage amount of the elastomer 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.

[0085] Examples of antioxidants include various antioxidants for plastics and rubbers such as phenolic, phosphorus-based, and amine-based antioxidants.

[0086] The coincidence composition is prepared by appropriately mixing the above components according to a known method. The mixing temperature is preferably -30 to 40°C, more preferably -20 to 35°C. Further, the mixed solution obtained by mixing the above components is preferably quickly cooled to a temperature within the range of [T1] or lower.

[0087] When preparing the polymerizable composition, a catalyst solution in which a metathesis polymerization catalyst is dissolved or dispersed 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. Aromatic hydrocarbons are preferred, and toluene is more preferred.

[0088] As the polymerizable composition, a polymerizable oligomer composition containing an oligomer derived from a cycloolefin monomer can also be used. The polymerizable oligomer composition is preferably obtained by adding a metathesis polymerization catalyst to a monomer solution containing a cycloolefin monomer and performing a polycondensation reaction of the cycloolefin monomer to obtain an oligomer liquid composition containing an oligomer derived from the cycloolefin monomer, and then cooling the oligomer liquid composition.

[0089] Here, the polycondensation reaction is preferably carried out so that the viscosity [μ1] of the liquid component in the oligomer liquid composition at 30°C is 3 to 150 cps higher than the viscosity [μ0] of the liquid component in the monomer solution at 30°C. The viscosity is measured using a B-type viscometer at a rotor rotation speed of 60 rpm.

[0090] <Method for manufacturing a molded body> The step of discharging the polymerizable composition by the discharging method of the present disclosure, and A molded article can be produced by a production method including a step of bulk polymerizing the discharged polymerizable composition. The present disclosure also relates to a method for producing such a molded article.

[0091] Bulk polymerization of the polymerizable composition is usually carried out by heating the discharged polymerizable composition. From the viewpoint of productivity, the heating temperature (initial temperature) in the polymerization step is preferably 0°C or higher, more preferably 10°C or higher. Usually, bulk polymerization is an exothermic reaction, and as the bulk polymerization progresses, 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 composition.

[0092] In the discharging method and the production method of the present disclosure, the object to which the polymerizable composition is discharged is not particularly limited and can be appropriately selected according to the structure of the target molded article and the like.

[0093] For example, in the production method of the present disclosure, by discharging the polymerizable composition into a mold having a desired microstructure, bulk polymerizing the discharged polymerizable composition, and then taking out the molded article from the mold, a molded article having a desired shape can be produced. Also, by discharging the polymerizable composition onto a substrate, coating at least a part of the substrate with a small amount of the polymerizable composition, and then bulk polymerizing the polymerizable composition, a molded article can be produced. Further, by discharging the polymerizable composition into recesses or pore portions provided in a component, injecting the polymerizable composition into the recesses or pore portions, and then bulk polymerizing the polymerizable composition, the recesses or pore portions can be filled with the molded article.

[0094] According to the discharge method and the manufacturing method of a molded body of the present disclosure, since the polymerizable composition can be discharged and molded in a minute amount with excellent stability over a long period of time, a minute molded body can be industrially manufactured with excellent stability. Further, a molded body obtained from a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst has properties such as heat resistance, low water absorption, and low dielectric constant. Therefore, the discharge method and the manufacturing method of a molded body of the present disclosure are suitably used for manufacturing minute molded bodies for which these properties are required. For example, the discharge method and the manufacturing method of a molded body of the present disclosure are suitably used for manufacturing minute encapsulants for protecting components in electric and electronic applications.

[0095] <Discharge device> The discharge method of the present disclosure can preferably be carried out using a discharge device 1 including a discharge head 10 that discharges the above-described polymerizable composition, a temperature control unit 20 that controls the temperature [T1] of the polymerizable composition in the discharge head 10 to -30 to 10°C, and a discharge control unit 30 that controls the discharge amount of the polymerizable composition from the discharge head 10 to 0.0001 to 0.1 g. The present disclosure also relates to such a discharge device.

[0096] The discharge head 10 includes a storage unit 11 for the polymerizable composition and a nozzle 12. The polymerizable composition is stored in the storage unit 11 for the polymerizable composition. Further, the discharge head 10 is connected to the discharge control unit 30.

