JP5949196B2 - Resin composition and molded product thereof - Google Patents

Description

The present invention relates to a resin composition having a high dielectric constant and low dielectric loss tangent to a high frequency, and a high frequency dielectric antenna formed from the resin composition.

With the spread of satellite broadcasting, satellite communication, high-definition television broadcasting, mobile phones, etc., high-density information transmission / reception via radio waves has become widespread, and the frequency of use has been increasing. Furthermore, miniaturization of radio wave transmission / reception antennas and circuit boards has been promoted for the purpose of improving space efficiency, including improvements in transport efficiency in mobile communication devices such as the global positioning system of navigation systems. ing.

A material having high dielectric constant and low dielectric loss tangent characteristics is used to reduce the size of a high-frequency antenna. The higher the dielectric constant, the higher the frequency of radio waves that can be received and transmitted by the antenna, and high frequency reception is possible even if the antenna substrate is made smaller. Further, the smaller the dielectric loss tangent, the smaller the signal transmission loss, and thus the noise is reduced.

In Patent Document 1, an antenna substrate having a high dielectric constant and a low dielectric loss tangent is easily formed by injection molding a resin composition in which a high dielectric material such as barium titanate is blended with a thermoplastic norbornene resin as a thermoplastic resin. Giving is disclosed. However, this resin composition is injectable, but it is easy to generate dirt in the injection molding machine, and as a result, the injection molding machine repeats injection molding and burns into the molded product, resulting in defective products. Was not enough.

JP-A-9-147626

An object of the present invention is to provide a high dielectric constant, low dielectric loss tangent material that can be easily molded and exhibits excellent moldability.

As a result of intensive studies, the present inventors have found that a resin composition containing a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer, a glass filler, and a paraelectric ceramic A resin composition containing a predetermined amount of a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer, a glass filler, and a paraelectric ceramic has high moldability. The present invention has been found to be suitable for materials for high-frequency small antenna substrates and to withstand high-temperature conditions such as a reflow process for manufacturing antennas.

Thus, according to the present invention, a resin composition comprising (A) a hydrogenated crystalline cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene monomer and (B) a glass filler. And the resin composition characterized by the weight ratio of the said crystalline cyclic olefin ring-opening polymer hydrogenated product and a glass filler being 95/5-40/60 is provided.
The resin composition preferably further contains 5 to 100 parts by weight of a paraelectric ceramic with respect to 100 parts by weight of the total amount of the crystalline cyclic olefin ring-opening polymer hydrogenated product and the glass filler.
The paraelectric ceramic is preferably a metal titanate.
The resin composition of the present invention is suitable as a material for an antenna substrate.

The resin composition of the present invention is a composition comprising a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer and a glass filler. A crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer used to constitute the resin composition is a polycyclic norbornene monomer that contains at least a monocyclic norbornene monomer. It is obtained by hydrogenating the main chain double bond of the ring-opening polymer obtained by carrying out ring-opening polymerization as a part of the monomer, and having crystallinity. .

A method for obtaining a crystalline cyclic olefin ring-opened polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer is not particularly limited, but is described in, for example, JP-A-2006-52333. By such a method, ring-opening polymerization is performed using a polycyclic norbornene-based monomer as at least a part of the monomer to obtain a cyclic olefin ring-opening polymer having syndiotactic stereoregularity, A method of hydrogenating it is preferred.

The cyclic olefin ring-opening polymer used to obtain a hydrogenated crystalline cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene monomer is a polycyclic ring having three or more rings. It can be obtained using a norbornene-based monomer as at least a part of the monomer. The polycyclic norbornene monomer may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule. From the viewpoint of particularly improving the heat resistance of the resulting resin composition, it is particularly preferable to use a compound represented by the following formula (1) or (2) as the polycyclic norbornene monomer. preferable.

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Specific examples of the polycyclic norbornene monomer represented by the formula (1) include dicyclopentadiene, methyldicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, 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), tetracyclo [10.2.1.0 ^{2 , 11} . 0 ^4,9] pentadeca -4,6,8,13- tetraene (1,4-methano -1,4,4a, 9,9a, also referred to as a 10-hexahydro-anthracene) can be mentioned.

Moreover, as a polycyclic norbornene-type monomer represented by Formula (2), the tetracyclododecene when m of Formula (2) is 1, and m of Formula (2) are 2. The hexacycloheptadecenes in the case can be mentioned. Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl 8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride Tetracyclododecenes having substituents containing oxygen atoms such as tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imides Decenes; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene Can be mentioned.

Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene and 12-cyclopentenylhexacycloheptadecene; having an aromatic ring such as 12-phenylhexacycloheptadecene Hexacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene Hexacycloheptadecenes having a substituent containing an oxygen atom such as 12,13-dicarboxylic acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13 -Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene compound having a substituent containing a silicon atom such as trimethoxysilyl hexamethylene cycloheptanone decene and the like.

