JP2005089743A - Molding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding material composed of an alicyclic structure-containing resin having excellent resistance to oxidative deterioration. <P>SOLUTION: This molding material contains (1) the alicyclic structure-containing resin and (2) a phenol compound having a hydrocarbon residue and a residue of R-O- (R is a hydrocarbon residue which may be substituted) as substituents, wherein the phenol compound (2) contains a phenol compound expressed by formula (I) (R<SP>1</SP>and R<SP>2</SP>are each H or a secondary or tertiary hydrocarbon residue, provided that at least one of R<SP>1</SP>and R<SP>2</SP>is a secondary or tertiary hydrocarbon residue; R<SP>3</SP>is a hydrocarbon residue which may be substituted; A is a hydrocarbon residue; (p) is 0, 1 or 2; and (q) is 1, 2 or 3). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a molding material containing an alicyclic structure-containing resin having excellent oxidation resistance.

Conventionally, resins obtained by polymerizing olefin monomers are excellent in heat resistance, low water absorption, moisture proofing, low dielectric properties, etc., so they are molded into desired shapes, optical parts, automobile parts, electrical / electronic parts, Used for molded products such as packaging materials. In particular, an alicyclic structure-containing resin obtained by polymerizing a cycloolefin monomer is preferably used because of good electrical characteristics. There are various methods for obtaining a molded body comprising an alicyclic structure-containing resin. For example, a polymerizable monomer containing a cycloolefin monomer is polymerized to obtain an alicyclic structure-containing resin, which is dissolved in a solvent as necessary. Then, a method of forming into an arbitrary shape by drying or crosslinking is mentioned.
In recent years, molded products used in various parts, especially electronic parts such as electrical insulation materials, have changed electrical characteristics under higher temperature and humidity conditions to ensure excellent electrical insulation and other quality. There is a need to suppress it. Such a change in electrical characteristics typified by a change in dielectric loss tangent is often caused by oxidative degradation of the resin, and therefore an antioxidant is added to the alicyclic structure-containing resin. As the antioxidant, a hindered phenol-based antioxidant such as an alkyl-substituted phenol-based compound or a phosphorus-based antioxidant is used (Japanese Patent Laid-Open No. 2000-143944, etc.).

JP 2000-143944 A

However, as a result of studies by the present inventors, it has been found that even when the general antioxidant described in the above publication is used, the dielectric loss tangent at 1 GHz, for example, is increased after storage under high temperature and high humidity conditions. . In a material having a very low dielectric loss tangent, an increase in dielectric loss tangent leads to a significant change in electrical characteristics, which is a problem in electrical and electronic materials, particularly in high frequency applications.
Based on this knowledge, the present inventors diligently studied to obtain a molded article having a higher antioxidant effect. As a result, secondary or tertiary hydrocarbon groups and R—O— groups (R is The use of a phenol compound having a hydrocarbon group which may have a substituent; hereinafter simply referred to as R—O— group provides a much superior antioxidant effect even under high temperature and high humidity conditions. As a result, the present invention has been completed.

  Thus, according to the present invention, there is provided a molding material containing (1) an alicyclic structure-containing resin and (2) a phenol compound having a secondary or tertiary hydrocarbon group and R—O— group.

Hereinafter, the present invention will be described in detail.
The molding material of the present invention contains an alicyclic structure-containing resin and a phenol compound having a specific structure.
<Alicyclic structure-containing resin>
The alicyclic structure-containing resin is polymerized using a cycloolefin monomer as a polymerizable monomer.
Moreover, the alicyclic structure containing resin can use together the monomer copolymerizable with a cycloolefin monomer other than a cycloolefin monomer as a polymerizable monomer. The ratio of the cycloolefin monomer is usually 10% to 100% by weight, preferably 20 to 100% by weight, more preferably 40 to 100% by weight, and particularly preferably 40 to 100% by weight, based on the total amount of the polymerizable monomer, from the viewpoint of electrical characteristics. Preferably it is 50-100 weight%, Most preferably, it is 60-100 weight%.

