JP2012121956A - Addition-type norbornene-based resin, method for producing the same, resin composition containing the resin, molding containing the resin, and composite member containing the molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition-type norbornene-based resin excellent in adhesion to an inorganic base material, dielectric characteristics, heat resistance and moldability, a molding containing the resin, a composite member having the molding, etc.SOLUTION: The addition-type norbornene-based resin is obtained by bulk polymerization of a reaction liquid containing a norbornene-based monomer, a group 10 transition metal catalyst and a silane compound represented by formula (1), and has a silicon atom content of 0.01-2.0 mass% and a number-average molecular weight of 50,000 to 10 million. In the formula, Ris a 2C-30C hydrocarbon group having a terminal olefin; Ris at least one group selected from the group consisting of 1C-10C alkoxy, alkyloyloxy or aryloyloxy; Ris at least one group selected from the group consisting of 1C-30C alkyl, aryl and aralkyl; p is an integer of 1-3, q is an integer of 1-3, and r is an integer of 0-2, provided that p+q+r=4.

Description

  The present invention relates to an addition-type norbornene-based resin, a method for producing the same, a resin composition containing the resin, a molded body including the resin, and a composite member including the molded body.

  Conventionally, it is known that an amorphous ring-opening norbornene resin can be obtained by ring-opening polymerization of a norbornene monomer in the presence of a metathesis polymerization catalyst. Amorphous ring-opening norbornene-based resins have characteristics such as excellent electrical characteristics, optical characteristics, low hygroscopicity, etc., and are used for various applications as molded products.

  As a method for producing such a molded article, there is a method in which a polymer obtained by solution polymerization of a norbornene-based monomer is formed into a molded article by a thermoforming method such as injection molding or calendar molding. Also known is a method of obtaining a molded product by bulk polymerization of norbornene monomers in a mold, such as a reaction injection molding method (RIM method). For example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-163959) discloses a method for producing a ring-opening norbornene resin by bulk polymerization using a ruthenium catalyst.

On the other hand, in recent years, for example, with the increase in speed and performance of electronic equipment, there is a demand for a molded article that has low dielectric constant and dielectric loss tangent (particularly, dielectric constant and dielectric loss tangent at high frequency) and requires excellent heat resistance. .
In response to these requirements, the glass transition temperature of the ring-opening norbornene-based resin described in the above literature is 200 ° C. or lower, and required properties such as heat resistance may not always be satisfied.

  On the other hand, it is known that an amorphous addition-type norbornene-based resin can be obtained by addition polymerization of a norbornene-based monomer in a solution in the presence of a group 10 transition metal catalyst. The amorphous addition-type norbornene-based resin has excellent characteristics such as electrical characteristics, optical characteristics, and low hygroscopicity in addition to the dielectric characteristics, and can give a molded article exhibiting a high glass transition temperature.

  However, it has been difficult to obtain a molded product of the addition-type norbornene-based resin from the high glass transition temperature by a thermoforming method such as injection molding or calendar molding.

  On the other hand, as a method for easily obtaining a molded product of addition-type norbornene-based resin, a method of bulk polymerization of monomers is known. For example, Patent Document 2 (Japanese Patent Publication No. 2002-53648) discloses a nickel catalyst or a palladium catalyst. Discloses a method for producing an addition-type norbornene-based resin by bulk polymerization using styrene.

  However, although the techniques described in these documents have been disclosed in the art of producing a resin having an excellent electrical property, optical property, low hygroscopic property including the dielectric property, and a high glass transition temperature, it has been increasing in recent years. The required characteristics regarding the adhesion between the resin and the inorganic material that have been obtained have not always been satisfactory.

  Further, a method for adjusting the molecular weight by using an olefin chain transfer agent during polymerization of the addition type norbornene resin and a method for introducing an olefinic end group are known. For example, Patent Document 3 (Japanese Patent Laid-Open No. 9-508649) is known. Etc.).

  These methods are methods for adjusting the molecular weight of the addition-type norbornene resin at the time of solution polymerization. As described above, it has been difficult to obtain a molded product by the thermoforming method.

JP 2001-163959 A JP-T-2002-53648 Japanese National Patent Publication No. 9-508649

  The present invention provides an addition-type norbornene-based resin having excellent adhesion to an inorganic substrate, low dielectric constant and dielectric loss tangent, excellent heat resistance and moldability, a method for producing the same, a resin composition containing the resin, and A molded body containing the resin and a composite member including the molded body are provided.

The above object is achieved by the following items (1) to (14).
(1) It is obtained by bulk polymerization of a reaction solution containing a norbornene-based monomer, a group 10 transition metal catalyst, and a silane compound represented by formula (1), and the silicon atom content is 0.01% by mass or more. Addition-type norbornene-based resin having a mass average molecular weight of 50,000 to 10,000,000 and 2.0% by mass or less.


(In the formula, R ¹ is a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin, R ² is a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ is a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, p is an integer of 1 to 3, q is an integer of 1 to 3, and r is 0 An integer of ˜2 and p + q + r = 4.)