In obtaining a cyclic olefin ring-opening polymer using a polycyclic norbornene-based monomer, one type of polycyclic norbornene-based monomer may be used alone, or two or more types of polycyclic norbornene-based monomers may be used. A combination of monomers can also be used.

From the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting molded product, a polycyclic ring for obtaining a cyclic olefin ring-opening polymer for use in the hydrogenation reaction As the formula norbornene-based monomer, it is preferable to use those containing 50% by weight or more of dicyclopentadiene based on the whole polycyclic norbornene-based monomer used, and it is particularly preferable to use dicyclopentadiene alone.

In addition, polycyclic norbornene monomers include endo isomers and exo isomers, both of which can be used as monomers, and one isomer can be used alone. Alternatively, an isomer mixture in which endo and exo isomers are present in an arbitrary ratio can be used. However, from the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting resin composition, it is preferable to increase the ratio of one stereoisomer, For example, the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

In obtaining a cyclic olefin ring-opening polymer, a monomer other than the polycyclic norbornene monomer is copolymerized with the polycyclic norbornene monomer within a range that gives a polymer having crystallinity. Also good. Examples of monomers that can be copolymerized with polycyclic norbornene monomers include bicyclic norbornene compounds, monocyclic olefins, cyclic dienes, and derivatives thereof that do not have a ring structure fused to a norbornene skeleton. Can do.

Specific examples of a bicyclic norbornene compound having no ring structure condensed to a norbornene skeleton include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5 -Norbornenes having an unsubstituted or alkyl group such as cyclohexyl norbornene and 5-cyclopentyl norbornene; Alkenyl groups such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene Norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl- -Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5 , 5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene and the like norbornenes having a polar group containing an oxygen atom; And norbornenes having a polar group containing a nitrogen atom such as 5-cyanonorbornene.

Specific examples of the monocyclic olefin include cyclohexene, cycloheptene, and cyclooctene. Specific examples of the cyclic diene include cyclohexadiene and cycloheptadiene.

From the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting molded product, a single amount for obtaining a cyclic olefin ring-opening polymer for use in the hydrogenation reaction It is preferable that 80% by weight or more of the polycyclic norbornene-based monomer is included as a body, and the monomer used is substantially composed of only the polycyclic norbornene-based monomer. It is particularly preferable.

When obtaining a hydrogenated product of a cyclic olefin ring-opening polymer having syndiotactic stereoregularity, it is necessary to subject the cyclic olefin ring-opening polymer having syndiotactic stereoregularity to a hydrogenation reaction. Therefore, in ring-opening polymerization of a polycyclic norbornene-based monomer, it is necessary to use a ring-opening polymerization catalyst capable of giving syndiotactic stereoregularity to the cyclic olefin ring-opening polymer. The ring-opening polymerization catalyst to be used is not particularly limited as long as it can give syndiotactic stereoregularity to the cyclic olefin ring-opening polymer, but comprises a metal compound represented by the following formula (3). A ring-opening polymerization catalyst is preferred.

(In the formula, M is a metal atom selected from group 6 transition metal atoms in the periodic table, N is a nitrogen atom, O is an oxygen atom, and R ⁸ is at least in positions 3, 4, and 5. A phenyl group which may have a substituent at one position, or a group represented by —CH ₂ R ¹⁰ , wherein R ⁹ has an alkyl group which may have a substituent and a substituent; X may be a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L may be an electron-donating neutral ligand, a is 0 or 1, b is an integer of 0 to 2. R ¹⁰ is selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Group.)

The metal atom (M in formula (3)) constituting the metal compound represented by formula (3) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.

The metal compound represented by the formula (3) includes a metal imide bond. The substituent on the nitrogen atom constituting the metal imide bond (R ⁸ in the formula (3)) is a phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions, or —CH ₂ R ¹⁰ (wherein R ¹⁰ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent). It is a group. Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an alkyl group such as a methyl group and an ethyl group; a fluorine atom, a chlorine atom, and a bromine atom A halogen atom such as; an alkoxy group such as a methoxy group, an ethoxy group, and an isopropoxy group; and the like, and further, substituents present in at least two positions of the 3, 4, and 5 positions are bonded to each other. Also good. Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, and 3-methoxyphenyl. Groups, monosubstituted phenyl groups such as 4-cyclohexylphenyl group, 4-methoxyphenyl group; 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group, 3,5-dimethoxyphenyl group Disubstituted phenyl groups such as 3,4,5-trimethylphenyl groups, 3,4,5-trichlorophenyl groups and the like; 2-naphthyl groups, 3-methyl-2-naphthyl groups, 4-methyl 2-naphthyl group which may have a substituent such as a 2-naphthyl group;

In the metal compound represented by the formula (3), in the group represented by —CH ₂ R ¹⁰ that can be used as a substituent on the nitrogen atom (R ⁸ in the formula (3)), R ¹⁰ is a hydrogen atom. Represents a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms of the alkyl group which may be a substituent and can be a group represented by R ¹⁰ is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Can be mentioned.