The cycloolefin monomer used for the production of the alicyclic structure-containing resin is an olefin having an alicyclic structure in the molecule. Examples of the alicyclic structure include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. Although carbon number which comprises an alicyclic structure does not have a special restriction | limiting, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is the range of 5-15 pieces.
Examples of such cycloolefin monomers include norbornene monomers and monocyclic olefin monomers. The norbornene-based monomer is a cycloolefin monomer having a norbornene feeling, and examples include norbornenes, dicyclopentadienes, tetracyclododecenes, and norbornene-based monomers having five or more rings.
In the case of using a norbornene-based monomer, a combination with a phenol compound having a secondary or tertiary hydrocarbon group and an R—O— group is preferable because the antioxidant effect can be obtained.

Specific examples of the norbornenes include bicyclo [2.2.1] hept-2-ene (also referred to as 2-norbornene), 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and 5-phenyl- 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), 5-norbornen-2-yl acrylate, 5-norbornene-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, 7-oxa-2-norbornene , 5-ethylidene-7-oxa-2-norbornene and the like.

Specific examples of the cyclopentadiene include cyclopentadiene, dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (tricyclo [5.2.1.0 ^2,6 ] dec-8-ene), cyclopentadiene trimer Examples include the body.

Specific examples of tetracyclododecenes include tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (hereinafter referred to as 4-tetracyclododecene), 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-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 the like.

Specific examples of the norbornene-based monomer having five or more pentacycles include pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and the like.

  Monocyclic olefinic monomers are compounds having only one unsaturated aliphatic ring, cyclobutene, cyclopentene, cyclooctene, cyclododecene, vinylcyclohexene, 1,5-cyclooctadiene, and derivatives thereof having functional groups And so on.

Among such cycloolefin monomers, norbornene monomers are preferred, in particular, 2-norbornene, 5-ethylidene-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), dicyclopentadiene, cyclopentadiene trimer, Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene is preferred. In the cycloolefin monomer to be used, the ratio of the norbornene-based monomer is preferably 50 mol% or more, and more preferably 70 mol% or more, from the viewpoint of heat resistance.
These cycloolefin monomers can be used alone or in combination of two or more.

  Examples of other polymerizable monomers include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1-pentene. 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1 An α-olefin having 3 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; 1,4-hexadiene, 4- Non-conjugated dienes such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; good examples such as styrene, α-methylstyrene, and divinylbenzene An aromatic olefin etc. are mentioned. These can be used alone or in combination of two or more thereof.

  The alicyclic structure-containing resin used in the present invention is a polymerizable monomer having the above cycloolefin monomer as an essential component, for example, disclosed in JP-A-06-100668 and JP-A-07-018021. It can be produced by a ring polymerization method or an addition polymerization method. In particular, since the catalytic activity at the time of polymerization is excellent, from the viewpoint of productivity, it is preferable to use a complex of molybdenum, ruthenium or osmium as a metathesis polymerization catalyst, and it is particularly preferable to produce by a metathesis polymerization using a ruthenium carbene complex. Further, some or all of the olefinic unsaturated groups (such as the main chain double bond and the unsaturated ring double bond) of the alicyclic structure-containing resin may be converted into hydrogen by a general method, for example, Japanese Patent Application Laid-Open No. 06-136057. It may be saturated by the addition method to obtain a hydrogenated product.

  Examples of the alicyclic structure-containing resin suitably used in the present invention include cycloolefin monomer ring-opening polymer and hydrogenated product thereof, cycloolefin monomer addition polymer, and monomer copolymerizable with cycloolefin monomer. Among these, a ring-opening polymer of a norbornene monomer and a hydrogenated product thereof, an addition polymer of a norbornene monomer, and an addition polymer of a norbornene monomer and a chain olefin are preferable.

  The molecular weight of the alicyclic structure-containing resin used in the present invention is appropriately selected according to the purpose of use, and is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), usually 1,000. ˜1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 250,000. When the weight average molecular weight (Mw) of the alicyclic structure-containing resin is within this range, the moldability, the heat resistance of the obtained molded article, the smoothness of the surface, etc. are highly balanced, which is preferable.