(2) The addition-type norbornene-based resin according to item (1), wherein the addition-type norbornene-based resin has a number average molecular weight of 100,000 to 1,000,000.

(3) The addition type norbornene resin according to item (1) or (2), wherein the addition type norbornene resin has a dispersity of 10 or less.

(4) The addition-type norbornene resin according to any one of (1) to (3), wherein the norbornene monomer includes a compound represented by the formula (2).


(In the formula, R represents any one of a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, and an aralkyl group having 1 to 30 carbon atoms; n represents an integer of 0 to 2.)

(5) Any one of items (1) to (4), wherein the additive norbornene resin has a dielectric constant at a frequency of 45 GHz of less than 4.0 and a dielectric loss tangent of less than 0.005. Addition type norbornene resin.

(6) The addition type norbornene resin according to any one of (1) to (5), wherein the glass transition temperature of the addition type norbornene resin is 250 ° C. or higher.

(7) The content of silicon atoms is 0.01% by mass or more by bulk polymerization of a reaction solution containing a norbornene-based monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1). A method for producing an addition-type norbornene-based resin, which obtains an addition-type norbornene-based resin having a number average molecular weight of 50,000 or more and 10 million or less.


(In the formula, R ¹ is a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin, R ² is a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ is a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, p is an integer of 1 to 3, q is an integer of 1 to 3, and r is 0 An integer of ˜2 and p + q + r = 4.)

(8) The method for producing an addition-type norbornene resin according to item (7), wherein a molar ratio of the norbornene monomer to the Group 10 transition metal catalyst is 1: 1,000 or more and 1: 500,000 or less.

(9) The addition type according to (7) or (8), wherein a mass ratio of the norbornene monomer to the silane compound represented by the formula (1) is 1: 5 or more and 1: 1000 or less. A method for producing a norbornene resin.

(10) The method for producing an addition-type norbornene resin according to any one of (7) to (9), wherein the reaction solution is bulk polymerized in a temperature range of 30 to 250 ° C.

(11) The method for producing an addition-type norbornene-based resin according to any one of (7) to (10), wherein the reaction solution is subjected to bulk polymerization in an inert gas atmosphere or under vacuum.

(12) A resin composition comprising the addition-type norbornene-based resin according to any one of (1) to (6).

(13) A molded article comprising the addition-type norbornene-based resin according to any one of (1) to (6).

(14) A composite member comprising a molded body containing the addition-type norbornene-based resin according to item (13).

  ADVANTAGE OF THE INVENTION According to this invention, addition norbornene-type resin excellent in adhesiveness with an inorganic base material, low dielectric constant and dielectric loss tangent, and excellent in heat resistance, the resin composition containing this resin, and the molded object containing this resin And a composite member provided with this molded object can be provided.

  Hereinafter, embodiments of an addition-type norbornene-based resin of the present invention and a manufacturing method thereof, a molded body including the resin, a manufacturing method thereof, and a composite member including the molded body will be described.

The addition-type norbornene resin of the present invention is obtained by bulk polymerization of a reaction solution containing a norbornene monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1), and has a silicon atom content. Is an addition-type norbornene-based resin having a number average molecular weight of 50,000 to 10,000,000.


(In the formula, R ¹ is a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin, R ² is a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ is a hydrocarbon group having no terminal olefin having 1 to 30 carbon atoms, p is an integer of 1 to 3, q is an integer of 1 to 3, r is an integer of 0 to 2, and p + q + r = 4)
The norbornene-based monomer used in the present invention has a structure represented by the following formula (3),


(Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, and 1 carbon atom. And a group containing -30 aralkyl groups and acetoxy groups, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different, and n ¹¹ represents an integer of 0 to 5.)

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the above formula (3) are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, carbon The alkyl group may be any group containing an aralkyl group or an acetoxy group of 1 to 30, but as the alkyl group, a methyl group, an ethyl group; a linear or branched propyl group; a linear, branched or cyclic butyl group, Examples include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an icosyl group, and a triacontyl group.

  As the aryl group, a monocyclic aromatic group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group and decylphenyl group, condensed polycyclic aromatic group such as naphthyl group, methylnaphthyl group and anthracenyl group, And polycyclic aromatic groups such as a biphenyl group and a terphenyl group. In addition, the hydrogen atom substituted with the carbon atom which comprises the aromatic ring of the said aromatic group may be substituted with the alkyl group, the halogen, etc.

  Examples of the aralkyl group include a benzyl group, a phenylethyl group, a methylphenylhexyl group, a phenylcyclohexyl group, and a naphthylethyl group.

  Examples of the group containing an acetoxy group include an acetoxymethyl group, an acetoxyethyl group, a diacetoxyethyl group, an acetoxybutyl group, an acetoxyhexyl group, an acetoxydecyl group, an acetoxycyclohexyl group, and an acetoxyphenyl group.