In the metal compound represented by the formula (3), an aryl group which may be used as a substituent on the nitrogen atom (R ⁸ in the formula (3)) and may have a substituent includes a phenyl group, Examples thereof include a 1-naphthyl group, a 2-naphthyl group, and an aryl group in which a hydrogen atom of these groups is replaced with another substituent. Further, the substituent of this aryl group is not particularly limited, but for example, a phenyl group which may have a substituent such as a phenyl group or a 4-methylphenyl group; an alkoxyl group such as a methoxy group or an ethoxy group; Can be mentioned.

The group represented by R ¹⁰ has 1 carbon number such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group. ˜20 alkyl groups are particularly preferably used.

The metal compound represented by Formula (3) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (3), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In addition, when there are two or more groups represented by X in the metal compound represented by the formula (3), these groups may be bonded to each other.

Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The metal compound represented by the formula (3) may have one metal alkoxide bond or one metal aryloxide bond. The substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R ⁹ in formula (3)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups. The alkyl group which may have a substituent and the aryl group which may have a substituent which can be the group represented by R ⁹ are the same as those in the group represented by R ¹⁰ described above. Can be used.

The metal compound represented by the formula (3) may have one or two electron-donating neutral ligands. As this electron-donating neutral ligand (L in Formula (3)), for example, an electron-donating compound containing an atom of Group 14 or Group 15 of the Periodic Table can be mentioned. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine; Among these, ethers are particularly preferably used.

As a ring-opening polymerization catalyst for obtaining a cyclic olefin ring-opening polymer having syndiotactic stereoregularity, the metal compound represented by the formula (3) particularly preferably used is a tungsten compound having a phenylimide group ( A compound in which M in the formula (3) is a tungsten atom and R ⁸ is a phenyl group), among which tetrachlorotungstenphenylimide (tetrahydrofuran) is particularly preferable.

The metal compound represented by the formula (3) includes a group 6 transition metal oxyhalide and phenyl isocyanates which may have a substituent at at least one of the 3, 4, and 5 positions, Alternatively, a mono-substituted methyl isocyanate, an electron-donating neutral ligand (L), and, if necessary, an alcohol, a metal alkoxide, a metal aryloxide, etc. are mixed (for example, JP-A-5-345817). It can be synthesized by the method described in the publication. The synthesized metal compound represented by the formula (3) may be purified and isolated by crystallization, or the catalyst synthesis solution may be used as it is as a ring-opening polymerization catalyst without purification. You can also.

The amount of the metal compound represented by the formula (3) used as the ring-opening polymerization catalyst is such that the molar ratio of (metal compound: whole monomer used) is usually 1: 100 to 1: 2,000,000, preferably Is used in an amount of 1: 500 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.

In using the metal compound represented by the formula (3) as a ring-opening polymerization catalyst, the metal compound represented by the formula (3) can be used alone, but from the viewpoint of increasing the polymerization activity, the formula (3 It is preferable to use a metal compound represented by 3) in combination with an organometallic reducing agent. Examples of the organometallic reducing agent that can be used include organometallic compounds of Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organic lithium, organic magnesium, organic zinc, organic aluminum, or organic tin is preferably used, and organic aluminum or organic tin is particularly preferably used. Examples of the organic lithium include n-butyl lithium, methyl lithium, and phenyl lithium. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Can be mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The amount of the organometallic reducing agent used is preferably 0.1 to 100 moles, more preferably 0.2 to 50 moles, and 0.5 to 20 moles relative to the metal compound represented by the formula (3). Double is particularly preferred. If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.

The polymerization reaction for obtaining the cyclic olefin ring-opening polymer is usually carried out in an organic solvent. The organic solvent to be used is not particularly limited as long as the target ring-opening polymer or a hydrogenated product thereof can be dissolved or dispersed under predetermined conditions and does not inhibit the polymerization reaction or the hydrogenation reaction. Specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclodecane. , Hexahydroindene, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Can mixtures of these solvents. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.

The ring-opening polymerization reaction can be started by mixing the monomer, the metal compound represented by the formula (3), and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a mixture of a metal compound represented by the formula (3) and the organometallic reducing agent may be added to the monomer and mixed, or the monomer and the organometallic reducing agent may be represented by the formula (3). A mixture with a metal compound to be added may be added and mixed, or a metal compound represented by formula (3) may be added to and mixed with a mixture of a monomer and an organometallic reducing agent. . Moreover, when mixing each component, the whole quantity of each component may be added at once, may be added in multiple times, and it is continuous over a comparatively long time (for example, 1 minute or more). It can also be added. Among these, from the viewpoint of controlling the polymerization temperature and the molecular weight of the resulting ring-opening polymer to obtain a resin composition particularly excellent in moldability, the monomer or the metal compound represented by the formula (3) It is preferable to add a plurality of times or continuously, and it is particularly preferable to add the monomer in a plurality of times or continuously.