  The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing resin used in the present invention is appropriately selected according to the purpose of use, and is usually 5 or less, preferably 4 or less, more preferably 3 or less. When the molecular weight distribution of the alicyclic structure-containing resin is within this range, the moldability and the strength of the molded body are highly balanced, which is preferable.

  The glass transition temperature of the alicyclic structure-containing resin used in the present invention is appropriately selected according to the purpose of use, and is usually 30 to 350 ° C, preferably 50 to 250 ° C, more preferably 70 to 200 ° C. . When the glass transition temperature of the alicyclic structure-containing resin is within this range, the moldability and the heat resistance of the molded body are highly balanced, which is preferable.

The melt index (MI) of the alicyclic structure-containing resin used in the present invention is appropriately selected depending on the purpose of use, and is usually measured when measured at a test temperature of 260 ° C. and a test load of 2.16 Kgf / cm ² in accordance with JIS K7210. The range is 1 to 100 g / 10 minutes, preferably 2 to 50 g / 10 minutes, and more preferably 5 to 30 g / 10 minutes. When the MI of the alicyclic structure-containing resin is excessively large, the strength of the molded body is inferior. Conversely, when the MI is excessively small, the moldability may be inferior. In order to adjust the MI of the resin within this range, for example, a monomer that also functions as a chain transfer agent such as 1-hexene or styrene as another polymerizable monomer is compared with the total polymerizable monomer. In general, the resin may be produced using 0.05 to 5% by weight, preferably 0.1 to 2% by weight.

<Phenol compound having secondary or tertiary hydrocarbon group and R—O— group>
The phenol compound having a secondary or tertiary hydrocarbon group and R—O— group used in the present invention has one or more secondary or tertiary hydrocarbon groups bonded as a phenol substituent, and R—O—. A compound in which one or more groups are bonded. The secondary or tertiary hydrocarbon group is preferably bonded to the ortho position with respect to the phenolic hydroxyl group.

  Secondary or tertiary hydrocarbon groups include isopropyl, s-butyl, t-butyl, 2-methylbutyl, 2,2-dimethylpropyl, cycloheptyl, 2-methylpentyl, 2- Ethylbutyl group, 2,2-dimethylbutyl group, 2-ethyl-2-methylpropyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylhexyl group, 2-ethylpentyl group, 2,2-dimethylpentyl group, 2-ethyl-2-methylbutyl group, 2-methylheptyl group, cycloheptyl group, 2-methylcyclohexyl group, 2-ethylhexyl group, cyclooctyl group, 2-methylcycloheptyl group, 2,2-dimethylhexyl group, 2 -Ethyl-2-methylpentyl group, 2-methyloctyl group, 2-ethylheptyl group, 2,2-dimethylheptyl group, -Ethyl-2-methylhexyl group, 2-methylnonyl group, 2,2-dimethyloctyl group, 2,2-dimethylnonyl group, 1-methylbenzyl group, 1,1-dimethylbenzyl group, diphenylmethyl group, triphenyl A methyl group, a phenyl group, etc. are mentioned. Among these, a secondary or tertiary alkyl group is preferable, and a tertiary alkyl group is particularly preferable.

Examples of the R—O— group include an alkoxy group, a phenoxy group, and an aralkyloxy group, and among these, an alkoxy group is preferable. These may have a substituent containing a hetero atom such as oxygen, nitrogen, phosphorus, sulfur, halogen, or silicon.
Examples of the alkoxy group include an alkyl group having 1 to 100 carbon atoms which may have a substituent and an oxygen atom. The number of carbon atoms of the alkyl group constituting the alkoxy group is preferably 1 to 50, more preferably 1 from the viewpoint of compatibility with an alicyclic structure-containing resin and a solvent used when a molded body is obtained using the resin as a solution. ˜30, particularly preferably about 1˜20. Further, the alkyl group moiety may be linear, branched or cyclic. Specific examples include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, a heptyloxy group, and an octadecyloxy group.
Examples of the phenoxy group include a phenoxy group and a hydroxyphenoxy group, and examples of the aralkyloxy group include a benzyloxy group.