[0097] The temperature control unit 20 controls the temperature of the polymerizable composition stored in the storage unit 11 of the discharge head 10. Examples of the temperature control mechanism of the temperature control unit 20 include a compression type including a compressor, an absorption type using a refrigerant, a cooling method using a Peltier element, a heating device such as a heater, and a mechanism using a cooling substance such as dry ice.

[0098] Examples of the drive method of the discharge control unit 30 include a screw method, a jet method, a plunger method, and an air method. Among these, the air method is preferable, and the air pulse method is more preferable. Hereinafter, the case of using the discharge control unit 30 of the air pulse method will be described.

[0099] The ejection control unit 30 of the air pulse method can eject the polymerizable composition from the nozzle 12 by supplying pressurized air to the polymerizable composition in the housing portion 11 of the ejection head 10. An intermediate member (float) called a plunger can also be interposed between the polymerizable composition and the air. The ejection amount of the polymerizable composition from the ejection head 10 can be controlled by the air supply pressure and the air supply time of the air supply device. When the ejection control unit 30 of the air pulse method is used, the ejection head 10 corresponding to the air method is mounted on the ejection device 1. Note that the air supply device is not particularly limited, and a device using a pressure reducing valve or the like can be used. When the ejection control unit 30 of the air pulse method is used, the ejection control unit 30 is connected to the housing portion 11 of the ejection head 10, and the ejection control unit 30 and the nozzle 12 are configured to be separated.

[0100] The ejection control unit 30 is not limited to the above-described aspect. Depending on the driving method of the ejection control unit 30, the ejection control unit 30 may be connected to the nozzle 12 of the ejection head 10.

[0101] The polymerizable composition is preferably cooled to the cooling temperature [T0] in advance. As means for using the polymerizable composition cooled to the cooling temperature [T0] in advance, the ejection device 1 of the present disclosure preferably further includes a tank 40 for storing the polymerizable composition while cooling it to the cooling temperature [T0], and a transfer device 41 for transferring the polymerizable composition from the tank 40 to the ejection head 10. In this case, the ejection head 10 and the tank 40 are connected via the transfer device 41 and the pipe 42.

Example

[0102] Hereinafter, the present invention will be described based on examples, but the present invention is not limited by these examples. Note that "parts" and "%" are based on mass unless otherwise specified.

[0103] <Device Configuration of Ejection Device 1> A plate-cooled cooler (product name: "OCE-F15P-D12", manufactured by Ohm Electric Co., Ltd.) including a cooling plate for cooling an object to be cooled, a Peltier cooling mechanism, and an air-cooled heat dissipation mechanism was used as the temperature control unit 20. As the discharge control unit 30, a digital dispenser of the air pulse method (product name: "ML-5000X II", manufactured by Musashi Engineering Co., Ltd.) was used. As the discharge head 10, a syringe having a storage part 11 for a polymerizable composition and a nozzle 12, and having a connection part with the digital dispenser at the upper part of the storage part 11 was used. The cooling plate of the cooler was fixed in a state of being in close contact with the syringe, and the cooling plate and the syringe (except near the discharge port of the nozzle 12) were covered with a heat insulating material. In order to measure the temperature [T1] of the polymerizable composition, a thermocouple was disposed near the nozzle 12 in the storage part 11.

[0104] <Device configuration of the discharge device 2> As the temperature control unit 20, a temperature control unit for heating and cooling an object was used. As the discharge control unit 30, the same one as the discharge device 1 was used. As the discharge head 10, a syringe having a storage part 11 for a polymerizable composition and a nozzle 12, having a connection part with the digital dispenser at the upper part of the storage part 11, and having a connection part for receiving the polymerizable composition supplied from the tank 40 at the side part of the storage part 11 was used. Further, a tank 40 for storing the polymerizable composition while cooling it, a transfer device 41 for transferring the polymerizable composition from the tank 40 to the syringe, and a pipe 42 for circulating the polymerizable composition were used. Note that, as the temperature control unit, one including an aluminum block member having a cavity with an inner diameter equal to the outer diameter of the syringe and a plate-cooled cooler similar to the discharge device 1 was used. Further, as the pipe 42, a double pipe was used, and the polymerizable composition was circulated inside the inner pipe, and a temperature control fluid whose temperature was adjusted by an external circulation type temperature adjuster was circulated inside the outer pipe.