  Among these, it is preferable that at least one selected from the group consisting of a hydrogen atom, a butyl group, a hexyl group, a decyl group, and a phenylethyl group because the brittleness of the resulting addition-type norbornene resin can be reduced and the rigidity can be increased. More preferably, it is composed of an atom, a butyl group, a hexyl group, a decyl group, and a phenylethyl group.

The integer n ¹¹ that defines the alicyclic structure of the norbornene-based monomer is not particularly limited, but is 1 or 2 (that is, a norbornene structure or a tetraoctodedecene structure) for ease of synthesis. Is preferred.

Specifically, preferred examples of the norbornene monomer include unsubstituted norbornene monomers such as norbornene and tetracyclododecene; methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylmethylnorbornene, propylnorbornene, butylnorbornene, hexylnorbornene Alkyl-substituted norbornene monomers such as octylnorbornene, decylnorbornene, dodecylnorbornene, methyltetracyclododecene, ethyltetracyclododecene; phenylnorbornene, diphenylnorbornene, diphenylnorbornene, naphthyl) norbornene, phenyltetracyclododecene, naphthyl Aryl-substituted norbornene monomers such as tetracyclododecene; phenylethyl norbornene Aralkyl-substituted norbornene-based monomers such as phenylbutylnorbornene, naphthylethylnorbornene, and phenylethyltetracyclododecene; groups containing acetoxy groups such as acetoxymethylnorbornene, acetoxyethylnorbornene, acetoxybutylnorbornene, acetoxymethyltetracyclododecene, and the like And norbornene-based monomers. These may be used alone or in combination of two or more.
As the arrangement of the substituents of the norbornene-based monomer used in the present invention, at least three of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen atoms and one is a substituent (that is, the following formula (2) The structure represented by


(In the formula, R includes a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, an aralkyl group having 1 to 30 carbon atoms, and an acetoxy group. And n represents an integer of 0 to 5.)

  Among these, as described above, R is preferably at least one selected from a hydrogen atom, a butyl group, a hexyl group, a decyl group, and a phenylethyl group, and is selected from a hydrogen atom, a butyl group, a hexyl group, a decyl group, and a phenylethyl group. More preferably, the integer n that defines the alicyclic structure of the norbornene-based monomer is not particularly limited, but is 1 or 2 (that is, the norbornene structure or tetracoctodedecene for ease of synthesis). Structure).

Specifically, preferred examples of such norbornene monomers include unsubstituted norbornene monomers such as norbornene and tetracyclododecene; 5-butyl-2-norbornene, 5-hexyl-2-norbornene, and 5-decyl-2. -Alkyl-substituted norbornene-based monomers such as norbornene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene; 5- (2-phenylethyl) -2-norbornene, 5- (4 Aralkyl-substituted norbornene-based monomers such as -phenylbutyl) -2-norbornene and 8- (2-phenylethyl) -2-tetracyclododecene;
Norbornene, tetracyclododecene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5- (2-phenylethyl) -2-norbornene, 5- (4-phenyl) More preferred is butyl) -2-norbornene.
As a result, the brittleness of the addition-type norbornene resin can be reduced, the rigidity can be increased, and the insulation can be increased.

The Group 10 metal catalyst used in the present invention is a catalyst containing at least one of palladium, nickel and platinum. Thereby, the cyclic olefin-based low molecular weight components can be subjected to bulk polymerization. As such a catalyst, it is more preferable to use a catalyst containing palladium.

Such a Group 10 transition metal catalyst is preferably selected from at least one palladium catalyst represented by the following formula (4) and / or (5).
[R ′ ″ _x Pd (L) _y (L ′) _z ] (4)
[R ″ ″ _x Pd (L) _y (L ″) _z ] _b [WCA] _d (5)
Wherein R ′ ″ and R ″ ″ represent an anionic ligand selected from a carboxylate group, a thiocarboxylate group, a dithiocarboxylate group, and a hydrocarbyl group; L ′ represents a halogen ligand; L ″ represents an unstable neutral electron donating ligand; WCA represents a weakly coordinating anion; x represents 0 to 2 Y is an integer from 0 to 2; z is an integer from 0 to 2, b and d are a cation complex and an anion complex used to balance the electronic charge of the entire catalyst complex. It is a number representing the number.)

More preferably, such a group 10 transition metal catalyst is [Pd (NCMe) (OAc) (P (i-propyl) ₃ ) ₂ ] B (C ₆ F ₅ ) ₄ , [Pd (NCC (CH ₃ ) ₃ ). (OAc) (P (i-propyl) ₃ ) ₂ ] B (C ₆ F ₅ ) ₄ , [Pd (OC (C ₆ H ₅ ) ₂ ) (OAc)] (P (i-propyl) ₃ ) ₂ ] B (C ₆ F ₅ ) ₄ , [Pd (HOCH (CH ₃ ) ₂ ) (OAc)] (P (i-propyl) ₃ ) ₂ ] B (C ₆ F ₅ ) ₄ , [Pd (NCMe) (OAc )] (P (cyclohexyl) ₃ ) ₂ ] B (C ₆ F ₅ ) ₄ , Pd (OAc) ₂ (P (cyclohexyl) ₃ ) ₂ , Pd (OAc) ₂ (P (i-propyl) ₃ ) ₂ , Pd (OAc) ₂ (P (i-propyl) ₂ (phenyl)) ₂ , or [Pd (NCMe) (OAc) (P (cyclohexyl) ₂ (t-butyl)) ₂ ] B (C ₆ F ₅ ) ₄ is selected.