  As a particularly suitable compound as a phenol compound having a secondary or tertiary hydrocarbon group and an R—O— group, a compound represented by the following formula (I) may be mentioned.

In formula (I), R ¹ and R ² are each a hydrogen atom or a secondary or tertiary hydrocarbon group, and either one is at least a secondary or tertiary hydrocarbon group. R ₃ is a hydrocarbon group which may have a substituent.
In formula (I), A is a hydrocarbon group.
In the formula (I), p is 0, 1 or 2, preferably 0 or 1, more preferably 0, and q is 1, 2 or 3, preferably 1 or 2, more preferably 1.

Specific examples of the secondary or tertiary hydrocarbon group that can be R ¹ or R ² are the same as those described above. R ¹ and R ² are preferably a secondary or tertiary hydrocarbon group, and more preferably a secondary or tertiary alkyl group having 3 or more carbon atoms, since they are excellent in antioxidant effect. In particular, it is preferably a secondary or tertiary hydrocarbon group having 3 to 10 carbon atoms.
R ₃ is a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. This hydrocarbon group may have a substituent containing a hetero atom such as oxygen, nitrogen, phosphorus, sulfur, halogen, or silicon. Of the hydrocarbon groups, an alkyl group is preferred. The alkyl group may be linear, branched or cyclic, and suitable examples include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, an o-tolyl group, a p-tolyl group, and a naphthyl group, and a phenyl group is preferable. Examples of the aralkyl group include a benzyl group and a triphenylmethyl group. The number of carbon atoms constituting R ₃ is not particularly limited, but is usually 1 to 50, preferably 1 to 35. The number of heteroatoms in the substituent is not particularly limited, but is usually 1 to 30, and preferably 1 to 15.
A is a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an aryl group, and an aralkyl group. This hydrocarbon group has no substituent. Specific examples are the same as R ₃ described above as specific examples and preferred examples.

  Specific examples of the phenol compound having a secondary or tertiary hydrocarbon group and an R—O— group include 2,6-di-t-butyl-4-methoxyphenol, 2,6-di-t-butyl- 4-ethoxyphenol, 2,6-di-t-butyl-4-octadecyloxyphenol, 2,6-dicyclohexyl-4-methoxyphenol, 2,6-diphenyl-4-methoxyphenol, 2-t-butyl-6 -Cyclohexyl-4-methoxyphenol, 2-cyclohexyl-6-t-butyl-4-methoxyphenol, 2-t-butyl-6-phenyl-4-methoxyphenol, 2-phenyl-6-t-butyl-4- Methoxyphenol, 2-cyclohexyl-6-phenyl-4-methoxyphenol, 2-phenyl-6-cyclohexyl-4-methoxypheno , Octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenoxy) pionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl- 4-hydroxyphenoxy) propionamide], hexamethylenebis [3- [3,5-di-t-butyl-4-hydroxyphenoxy] propionate, 1,3,5-tris [(3,5-di-t- Butyl-4-hydroxyphenoxy) propyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, tetrakis [methylene 3- (3,5-di-t-butyl-4 -Hydroxyphenoxy) propionate] like methane. Among these, 2,6-di-t-butyl-4-methoxyphenol and 2-t-butyl-4-methoxyphenol, which are particularly excellent in antioxidant action, are preferable, and 2,6-di-t-butyl is particularly preferable. -4-Methoxyphenol is preferred.

  The phenol compound having a secondary or tertiary hydrocarbon group and R—O— group can be used alone or in combination of two or more, and the blending amount thereof is 100 parts by weight of the alicyclic structure-containing resin. The range is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. If it is this range, the antioxidant effect and electrical property of the molding which are obtained will be balanced.

<Additives>
The molding material of this invention can contain components other than the component mentioned above as an additive.
As the additive, those generally used for molding materials can be used without particular limitation. For example, an antioxidant other than the above-described phenol compound having a secondary or tertiary hydrocarbon group and an R—O— group. (Hereinafter referred to as other antioxidants), ultraviolet absorbers, light stabilizing additives, reinforcing materials, modifiers, flame retardants, fillers, colorants, and the like.