[0105] The syringe and the tank 40 were connected via a transfer device 41 and a pipe 42. After covering the syringe with the aluminum block member of the temperature control unit, the temperature control unit was installed on the outer periphery of the syringe by fixing the cooling plate in close contact with the aluminum block member. The aluminum block portion of the temperature control unit, the cooling plate, and the syringe (excluding the vicinity of the discharge port of the nozzle 12) were covered with a heat insulating material. A thermocouple was disposed near the nozzle in the storage portion 11 to measure the temperature [T1] of the polymerizable composition. The syringe was connected to a digital dispenser.

[0106] <Example 1> (Preparation of Polymerizable Composition) 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, 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. While adjusting the temperature of the monomer solution to 12°C, 0.04 part of the compound (7) was added to the monomer solution as a metathesis polymerization catalyst, and then the mixture was stirred to obtain a polymerizable composition.

[0107] In Example 1, the ejection device 1 was used. The polymerizable composition obtained above was supplied to the storage unit 11 of the ejection device 1, and a syringe and a digital dispenser were connected. The cooling plate in close contact with the syringe was cooled to adjust the temperature [T1] of the polymerizable composition to -3°C. Also, the digital dispenser was set to an ejection pressure of 300 kPa and an ejection time of 0.005 seconds. The target ejection amount in this setting was 0.015 g. Then, 10 minutes after the polymerizable composition was supplied to the storage unit 11, the digital dispenser was operated to eject the droplets of the polymerizable composition once. The ejection amount of the ejected polymerizable composition was measured. Thereafter, the droplets of the polymerizable composition were ejected once every 5 minutes, and the ejection amount of the ejected polymerizable composition was measured. The ejection was performed a total of 11 times by the time 60 minutes had elapsed after the polymerizable composition was supplied to the storage unit 11. Table 1 shows the ejection amount for each time, the average value of the ejection amounts, the standard deviation σ of the ejection amounts, and the coefficient of variation cv.

[0108]

Table 1

[0109] <Example 2> In Example 2, the polymerizable composition obtained in the same manner as in Example 1 was used. Also, as the ejection device, the ejection device 2 was used. The obtained polymerizable composition was supplied to the tank 40 of the ejection device 2, and the cooling temperature [T0] of the polymerizable composition was adjusted to -40°C.

[0110] While adjusting the temperature of the pipe 42, the transfer device 41 and the temperature control unit installed on the outer periphery of the syringe were operated to transfer the polymerizable composition from the tank 40 to the syringe, and the temperature [T1] of the polymerizable composition in the syringe was adjusted to -3°C. Also, the digital dispenser was set to a discharge pressure of 300 kPa and a discharge time of 0.005 seconds. Then, 10 minutes after the polymerizable composition was transferred to the storage unit 11, the digital dispenser was operated to discharge the droplets of the polymerizable composition once. The discharge amount of the discharged polymerizable composition was measured. Thereafter, the droplets of the polymerizable composition were discharged once every 5 minutes, and the discharge amount of the discharged polymerizable composition was measured. The discharge was performed a total of 11 times by 60 minutes after the polymerizable composition was transferred to the storage unit 11. Table 2 shows the discharge amount for each time, the average value of the discharge amounts, the standard deviation σ of the discharge amounts, and the coefficient of variation cv.

[0111]

Table 2

[0112] <Comparative Example 1> In Comparative Example 1, the polymerizable composition obtained in the same manner as in Example 1 was used. Also, as the discharge device, Discharge Device 2 was used. The obtained polymerizable composition was supplied to the tank 40 of Discharge Device 2, and the temperature of the polymerizable composition (corresponding to the cooling temperature [T0]) was adjusted to 30°C.