  As a result, the polymerization rate of the norbornene-based monomer can be increased, and the conversion rate to the addition-type norbornene-based resin can be increased.

The silane compound used in the present invention is represented by the following formula (1).


(In the formula, R ¹ represents a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin; R ² is selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ represents a hydrocarbon group having no terminal olefin having 1 to 30 carbon atoms; p represents an integer of 1 to 3; q represents an integer of 1 to 3; and r represents 0 to 2 Indicates an integer; p + q + r = 4)

Specific examples of the hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin as R ¹ in the above formula are not particularly limited, but include a vinyl group, an allyl group, a 3-butenyl group, and a 5-hexenyl group. Group, aliphatic alkenyl group such as 9-decenyl group; aromatic alkenyl group such as styryl group, 3,5-divinylphenyl group, methylvinylphenyl group, vinylnaphthyl group; styrylethyl group, (vinylnaphthyl) ethyl group , An aralkyl group having a vinyl group such as a styrylbutyl group, a styrylhexyl group, or a styryldecyl group;

Specific examples of the alkoxy group having 1 to 10 carbon atoms which is R ² in the above formula are not particularly limited, but include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a decyloxy group, a methoxyethoxy group, Alkoxy groups composed only of aliphatic groups such as methoxypropoxy group; benzyloxy group, phenylethyloxy group, tolylethyloxy group, (ethylphenyl) ethyloxy group, (dimethylphenyl) ethyloxy group, (methoxyphenyl) ethyloxy An alkoxy group having an aralkyl skeleton such as a group; and an aryloxy group such as an alkyloxy group such as an acetoxy group and a benzoyloxy group.

Specific examples of the hydrocarbon group having no terminal olefin having 1 to 30 carbon atoms, which is R ³ in the above formula, are not particularly limited, but include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. A linear or branched alkyl group such as a group or a decyl group; a cyclic alkyl group such as a cyclohexyl group, a cyclooctyl group, a norbornyl group or an adamantyl group; an aromatic group such as a phenyl group, a naphthyl group or an anthracenyl group; And aralkyl groups such as benzyl group, phenylethyl group, (naphthyl) ethyl group, phenylbutyl group, and the like.

Specifically, preferred examples of such silane compounds include vinyltrimethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, vinyltriethoxysilane, vinyltriisopropyloxysilane, vinyl-tris (decyloxy) silane, vinyltris (2 -Methoxyethoxy) silane, vinyltriacetoxysilane and other vinylsilanes; allyltrimethoxysilane, diallyldimethoxysilane, triallylmethoxysilane, allyltriethoxysilane, allyltriisopropyloxysilane, allyl-tris (decyloxy) silane, allyl- Allylsilanes such as tris (2-methoxyethoxy) silane; 3-butenyltrimethoxysilane, di (3-butenyl) dimethoxysilane, tri (3-butenyl) methoxysila Butenylsilanes such as 3-butenyltriethoxysilane, 3-butenyltriisopropyloxysilane, 3-butenyl-tris (decyloxy) silane, 3-butenyl-tris (2-methoxyethoxy) silane; Styrylsilanes such as distyryldimethoxysilane, tristyrylmethoxysilane, styryltriethoxysilane, styryltriisopropyloxysilane, styryl-tris (decyloxy) silane, styryl-tris (2-methoxyethoxy) silane, styryltriacetoxysilane; 1- (4-vinylnaphthyl) trimethoxysilane, bis-1- (4-vinylnaphthyl) dimethoxysilane, tris-1- (4-vinylnaphthyl) methoxysilane, 1- (4-vinylnaphthyl) trieth Vinyl such as silane, 1- (4-vinylnaphthyl) triisopropyloxysilane, 1- (4-vinylnaphthyl) -tris (decyloxy) silane, 1- (4-vinylnaphthyl) -tris (2-methoxyethoxy) silane Naphthylsilanes; and the like.
These may be used alone or in combination of two or more.
Examples of the silane compound used in the present invention include vinylsilanes such as vinyltrimethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, vinyltriethoxysilane, vinyltriisopropyloxysilane, and vinyl-tris (decyloxy) silane;
More preferred are styryl silanes such as styryl trimethoxy silane, distyryl dimethoxy silane, tristyryl methoxy silane, styryl triethoxy silane, styryl triisopropyl oxy silane, and the like, more preferably vinyl trimethoxy silane and styryl trimethoxy silane. Is more preferable. Thereby, while improving the reactivity as a chain transfer agent at the time of addition polymerization of a norbornene-type monomer, the adhesiveness with the inorganic base material of the addition-type norbornene-type resin obtained can be improved.