The concentration of the monomer during the polymerization reaction in the organic solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly 3 to 40% by weight. preferable. If the monomer concentration is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

An activity regulator may be added to the polymerization reaction system. The activity adjusting agent can be used for the purpose of stabilizing the ring-opening polymerization catalyst, adjusting the polymerization reaction rate and the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Triisopropylamine, quinuclidine, amines such as N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as triphenyl phosphate and trimethyl phosphate; triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphate, trimethyl phosphate - phosphines such as preparative; phosphine oxides such as triphenylphosphine oxide; but like, but not limited to. These activity regulators can be used singly or in combination of two or more. The amount of the activity regulator to be added is not particularly limited, but it may be usually selected between 0.01 and 100 mol% with respect to the metal compound used as the ring-opening polymerization catalyst.

Further, a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight regulators include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1 3-pentadiene, a conjugated diene such as 1,3-hexadiene; can be mentioned. The amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer used.

Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.

Using the ring-opening polymerization catalyst containing the metal compound represented by the formula (3) as described above, the ring-opening polymerization reaction of the monomer containing the polycyclic norbornene monomer is performed under the conditions as described above. Thus, a cyclic olefin ring-opening polymer having syndiotactic stereoregularity can be obtained. Since the tacticity of the polymer does not change during the hydrogenation reaction, the cyclic olefin ring-opening polymer having this syndiotactic stereoregularity is subjected to a hydrogenation reaction, thereby having syndiotactic stereoregularity. A crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer having crystallinity can be obtained.

The ratio of racemo dyad in the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is usually 60% or more, preferably 65% or more, more preferably 70 to 99%. The ratio of racemo dyad (degree of syndiotactic stereoregularity) in the cyclic olefin ring-opening polymer can be adjusted by selecting the kind of the ring-opening polymerization catalyst.

Although the weight average molecular weight (Mw) measured by the gel permeation chromatography which used tetrahydrofuran as a solvent of the cyclic olefin ring-opening polymer with which it uses for hydrogenation reaction is not specifically limited, It is 10,000-100,000 in polystyrene conversion. It is preferable that it is 15,000-80,000. Use of a cyclic olefin ring-opened polymer hydrogenated product obtained from a cyclic olefin ring-opened polymer having such a weight average molecular weight is preferable in terms of excellent moldability and excellent heat resistance of the obtained molded body. The weight average molecular weight of the cyclic olefin ring-opening polymer can be adjusted by adjusting the addition amount of the molecular weight modifier used during the polymerization.

The molecular weight distribution of the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction [ratio of number average molecular weight and weight average molecular weight (Mw / Mn) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent] Although not limited, it is usually 1.5 to 4.0, preferably 1.6 to 3.5. Use of a cyclic olefin ring-opened polymer hydrogenated product obtained from a cyclic olefin ring-opened polymer having such a molecular weight distribution is preferred in terms of excellent moldability. The molecular weight distribution of the cyclic olefin ring-opening polymer hydrogenated product can be adjusted by the monomer addition method and the monomer concentration during the ring-opening polymerization reaction.

The hydrogenation reaction of the cyclic olefin ring-opened polymer (hydrogenation of the main chain double bond) can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. Any hydrogenation catalyst can be used as long as it is generally used in the hydrogenation of olefin compounds, and is not particularly limited. Examples thereof include the following.

As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Examples include butyl lithium, tetrabutoxy titanate / dimethyl magnesium, and the like. Further, noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium, etc. Can do.

As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like. The inert organic solvent is usually the same as the solvent used in the polymerization reaction, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.

Although the suitable range of conditions varies depending on the hydrogenation catalyst system used, the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required. Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 10 hours.

The hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the cyclic olefin ring-opening polymer is not particularly limited, but is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more, most preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the cyclic olefin ring-opening polymer hydrogenated product.

The cyclic olefin ring-opening polymer hydrogenated product obtained as described above has a repeating unit derived from a polycyclic norbornene-based monomer as represented by the following formula (4) or formula (5). Is.

(Wherein R ¹ and R ² are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

(Wherein R ^{4 to} R ⁷ are each independently a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a substitution containing a silicon atom, an oxygen atom or a nitrogen atom) And R ⁴ and R ⁶ may be bonded to each other to form a ring, and m is 1 or 2.)