[0113] While adjusting the temperature of the pipe 42, the transfer device 41 and the temperature control unit installed on the outer periphery of the syringe were operated to transfer the polymerizable composition from the tank 40 to the syringe, and the temperature [T1] of the polymerizable composition in the syringe was adjusted to 30°C. Also, the digital dispenser was set to a discharge pressure of 300 kPa and a discharge time of 0.005 seconds. Then, when the digital dispenser was operated 10 minutes after the polymerizable composition was transferred to the storage unit 11, the polymerizable composition could not be discharged.

[0114] Similarly, the ejection device 2 was set as described above. After one minute had elapsed since the polymerizable composition was transferred to the storage section 11, the digital dispenser was operated to eject droplets of the polymerizable composition once. The ejection amount of the ejected polymerizable composition was measured. Thereafter, droplets of the polymerizable composition were ejected once every minute, and the ejection amount of the ejected polymerizable composition was measured. After nine minutes had elapsed since the polymerizable composition was transferred to the storage section 11, it was no longer possible to eject the polymerizable composition. Therefore, the ejection was performed a total of eight times by eight minutes after the polymerizable composition was transferred to the storage section 11. Table 3 shows the ejection amount for each time, the average value of the ejection amounts, the standard deviation σ of the ejection amounts, and the coefficient of variation cv.

[0115]

Table 3

[0116] When the temperature [T1] of the one-component polymerizable composition containing the cycloolefin monomer and the metathesis polymerization catalyst was adjusted to -30 to 10°C and ejected in amounts of 0.0001 to 1 g each (Examples 1 to 2), long-term ejection molding was possible. Furthermore, in this case, since the standard deviation σ and the coefficient of variation cv of the ejection amount were small over a long period of time, it was confirmed that the stability of the ejection molding was also excellent.

[0117] In particular, when the polymerizable composition cooled to a cooling temperature [T0] lower than the temperature [T1] was heated to the temperature [T1] and ejected (Example 2), since the standard deviation σ and the coefficient of variation cv of the ejection amount were extremely small, it was confirmed that the stability of the ejection molding was extremely excellent.

[0118] On the other hand, when the temperature [T1] of the one-component polymerizable composition was not appropriately adjusted, long-term ejection molding was not possible. Furthermore, when the temperature [T1] of the one-component polymerizable composition was not appropriately adjusted, even in the case of short-term ejection molding, the standard deviation σ and the coefficient of variation cv of the ejection amount were large, and it was confirmed that the stability of the ejection molding was also poor.

Explanation of symbols

[0119] 1 Spit-out device 10 Spit-out head 20 Temperature control unit 30 Spit-out control unit 40 Tank 41 Transfer device 42 Pipe

Claims

1. A method of discharging a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, wherein the polymerizable composition having a temperature [T １ of -30 to 10°C is discharged in amounts of 0.0001 to 0.1 g each.

2. The temperature [T １ , a cooling temperature [T ０ that is 5°C or more lower than the temperature [T], and storing the polymerizable composition cooled to the cooling temperature [T] in a storage means. The step of discharging the polymerizable composition after heating the polymerizable composition from the cooling temperature [T ０ to the temperature [T １ , and the discharging method according to claim 1.

3. The discharging method according to claim 1 or 2, wherein discharging is performed using an air pulse type dispenser.

4. The discharging method according to claim 1 or 2, wherein the cycloolefin monomer contains a cycloolefin monomer having no polar group.

5. The discharging method according to claim 1 or 2, wherein the cycloolefin monomer contains dicyclopentadienes.

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

7. A method for producing a molded article, comprising: a step of discharging a polymerizable composition by the discharging method according to claim 1 or 2, and a step of bulk-polymerizing the discharged polymerizable composition.

8. A discharging device comprising: a discharging head that discharges a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, and The temperature [T １ of the polymerizable composition in the ejection head is controlled to -30 to 10°C by a temperature control unit, a discharge control unit that controls the discharge amount of the polymerizable composition from the discharge head to 0.0001 to 0.1 g.

9. The polymerization composition is stored while being cooled to a cooling temperature [T １ that is 5°C or more lower than the temperature [T ０ in a tank The discharging device according to claim 8, further comprising a transfer device that transfers the polymerizable composition from the tank to the discharging head.

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