Unlike the ring-opening metathesis polymerization, the addition type norbornene resin of the present invention includes a repeating unit in which norbornane skeletons are directly bonded. Specifically, it includes a repeating unit represented by the following formula (6).


(Wherein R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are derived from a substituent of the norbornene-based monomer represented by the formula (3), and have a hydrogen atom, linear, branched, or cyclic carbon number of 1 A group containing 1 to 30 alkyl groups, an aryl group having 1 to 30 carbon atoms, an aralkyl group having 1 to 30 carbon atoms, and an acetoxy group, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are the same. And n ¹¹ is derived from the structure of the norbornene monomer represented by the formula (3) and represents an integer of 0 to 5.)

  The addition-type norbornene-based resin of the present invention has a silane compound represented by the formula (1) as a chain transfer agent during bulk polymerization and is incorporated in the resin. It contains 0 mass% or less of silicon atoms. In addition, the structure derived from this silane compound can improve adhesiveness with an inorganic base material by having a coupling agent-like effect.

In the present invention, the silicon atom content is measured using an alkali melting to absorptiometry. Specifically, 1 g of the addition type norbornene resin of the present invention is sampled, ground to a size of several millimeters, mixed with 30 g of 1,2,4-trichlorobenzene, stirred for 72 hours at room temperature, The sample obtained by filtering off the solvent and removing the solvent was placed in a platinum crucible, 0.5 mL of 10% KOH-PGME solution was added and infiltrated at room temperature for 1 hour, and 1.0 g of sodium carbonate was further added. In addition, the mixture is gradually heated and finally heated to 800 ° C. to fix organic Si as SiO ₃ ²⁻ . After allowing to cool to room temperature, it was dissolved in 15 mL of water to obtain a test solution. After constant volume, the test solution is colored by molybdenum blue absorptiometry (JIS-K0101-44), the color developing solution is introduced into a spectrophotometer (Shimadzu UV3100 type UV-visible spectrophotometer), and the absorbance at a wavelength of 815 nm is measured. Thus, the content of silicon atoms in the sample was converted.

  Since such an addition-type norbornene-based resin containing a silicon atom has an olefin skeleton having a silyl group that exhibits a coupling agent-like effect, it has excellent adhesion to an inorganic substrate due to the effect of the silyl group. Since the silicon atom content is very low, the dielectric loss tangent is low.

  In addition, the addition-type norbornene-based resin of the present invention has sufficient mechanical strength and the application range of the monomer and catalyst of the present invention, the number average molecular weight in terms of polystyrene is 50,000 to 10,000,000, preferably 10 It is from 10,000 to 1,000,000, more preferably from 200,000 to 1,000,000, and even more preferably from 500,000 to 1,000,000.

  The addition type norbornene resin of the present invention has a dispersity of 10 or less, preferably 8 or less, because the silane compound represented by the formula (1) acts as a chain transfer agent during bulk polymerization. More preferably, the degree of dispersion is 5 or less.

  The weight average molecular weight, number average molecular weight, and dispersity can be calculated as polystyrene equivalent values using a GPC (gel permeation chromatogram) apparatus, solvent: 1,2,4-trichlorobenzene, column temperature: 140 ° C. it can.

  In particular, the addition-type norbornene resin of the present invention has a dielectric constant (relative dielectric constant) at a frequency of 45 GHz of 4.0 or less and a dielectric loss tangent at a frequency of 45 GHz of less than 0.005. Thus, the present invention can be applied to a molded body that requires a low dielectric constant and a low dielectric loss tangent, such as an electronic device such as an antenna device that transmits / receives a carrier wave in a high frequency range such as a millimeter wave or a circuit board for high frequency transmission. Can be applied. Such a high-frequency antenna device or circuit board to which the present invention is applied has a high carrier wave transmission speed and a small transmission loss.

  Here, the measuring method of the relative dielectric constant and the dielectric loss tangent is in accordance with JIS1660-1 and IEC613338-1-4. Further, the above-described dielectric constant and dielectric loss tangent are not strictly values at 45 GHz, but are the same at the surrounding frequencies.

  The addition-type norbornene resin of the present invention has a glass transition temperature in DMS measurement of 200 ° C. or higher, preferably 250 ° C. or higher. Thereby, it can apply to the various molded object for which high heat resistance is requested | required.

  The glass transition temperature of the addition-type norbornene resin is measured with a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number: DMS6100). Measurement sample size: 4 mm (width) × 20 mm (length) × 500 μm (thickness) It is measured at a frequency of 1 Hz, a measurement temperature range of 30 to 300 ° C., and a heating rate of 10 ° C./min, and can be calculated as a Tan δ peak.