Moreover, in the cyclic olefin ring-opened polymer hydrogenated product obtained as described above, the syndiotactic stereoregularity of the ring-opened polymer subjected to the hydrogenation reaction is maintained. Therefore, the cyclic olefin ring-opening polymer hydrogenated product obtained as described above has syndiotactic stereoregularity. The ratio of racemo dyad in the cyclic olefin ring-opening polymer hydrogenated product used in the present invention is not particularly limited as long as the hydrogenated product has crystallinity, but is usually 55% or more, preferably 60% or more, more preferably Is 65-99%. By using such a cyclic olefin ring-opening polymer hydrogenated product having syndiotactic stereoregularity, the obtained resin composition can give a molded product that is hardly deformed by the influence of heat. Become. The ratio of the racemo dyad of the cyclic olefin ring-opening polymer hydrogenated product depends on the ratio of the racemo dyad of the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction.

The ratio of the racemo dyad of the cyclic olefin ring-opening polymer hydrogenated product can be measured and quantified by ¹³ C-NMR spectrum analysis. The method of quantification varies depending on the polymer. For example, in the case of a hydrogenated ring-opened polymer of dicyclopentadiene, ¹³ C-NMR measurement is performed at 150 ° C. using orthodichlorobenzene-d4 as a solvent, and meso-dyad. The ratio of racemo dyad can be determined from the intensity ratio of the 43.35 ppm signal from the origin and the 43.43 ppm signal from the racemo dyad.

As long as the crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer used for constituting the resin composition of the present invention has crystallinity, The melting point is not particularly limited, but preferably has a melting point of 200 ° C. or higher, more preferably 230 to 290 ° C. By using a hydrogenated cyclic olefin ring-opening polymer having such a melting point, it is possible to obtain a resin composition particularly excellent in the balance between moldability and heat resistance. The melting point of the cyclic olefin ring-opening polymer hydrogenated product can be adjusted by adjusting the degree of syndiotactic stereoregularity (racemo dyad ratio) and the type of monomer used. can do.

As the glass filler used in the present invention, known ones can be used, and the shape thereof is not limited. For example, glass fiber, glass bead, glass powder, glass flake, glass balloon, etc. are mentioned. Among these, it is preferable to use glass fiber because of the high mechanical strength of the molded product. The shape and form of the glass fiber used in the present invention are not particularly limited. Specific examples include milled fiber, cut fiber, chopped strand, roving and the like, and chopped strand is particularly preferred from the viewpoint of high mechanical strength of the molded product and ease of handling. Moreover, it is preferable that it is 3-40 mm, and, as for the length of the glass fiber used for this invention, it is more preferable that it is 5-30 mm. If the length is short, the mechanical strength of the molded product is low, and if it is long, there is a problem in handling during kneading. The cross-sectional shape of the glass fiber used in the present invention is arbitrary, such as a circle, an ellipse, a flat shape, and a rectangle, and these glass fibers can be used in any ratio. The glass filler used in the present invention may be surface-treated with a silane compound, an epoxy compound, a urethane compound, or the like.

The blending amount of the glass filler in the present invention is such that the weight ratio of the crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene monomer and the glass filler is 95/5 to 40. / 60, preferably in the range of 85/15 to 50/50. If the blending amount of the glass filler is too small, the heat resistance during reflow and the strength of the molded product are inferior, and if the blending amount of the glass filler is too large, the dielectric loss tangent is increased and the moldability is poor.

Ceramics can be blended in the resin composition of the present invention. As ceramics, paraelectric ceramics are preferable from the viewpoints of suppressing changes in electrical characteristics with respect to temperature changes and suppressing the dielectric loss tangent to be low. Furthermore, paraelectric ceramics having a dielectric constant in the range of 30 to 1000, preferably 50 to 800, and more preferably 70 to 500 are preferred as a material for a high frequency small antenna. When ceramics with a dielectric constant of less than 30 is blended, the dielectric constant is low and does not contribute to the miniaturization of the antenna. When ceramics with a dielectric constant of greater than 1000 are blended, the value of the dielectric loss tangent also increases. Occurrence becomes large, which is not preferable.

As such a paraelectric ceramic, a metal oxide is preferably used, and a metal titanate is particularly preferable. Here, “metal titanate” refers to a compound containing titanium element, other metal elements other than titanium, and oxygen element as essential elements.

Specific examples of paraelectric ceramics include metal titanates such as strontium titanate, calcium titanate, magnesium titanate, neodymium titanate, lanthanum titanate, and zinc titanate (however, ferroelectric barium titanate) And potassium titanate). These paraelectric ceramics can be surface-treated with a coupling agent in advance, or can be surface-treated by an integral method in which a coupling agent is added at the time of blending. A preferred coupling agent is a titanate coupling agent. The shape of the high dielectric constant filler is arbitrary such as granular, irregular, flake, and fibrous, and the high dielectric constant filler of these shapes can be used in any ratio. The weight average particle size of the high dielectric constant filler is preferably 0.05 μm or more from the viewpoint of bulk density and resin filling properties, preferably 100 μm or less from the viewpoint of thickness accuracy of the resin layer, and more preferably. Is 0.1 to 70 μm.