  As other antioxidants, conventionally known ones can be used. For example, phenolic antioxidants other than phenolic compounds having secondary or tertiary hydrocarbon groups and R—O— groups (hereinafter, other A phenolic antioxidant), a phosphorus antioxidant, a sulfur antioxidant, and a lactone antioxidant, and other phenolic antioxidants are preferred. The amount added is in a range not contrary to the object of the present invention, usually 10 parts by weight or less, and 50% by weight or less based on the phenol compound having a secondary or tertiary hydrocarbon group and R—O— group. It is preferably 30% by weight or less.

Examples of the ultraviolet absorber include organic compounds such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, cyanoacrylate compounds, and benzoate compounds; nickel bis (octylphenyl) sulfide, and [2,2′- Organic metal compounds such as thiobis (4-t-octylphenolate)]-n-butylamine nickel; inorganic compounds such as zinc oxide, tin oxide, titanium oxide, calcium carbonate, silica, and clay;
As the light stabilizing additive, a hindered amine system (HALS) is usually used, in particular, a 3,5-di-tert-butyl-4-hydroxyphenyl group, and a 2,2,6,6-pentamethylpiperidyl group or A compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group is used.

  Examples of the reinforcing material include glass fiber, glass cloth, paper base material, and glass nonwoven fabric. Examples of the modifier include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-isoprene-styrene copolymer (SIS). , Elastomers such as ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrates thereof.

Examples of the flame retardant include phosphorus flame retardant, nitrogen flame retardant, phosphazene flame retardant having phosphorus and nitrogen, halogen flame retardant, metal hydroxide flame retardant such as aluminum hydroxide and magnesium hydroxide, and the like. Can be mentioned.
Examples of the filler include glass powder, carbon black, silica, talc, calcium carbonate, mica, alumina, titanium dioxide, zirconia, mullite, cordierite, magnesia, clay, barium sulfate and other inorganic fillers, wood powder, polyethylene Organic fillers such as powder can be used. Further, when graphite powder, charcoal powder, bamboo charcoal powder, metal powder, or the like is used, conductivity and electromagnetic wave shielding can be improved. Use of powders such as barium titanate, strontium titanate, lead titanate, magnesium titanate, bismuth titanate and lead zirconate can increase the dielectric constant. Ferromagnetic metal powders such as Mn-Mg-Zn-based, Ni-Zn-based, Mn-Zn-based ferrite, carbonyl iron, iron-silicon based alloy, iron-aluminum-silicon based alloy, iron-nickel based alloy, etc. When used, ferromagnetism can be imparted. Moreover, what was surface-treated with the silane coupling agent etc. can also be used for a filler.
As the colorant, dyes, pigments and the like are used. There are various types of dyes and pigments, and known ones may be appropriately selected and used.

Additives other than the antioxidant can be used alone or in combination of two or more.
The amount of each additive is appropriately selected depending on the purpose of use, but all are usually 0.001 to 1,000 parts by weight, preferably 0.01 to 100 parts by weight of the alicyclic structure-containing resin. It is in the range of ˜100 parts by weight.

The molding material of this invention is obtained by mixing the said component, The shape is a pellet form normally. The mixing method is not particularly limited, and can be performed by a wet mixing method or a dry mixing method according to a conventional method.
Examples of the wet mixing method include secondary or tertiary hydrocarbon groups in the reaction solution after obtaining the alicyclic structure-containing resin or in a solution obtained by dissolving the alicyclic structure-containing resin in an arbitrary solvent. And a phenol compound having an R—O— group and, if necessary, other additives may be blended and mixed, and then the solvent may be removed. As the solvent, a good solvent for the alicyclic structure-containing resin is preferably used. Specific examples of good solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; halogenated carbonization such as methylene dichloride and dichloroethane. Examples thereof include hydrogen; ethers such as diethyl ether and tetrahydrofuran; and these may be used alone or in admixture of two or more.