The reaction solution of the present invention includes a norbornene monomer, a group 10 transition metal catalyst, a silane compound, a cocatalyst, a filler, the same as the silane compound or other silane coupling agents, antioxidants, flame retardants Such additives may be included.
The cocatalyst preferably contains an ionic complex containing a weakly coordinating anion salt. That is, when synthesizing the addition-type norbornene resin, it is preferable to add a promoter in addition to the catalyst. Thereby, the polymerization rate of the addition-type norbornene-based monomer can be further increased.

  The cocatalyst is not particularly limited, and examples thereof include alkylaluminum, Lewis acid, or an ion complex containing a weakly coordinating anion (WCA) salt. An ionic complex containing an anionic (WCA) salt is preferred.

Moreover, as said co-catalyst, what is represented by following formula (7) is more preferable.

[C] _e [WCA] _d formula (7)

[In the above formula, C represents a proton (H ⁺ ), an organic group-containing cation, or an alkali metal, alkaline earth metal or transition metal cation, WCA is as defined above, and e and d are , Respectively, are numbers determined so as to balance the electronic charges on the total salt complex of the cation complex (C) and the weakly coordinating anion salt (WCA). ]

The ion complex containing the weakly coordinating anion (WCA) salt is not particularly limited, but lithium (diethyl ether) _2.5 tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluoro). phenyl) borate, dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, H _{(OEt 2) x} tetrakis (pentafluorophenyl) borate, tetrakis [(4-methyl)-.alpha., alpha- Bis (trifluoromethyl) benzene methanolato-κO] aluminate, sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, trialkyl and triarylphosphonium tetrakis (pentafluorophenyl) borate, and tritium And tetrakis (pentafluorophenyl) borate.

  The molar ratio of the norbornene monomer to the Group 10 transition metal catalyst (that is, the number of moles of the Group 10 transition metal catalyst: the number of moles of the norbornene monomer) is 1: 1,000 or more and 1: 500,000 or less. It is more preferable that it is 1: 10,000 or more and 1: 250,000 or less, and it is more preferable that it is 1: 25,000 or more and 1: 100,000 or less. Thus, the norbornene-based monomer can be reliably polymerized to obtain an addition-type norbornene-based resin, and the amount of the transition metal catalyst contained in the addition-type norbornene-based resin can be reduced.

  The amount of the cocatalyst added is not particularly limited, but the molar ratio of the cocatalyst to the group 10 transition metal catalyst (that is, the number of moles of the group 10 transition metal catalyst: the number of moles of the cocatalyst) is 1: It is preferably 0.1 or more and 1:10 or less, more preferably 1: 0.3 or more and 1: 8 or less, and further preferably 1: 0.5 or more and 1: 5 or less. As a result, the polymerization rate of the norbornene-based monomer is increased, and unintended reactions can be suppressed.

  The mass ratio of the norbornene monomer to the silane compound represented by the formula (1) (that is, the mass of the silane compound represented by the formula (1): the mass of the norbornene monomer) is 1: 5 or more and 1: 1. Is preferably 1,000 or less, more preferably 1:20 or more and 1: 500 or less, and further preferably 1: 100 or more and 1: 300 or less. As a result, it is possible to obtain a molded article having improved adhesion between the addition-type norbornene-based resin and the inorganic base material and having a low dielectric constant and dielectric loss tangent.

  The method of heating the reaction liquid is not particularly limited. For example, the reaction liquid is heated by placing a mold on a heated hot plate, or the reaction liquid is placed by placing the mold in a heated oven. Examples thereof include a method of heating, a method of heating a reaction liquid by hot pressing a mold, and a method of heating by irradiating the reaction liquid with infrared rays.

This heating temperature is appropriately set according to the composition of the reaction solution, the heating time, etc., and the norbornene monomer described above is bulk polymerized to cure or solidify the reaction solution to form an addition type norbornene resin. Although it will not be specifically limited if it can do, For example, it is preferable that it is 20 degreeC or more and 250 degrees C or less, It is more preferable that they are 30 degreeC or more and 250 degrees C or less, It is 50 degrees C or more and 200 degrees C or less. Further preferred.
Although the pressure of pressurization at the time of using a hot press as a heating method is not specifically limited, 0.5-8 MPa is preferable and 1-5 MPa is further more preferable.

  The heating time is appropriately set according to the composition of the reaction solution, the heating temperature, etc., and the norbornene monomer described above is bulk polymerized to cure or solidify the reaction solution to form an addition type norbornene system. Although it will not specifically limit if it can do, It is about 10 minutes-24 hours.

  Part or all of the heating of the reaction solution is preferably performed in a nitrogen atmosphere or a vacuum atmosphere. Thereby, while being able to improve the polymerization rate of a norbornene-type monomer, the unintended reaction can be suppressed.