Paraelectric ceramics can be added singly or in combination of two or more. The compounding amount of the paraelectric ceramic is usually 5 with respect to 100 parts by weight of the total amount of the crystalline cyclic olefin ring-opening polymer hydrogenated product and glass filler having a repeating unit derived from a polycyclic norbornene monomer. It is selected in the range of -100 parts by weight, preferably 10-90 parts by weight. If the blending amount of the paraelectric ceramic is small, the dielectric constant is low, and if the blending amount of the paraelectric ceramic is large, it is not preferable because it becomes difficult to manufacture a molded product and mechanical strength such as bending strength is lowered.

The resin composition used in the present invention may be composed of only a crystalline cyclic olefin ring-opening polymer hydrogenated product and a glass filler, or may be composed of other materials as additives. Other materials that can be blended include antioxidants, fillers, colorants, flame retardants, flame retardant aids, antistatic agents, plasticizers, ultraviolet absorbers, light stabilizers, near infrared absorbers, and optical brighteners. Other than lubricants, lubricants, nucleating agents, metal oxides capable of forming single metal nuclei upon irradiation with electromagnetic radiation, and crystalline cyclic olefin ring-opening polymer hydrogenated products having repeating units derived from polycyclic norbornene monomers A polymer material can be exemplified.

The mixing order of crystalline cyclic olefin ring-opening polymer hydrogenated product with repeating units derived from polycyclic norbornene monomers, glass filler, paraelectric ceramics and other additives blended as required Is optional. A crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a glass filler and a polycyclic norbornene monomer may be blended in advance, or a paraelectric ceramic and a polycyclic norbornene monomer A crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from the product may be blended in advance. The mixing method is a method in which these compounding agents are sufficiently dispersed in the polymer, and is not limited to a specific method. Specific examples of the mixing method include a method of kneading a resin in a molten state with a mixer, a single-screw kneader, a twin-screw kneader, a roll, a brabender, an extruder, etc., and a solidifying method by dissolving and dispersing in an appropriate solvent. Or a method of removing the solvent by a direct drying method.

When a biaxial kneader is used, the resin composition is usually extruded into a rod shape in a molten state after kneading, cut into an appropriate length with a strand cutter, and pelletized.

The molded product of the present invention is obtained by molding the above-described resin composition of the present invention. As the molding method, a conventionally known molding method suitable for a molded product can be adopted. Specific examples thereof include injection molding, press molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, and rotational molding. The melting temperature of the resin at the time of molding varies depending on the kind of the crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer, but is usually 250 to 400 ° C., preferably 260 ~ 350 ° C. The shape and size of the molded product may be determined according to the purpose of use, and are not particularly limited.

Molded articles obtained using the resin composition of the present invention include, for example, automobile exterior members such as bonnets, trunk doors, doors, fenders, grills; engine members such as air intakes and engine covers; housings for headlamps, rear lamps Vehicle casings, reflectors, extension reflectors and other vehicle lighting components; instrument panel, seat housing and other automotive interior parts; automotive motor cases, sensor cases, module component cases, fuel cell stack separators, and other automotive parts; power assist Bicycle members such as battery members; Housings for robot parts such as power assists, industrial robots, electric wheelchair members; aircraft interior members; hull members; TVs, refrigerators, air conditioners, electric fans, humidifiers, dehumidifiers , Drying washing machine, dishwasher, microwave oven, rice cooker, electric Household appliance parts such as jarpots and dryers; PCs, printers, copiers, telephones, fax machines, audio equipment, cameras, game machines, hard disk drives, mobile phones, smartphones, and other electronic products; connectors, relays, capacitors, sensors Electronic components such as antennas, IC trays, chassis, coil seals, motor cases, power supply boxes, etc .; backlight light source lighting fixtures for liquid crystal displays of large liquid crystal display devices; liquid crystals for small electronic devices such as mobile phones, smartphones, tablets, etc. Light source illuminator for display backlight; LED reflector used as light source for electric display boards such as road traffic display boards; Optical lens barrel; Flexible printed circuit board; Release film for laminated printed wiring board; Substrate for solar cell Packaging, packaging film, food Sheets, trays; LED molding materials; pump casings, impellers, pipe joints, bathtubs, septic tanks, bathroom panels, exterior panels, window sash rails, window insulation, wash bowls, and other housing parts; road reflectors, signs, It can be used as a road facility member such as a signal; an industrial member such as an infusion container, a chemical solution layer, a chemical solution pipe, a gas pipe, a container, a pallet, a rack column; and a sporting article such as a fishing rod or a golf club shaft.