  As a dry mixing method, it can carry out using melt-kneading machines, such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roller, a feeder ruder, and a laboratory frust mill, for example. Although mixing temperature is suitably selected by the glass transition temperature of alicyclic structure containing resin, it is 50-500 degreeC normally, Preferably it is 100-400 degreeC, More preferably, it is 200-350 degreeC. Moreover, when mixing, each component may be mixed in a lump or may be mixed while being added in several times.

  Since the molding material of the present invention has excellent heat resistance and excellent moldability, it can be formed into a molded body using various molding means. There is no particular limitation on the molding means, and a known method can be used. For example, injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, Examples thereof include rolling and cutting.

EXAMPLES Next, an Example and a comparative example are given and this invention is further demonstrated. The present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” is based on mass unless otherwise specified.
In addition, the evaluation method in each Example is as follows.
-Weight average molecular weight (Mw), number average molecular weight (Mn)
It measured as polystyrene conversion value by the gel permeation chromatography using tetrahydrofuran under 30 degreeC.
・ Melt index (MI)
According to JIS K7210, the test temperature was 260 ° C. and the test load was 2.16 kgf / cm ² .
-Relative permittivity, dielectric loss tangent A value at 1 GHz was measured with an RF impedance / material analyzer E4991A (manufactured by Agilent Technologies).

(Example 1)
In a glass flask, 51 parts of benzylidene (1,3-dimesityrimimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine were dissolved in 952 parts of toluene to obtain a catalyst solution. Was prepared.
Tetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] 70.0 parts of dodec-4-ene and 30 parts of 2-norbornene and 0.3 part of 1-hexene were dissolved in 3000 parts of cyclohexane. 6 parts of the above catalyst solution was added with stirring, and polymerization was carried out for 2 hours while maintaining at 100 ° C., then the polymerization solution was returned to room temperature, and added to 12,000 parts of 2-propanol to solidify the produced alicyclic structure-containing resin. I let you. The coagulated alicyclic structure-containing resin was washed with 2-propanol and then dried under reduced pressure in an oven at 120 ° C. for about 3 hours. As a result of measuring the weight of the dried polymer, the yield was 90%, polymerization average molecular weight (Mw) 38000, number average molecular weight (Mn) 27000, molecular weight distribution 1.4 (Mw / Mn), melt index at 260 ° C. (MI) was 17 g / 10 min.

  To 100 parts of the resulting alicyclic structure-containing resin, 0.3 part of 2,6-di-t-butyl-4-methoxyphenol is added as an antioxidant, and a lab frust mill is used under a nitrogen atmosphere. A molding material was obtained by mixing. Using this molding material, a flat molded body of 2.2 mm × 120 mm × 120 mm was produced by hot pressing at a mold temperature of 200 ° C. The conditions for hot pressing were a press temperature of 200 ° C. × 15 minutes and a press pressure of 5 MPa.

The weight of the plate-like molded product thus obtained was measured, and the relative dielectric constant and dielectric loss tangent were further measured, and then stored in a high temperature and high humidity tank (60 ° C., humidity 95%) for 1000 hours. The relative dielectric constant and dielectric loss tangent at 1 GHz after storage were measured.
As a result, the change in relative dielectric constant was 10% or less. The dielectric loss tangent before and after storage was less than 0.001, and the dielectric loss tangent after storage could be suppressed to 1.2 times the value before storage.

(Example 2)
A molding material was obtained in the same manner as in Example 1 except that 2-t-butyl-4-methoxyphenol was used as an antioxidant, and a plate-like molded product was obtained using this molding material. The dielectric constant and dielectric loss tangent were determined. evaluated. As a result, the change in relative dielectric constant was 10% or less, and the dielectric loss tangent before storage was less than 0.001, and the dielectric loss tangent after storage exceeded 0.001, but the value before storage It was possible to suppress to 1.5 times.