  The method for producing an addition-type norbornene-based resin of the present invention includes the step of bulk polymerization of a reaction solution containing a norbornene-based monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1), thereby containing silicon atoms. The addition-type norbornene-based resin having a rate of 0.01% by mass or more and 2.0% by mass or less and a number average molecular weight of 50,000 or more and 10 million or less may be obtained. The reaction can be carried out appropriately under the reaction conditions.

  Examples of the filler that can be used in the norbornene-based resin of the present invention include various inorganic fillers and organic fillers.

  Examples of the inorganic filler include silica, alumina, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, oxides such as metal ferrite, hydroxides such as aluminum hydroxide and magnesium hydroxide, calcium carbonate ( Light, heavy), carbonates such as magnesium carbonate, dolomite, dosonite, sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, talc, mica, clay, glass fiber, calcium silicate, montmorillonite, Silicates such as bentonite, borate such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, carbon such as carbon black, graphite, carbon fiber, other iron powder, copper powder, Aluminum powder, zinc white, molybdenum sulfide, bo Down fibers, potassium titanate, and a lead zirconate titanate.

  Moreover, synthetic resin powder is mentioned as an organic filler. Examples of the synthetic resin powder include alkyd resin, epoxy resin, silicone resin, phenol resin, polyester, acrylic resin, acetal resin, polyethylene, polyether, polycarbonate, polyamide, polysulfone, polystyrene, polyvinyl chloride, fluororesin, and polypropylene. And various thermosetting resins such as ethylene-vinyl acetate copolymers or powders of thermoplastic resins, or powders of copolymers of these resins. Other examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, and aramid fibers.

  In particular, the filler is preferably an inorganic filler. Thereby, the thermal expansion coefficient of the molded object containing the addition type norbornene resin obtained can be lowered effectively. Moreover, the heat resistance of a molded object can be made excellent. The inorganic filler is preferably a silica filler. Thereby, the thermal expansion coefficient of a molded object can be lowered | hung while making the dielectric property of the molded object containing the addition type norbornene resin obtained excellent. Examples of the silica filler include fused silica (fused spherical silica, fused crushed silica), crystalline silica, and the like. It is preferable to use a fused silica filler, and more preferred is a spherical silica because the maximum filling amount can be increased. Thereby, the dielectric properties of the molded body can be made particularly excellent.

  Moreover, as a base material, the base material used by the laminated board and circuit board well-known to those skilled in the art which used materials, such as glass, carbon fiber, an aramid fiber, and paper suitably, such as a woven fabric and a nonwoven fabric, can be used.

Additives that can be used as needed in the present invention are not particularly limited, and examples thereof include those similar to the silane compound or other silane coupling agents, flame retardants, antioxidants, and the like. It is done.
As a silane coupling agent other than the same as the silane compound, a known effect such as an affinity between a filler and a resin or a substrate such as a glass cloth and a resin can be provided as long as the characteristics of the present invention are not impaired. Examples thereof include alkyl silane, aryl silane, epoxy silane, acrylic silane, silazane and the like.

  Typical examples of the flame retardant include phosphorus series such as trixylenyl phosphate, dixylenyl phosphate, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide. Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resins, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, and the flame retardancy of the molded article can be improved.

  Representative examples of the antioxidant include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis- (3-methyl-6- tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), tetrakis- (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate) Methane, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5- Di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis (3,5-di-tert-butyl-4 Hinders such as hydroxy-hydrocinnamamide, 2,4-bis ((octylthio) methyl) -o-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate A dophenol compound is mentioned.

  Examples of the resin composition of the present invention include a state in which an addition-type norbornene resin produced in the bulk polymerization process and reaction liquid components such as unreacted monomers are mixed, for example, a B-staged state.

In the present invention, an addition-type norbornene resin can be obtained by bulk polymerization using a reaction solution containing a norbornene monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1). .
The “bulk polymerization” generally means a polymerization reaction carried out substantially without a solvent, but depending on the case, a small proportion of a solvent may be added to the norbornene-based monomer. In addition, when it is desirable to dissolve the group 10 transition metal catalyst and the silane compound represented by the formula (1) in the solvent before adding the silane compound to the norbornene-based monomer, a solvent such as ethyl acetate, THF, or toluene is used. It may be used. In that case, the content of the solvent in the reaction solution is preferably 10% by mass or less, and more preferably 5% by mass or less.

The molded article of the present invention is the norbornene-based monomer of the present invention, a group 10 transition metal catalyst, a silane compound represented by the formula (1), or, if necessary, the aforementioned promoter, filler, base material, and other additives. It can be obtained by adding an agent and filling the reaction solution into a predetermined mold, etc.
Industrially, when producing a bulk molded body, a known method such as a reaction injection molding method (RIM method), injection molding, compression molding or transfer molding may be used, and a plate-shaped molded body such as a laminate. Is impregnated with inorganic base materials such as glass cloth and glass nonwoven fabric, organic woven fabrics typified by paper, nanocellulose, and aramid fiber, and organic base materials such as the nonwoven fabric, and if necessary, B stage After the prepreg is laminated, a single or a plurality of prepregs are laminated, and if necessary, sandwiched between release sheets and cured using means such as heat and pressure.