A suitable molded article made of the resin composition of the present invention is a high frequency dielectric antenna. A high frequency dielectric antenna is formed by forming an antenna substrate made of a resin composition and providing a radiation electrode, a feeding electrode, and a ground electrode on the surface thereof. As an electrode, well-known things, such as copper, silver, gold | metal | money, platinum, aluminum, palladium, can be used. Also, the electrodes can be prepared by etching, sputtering, plating, three-dimensional circuit forming method by MID (Molded Interconnect Device), vacuum deposition, LDS (Laser) using a metal oxide capable of forming a single metal nucleus by electromagnetic radiation. A known method such as a Direct Structure method can be used.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the part and% in each example are a basis of weight unless there is particular notice.

Moreover, the measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight (weight average molecular weight and number average molecular weight) of cyclic olefin ring-opening polymer
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was used and measured at 40 ° C. using tetrahydrofuran as a solvent to obtain a polystyrene equivalent value.
(2) Hydrogenation rate in cyclic olefin ring-opening polymer hydrogenated product
^It was determined by ¹ H-NMR measurement.
(3) Measured by raising the temperature of the cyclic olefin ring-opened polymer hydrogenated product at 10 ° C./min using a differential melting scanning calorimeter.
(4) Ratio of racemo dyad of cyclic olefin ring-opening polymer hydrogenated product Using orthodichlorobenzene-d ₄ as a solvent, ¹³ C-NMR measurement was performed at 150 ° C., and a 43.35 ppm signal derived from meso dyad , Based on the intensity ratio of the 43.43 ppm signal from Racemo Dyad.
(5) The bending strength test piece 1 was subjected to a bending test at a test speed of 2 mm / min according to JIS K 7171 using an autograph (product name “AGS-5kNJ · TCR2”, manufactured by Shimadzu Corporation) to obtain a bending strength. Was measured.
(6) The reflow resistance test piece 1 was subjected to heat treatment at 260 ° C. for 10 seconds using an oven three times, and then the reflow resistance was evaluated by visually observing the test piece. Here, the test piece maintained the shape without being deformed and melted before and after the heat treatment, and the case where the test piece was deformed and melted was rated as x.
(7) Dielectric constant and dielectric loss tangent test piece 2 were measured for dielectric constant and dielectric loss tangent according to ASTM D2520 by a cylindrical cavity resonator method using a network analyzer (product name “N5230A”, manufactured by Agilent). . The frequency at the time of measurement was 1 GHz, 5 GHz, and 10 GHz.

[Synthesis Example 1]
After fully drying, a pressure-resistant reaction vessel made of nitrogen-substituted glass was charged with 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene). 738 parts of cyclohexane and 3.3 parts of 1-hexene were added and heated to 50 ° C. Meanwhile, 4.6 parts of a 19 wt% diethylaluminum ethoxide / n-hexane solution was added to a solution of 1.1 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 56 parts of toluene and stirred for 10 minutes. A catalyst solution was prepared. This catalyst solution was added to the reactor to initiate a ring-opening polymerization reaction. Thereafter, while maintaining 50 ° C., 40 parts of a 75% dicyclopentadiene / cyclohexane solution was added 9 times every 5 minutes, and then the reaction was continued for 2 hours. Next, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the polymer. The solidified polymer was separated from the solution by filtration, and the polymer was recovered. The obtained ring-opening polymer was dried at 40 ° C. under reduced pressure for 20 hours. The yield of the polymer was 296 parts (yield = 99%). Further, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of this polymer are 10,100 and 17,200, respectively, and the molecular weight distribution (Mw / Mn) obtained therefrom is 1.70. It was. Subsequently, 60 parts of the obtained polymer and 261 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred. After the polymer was dissolved in cyclohexane, 0.039 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium was added to 40 parts of toluene. A hydrogenation catalyst solution dissolved in was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The obtained hydrogenation reaction solution is poured into a large amount of isopropyl alcohol to completely precipitate a polymer, washed by filtration, dried under reduced pressure at 60 ° C. for 24 hours, and a crystalline cyclic olefin ring-opening polymer hydrogenated product. A was obtained. The hydrogenation rate of the cyclic olefin ring-opening polymer hydrogenated product A was 99% or more, the ratio of racemo dyad was 79%, and the melting point was 260 ° C. In addition, the amount of 1-hexene used in the polymerization reaction, the number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the obtained ring-opening polymer, and the obtained ring-opening weight The hydrogenation rate and melting point of the combined hydrogenated product are summarized in Table 1.

[Synthesis Examples 2 and 3]
Cyclic olefin ring-opening polymer hydrogenated product B and cyclic olefin ring-opening polymer hydrogenated product as in Synthesis Example 1 except that the amount of 1-hexene used in the polymerization reaction was changed as shown in Table 1. C was obtained. Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained ring-opening polymer, hydrogenation rate of the obtained ring-opening polymer hydrogenated product, racemo dyad The ratio and melting point are summarized in Table 1.