(Comparative Example 1)
Except that 2,6-di-t-butyl-4-methylphenol was used as an antioxidant, a molding material was obtained in the same manner as in Example 1, and a flat molded body was obtained using this molding material. And dielectric loss tangent were evaluated. As a result, the change in relative permittivity was 10% or less, and was less than 0.001 before storage, but the dielectric loss tangent after storage exceeded 0.002, more than twice the value before storage. It has changed.

(Comparative Example 2)
A molding material was obtained in the same manner as in Example 1 except that an antioxidant represented by the following formula (II) (IRGANOX168 (manufactured by Ciba-Geigy)) was used as an antioxidant. The molded product was obtained and the dielectric constant and dielectric loss tangent were evaluated. As a result, the change in relative permittivity was 10% or less, and was less than 0.001 before storage, but the dielectric loss tangent after storage exceeded 0.002, more than twice the value before storage. It has changed.

(Comparative Example 3)
A molding material was obtained in the same manner as in Example 1 except that an antioxidant represented by the following formula (III) (IRGANOX1010 (manufactured by Ciba-Geigy)) was used as an antioxidant, and a flat plate shape was obtained using this. The molded body was obtained, and the dielectric constant and dielectric loss tangent were evaluated. As a result, the change in relative permittivity was 10% or less, and was less than 0.001 before storage, but the dielectric loss tangent after storage exceeded 0.002, more than twice the value before storage. It has changed.

  From these results, when a phenol compound having a hydrocarbon group and an R—O— group was used (Examples 1 and 2), the relative dielectric constant change rate at 1 GHz was small and the dielectric loss tangent value was 0.002 In contrast, when a phenol compound without an R—O— group is used (Comparative Example 1) or when a compound without R—O— is used but without a phenolic hydroxyl group (Comparative Example 2), Since the value of the dielectric loss tangent after storage under high temperature and high humidity conditions has changed more than twice, the use of a phenol compound having a hydrocarbon group and an R—O— group can improve the oxidation resistance. I understand.

The molding material containing the alicyclic structure-containing resin and the phenol compound having a secondary or tertiary hydrocarbon group and R—O— group has, for example, an excellent antioxidant effect, so that the coating material for electric wires, cables, General insulation materials for consumer and industrial electronic equipment, OA equipment such as copiers, computers and printers, instruments, etc .; circuit boards such as hard printed boards, flexible printed boards and multilayer printed wiring boards, especially high frequency characteristics are required High-frequency circuit boards for satellite communications equipment, etc .; Liquid crystal substrates, optical memories, transparent conductive film substrates such as surface heating elements such as automobiles and aircraft defrosters, and electrical / conductor seals for transistors, ICs, LSIs, LEDs, etc. Sealing materials and parts, sealing materials for electric and electronic parts such as motors, capacitors, switches and sensors, body materials such as TVs and video cameras, parabolas It can be used for electrical insulation materials such as antennas, flat antennas, radar dome structural members, etc.

Claims (7)

(1) A phenol having an alicyclic structure-containing resin and (2) a secondary or tertiary hydrocarbon group and R—O— group (R is a hydrocarbon group which may have a substituent) as a substituent. A molding material containing a compound. The molding material according to claim 1, wherein the (2) phenol compound is a phenol compound represented by the following formula (I).

(In the formula (I), R ¹ and R ² are each a hydrogen atom or a secondary or tertiary hydrocarbon group, and either one is at least a secondary or tertiary hydrocarbon group. ₃ is a hydrocarbon group which may have a substituent, A is a hydrocarbon group, p is 0, 1 or 2, and q is 1, 2 or 3. 3. The molding material according to claim ² , wherein R ¹ and R ^{2 in the} formula (I) are both secondary or tertiary hydrocarbon groups. Wherein (I), q is 1, the molding material as claimed in claim 2, wherein R ³ is a hydrocarbon group of primary 1 to 6 carbon atoms. The molding material according to claim 1, wherein the (2) phenol compound is 2,6-di-t-butyl-4-methoxyphenol or 2-t-butyl-4-methoxyphenol. The molding material according to claim 1, wherein the alicyclic structure-containing resin has a melt index (MI) at 260 ° C of 1 to 100 g / 10 min. A molded body formed by molding the molding material according to claim 1.