[Synthesis Example 4]
After sufficiently drying, in a reaction vessel equipped with a stirrer purged with nitrogen, 300 parts of dehydrated cyclohexane, 0.5 part of 1-hexene, 0.15 part of dibutyl ether and 1.5 parts of a 10% by weight tricyclobutylaluminum cyclohexane solution were added. Added and warmed to a temperature of 40 ° C. While maintaining the temperature and stirring the reaction solution, a mixture of 70 parts of tetracyclododecene and 30 parts of dicyclopentadiene and 11 parts of a tungsten hexachloride 0.6 wt% cyclohexane solution were continuously added to the polymerization reaction at the same time. I was allowed to. After completion of the polymerization reaction, 0.5 part of butyl glycidyl ether and 0.2 part of isopropyl alcohol were added to terminate the polymerization reaction.
400 parts of the polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 4 parts of a diatomaceous earth-supported nickel catalyst (manufactured by Sud Chemie Catalysts; T8400RL, nickel support rate 57%) was added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the liquid, and a hydrogenation reaction was performed at a temperature of 170 ° C. and a pressure of 4.5 MPa for 5 hours.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then 0.1 part of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added. Then, using a thin film evaporator (product name “Film Truder”, manufactured by Buss), the volatile matter was removed under the conditions of a temperature of 260 ° C. (533 ° K), a pressure of 1 kPa or less, and a residence time of 1.2 hours. Evaporation yielded a hydrogenated product D of tetracyclododecene-dicyclopentadiene ring-opening copolymer. The glass transition temperature of the ring-opening copolymer hydrogenated product D was 142 ° C. Number-average molecular weight (Mn), weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of tetracyclododecene-dicyclopentadiene ring-opening copolymer hydrogenated product D, and obtained ring-opening polymer hydrogen The hydrogenation rates of the additives are summarized in Table 1.

<Example 1>
Cyclic olefin ring-opening polymer hydrogenated product A 85 parts, glass fiber (trade name “CSG 3PA-830”, manufactured by Nittobo), calcium titanate (average particle size 2.3 μm, trade name “CT”, Kyoritsu 40 parts by Material Co., antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, trade name “Irganox® 1010”) After mixing 0.8 parts of BASF Japan Ltd., the mixture was pelletized by kneading for 2 minutes at 290 ° C. and 100 RPM using a small kneader (Micro15 Compounder, DSM Xplore).
Then, using a small injection molding machine (Micro Injection Molding Machine 10cc, manufactured by DSM Xplore), the molding temperature is 290 ° C, the injection pressure is 0.7MPa, the mold temperature is 150 ° C, and the holding time in the mold is 80mm. A test piece 1 having a thickness of 10 mm and a thickness of 4 mm and a test piece 2 having a length of 100 mm, a width of 1 mm, and a thickness of 1 mm were formed. The composition of the composition and each evaluation result are summarized in Table 2.
<Examples 2-5 and Comparative Examples 1-3>
Except having changed the composition of the composition as shown in Table 2, a molded product was obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2. As for the paraelectric ceramics, magnesium titanate is trade name “MT-1S” (average particle size 2.6 μm, manufactured by Kyoritsu Materials Co., Ltd.), and strontium titanate is trade name “ST” (average particle size 1.6 μm). , Manufactured by Kyoritsu Material Co., Ltd.).

As can be seen from Table 2, the resin compositions (Examples 1 to 5) of the present invention had good mechanical strength and electrical characteristics and had reflow resistance. On the other hand, when the amount of glass filler is small, deformation is observed during the reflow test (Comparative Example 3), and when the amount of glass filler is large, the electrical characteristics deteriorate (Comparative Example 2). Moreover, when the alicyclic structure containing polymer hydrogenation which is not a crystalline cyclic olefin ring-opening polymer hydrogenation was used, it turned out that it does not have reflow resistance (comparative example 4).

Claims (4)

(A) A resin composition comprising a hydrogenated crystalline cyclic olefin ring-opening polymer having a repeating unit derived from a polycyclic norbornene-based monomer, and (B) a glass filler, wherein the crystalline property weight ratio of 95 / 5-40 / 60 der of the cyclic olefin ring-opening polymer hydrogenation product and the glass filler is,
The crystallinity of the cycloolefin ring-opening polymer hydrogenation product and the total amount 100 parts by weight of a glass filler, further paraelectric ceramics resin composition characterized that you containing 5-100 parts by weight. Claim 1 resin composition wherein the paraelectric ceramics metal titanate. A molded article comprising the resin composition according to claim 1 or 2 . The molded article according to claim 3 , which is a high-frequency dielectric antenna.