  In addition, if the composite member of the present invention is a composite member using a bulk insert in accordance with the procedure for producing the molded body, the insert is fixed in advance to the mold, and the reaction solution or resin composition of the present invention is used. What is necessary is just to pour and harden | cure, and if it is a thing like a circuit board, it can manufacture, if it replaces with a mold release sheet and uses metal foil etc. in manufacture of the said laminated board.

<Example 1>
(Preparation of polymerizable reaction solution)
The following monomer (A) and the following compound (B) were mixed and stirred at room temperature for 5 minutes. Furthermore, the following Pd catalyst (C) and the following cocatalyst (D) were added and stirred at room temperature for 1 minute to obtain a polymerizable reaction liquid R.
Monomer (A): HexNB (5-hexylnorbornene)
Compound (B): Vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)
Catalyst (C): bis (triisopropylphosphine) palladium acetate (acetonitrile) tetrakis (pentafluorophenyl) borate (Pd catalyst 1)
Cocatalyst (D): N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate In preparing the polymerizable reaction liquid R, the weight ratio of the monomer (A) and the compound (B) is (A) :( B) = 20: 1 ratio. The molar ratio of monomer (A), Pd catalyst (C) and promoter (D) was set to a ratio of (A) :( C) :( D) = 50,000: 1: 1.

(Production of molded body)
Two pieces of copper foil with a center line average roughness Ra of 0.06 μm (DFF-NA 18 μm thickness, manufactured by Mitsui Metal Foil Manufacturing Co., Ltd.) attached to a stainless steel plate (15 cm square) so that the copper foil rough surface is inside. Prepared. U-shaped silicone rubber spacer (thickness 0.5mm, 150mm square cut out from 140mm x 130mm), sandwiched between two stainless steel plates with copper foil so that the copper foil is inside and fixed with clamp A mold was produced. 8 mL of the polymerizable reaction liquid R was poured into the produced mold, heated at 80 ° C. for 1 hour using an oven in the atmosphere, and further heated at 150 ° C. for 1 hour. After cooling the mold at room temperature, the molded body with copper foil was taken out.

<Example 2>
In the preparation of the polymerizable reaction solution, the same procedure as in Example 1 was performed except that the weight ratio of the monomer (A) and the compound (B) was (A) :( B) = 10: 1. Thus, a molded body with a copper foil was produced.

<Example 3>
In the preparation of the polymerizable reaction solution, the same procedure as in Example 1 was performed except that the weight ratio of the monomer (A) and the compound (B) was (A) :( B) = 33: 1. Thus, a molded body with a copper foil was produced.

<Example 4>
In the preparation of the polymerizable reaction solution, the same procedure as in Example 1 was performed except that the weight ratio of the monomer (A) and the compound (B) was (A) :( B) = 100: 1. Thus, a molded body with a copper foil was produced.

<Example 5>
In the preparation of the polymerizable reaction solution, the same procedure as in Example 1 was performed except that the weight ratio of the monomer (A) and the compound (B) was (A) :( B) = 200: 1. Thus, a molded body with a copper foil was produced.

<Example 6>
In the preparation of the polymerizable reaction solution, the molar ratio of the monomer (A), the catalyst (C) and the cocatalyst (D) becomes a ratio of (A) :( C) :( D) = 10,000: 1: 1. A molded body with a copper foil was produced in the same manner as in Example 1 except for the above.

<Example 7>
In the preparation of the polymerizable reaction solution, the molar ratio of the monomer (A), the catalyst (C) and the promoter (D) is (A) :( C) :( D) = 100,000: 1: 1. A molded body with a copper foil was produced in the same manner as in Example 1 except for the above.

<Example 8>
In the production of the molded body, the above-mentioned implementation was performed except that after heating at 80 ° C. for 1 hour using an oven in the atmosphere, and further heating at 50 ° C. for 5 hours using an oven in the atmosphere instead of heating at 150 ° C. for 1 hour. A molded body with a copper foil was produced in the same manner as in Example 1.

<Example 9>
In the production of the molded body, the above-mentioned implementation was performed except that after heating at 80 ° C. for 1 hour using an oven in the atmosphere, and further heating at 200 ° C. for 1 hour using an oven in the atmosphere instead of heating at 150 ° C. for 1 hour. A molded body with a copper foil was produced in the same manner as in Example 1.

<Example 10>
In the production of the molded body, after heating at 80 ° C. for 1 hour using an oven in the atmosphere, and further heating at 150 ° C. for 1 hour, after heating at 80 ° C. for 1 hour using an oven under nitrogen, the temperature is further increased to 1 at 150 ° C. A molded body with a copper foil was produced in the same manner as in Example 1 except that heating was performed for a period of time.

<Example 11>
In the production of the molded body, after heating at 80 ° C. for 1 hour using an oven in the atmosphere, instead of heating at 150 ° C. for 1 hour, holding at 120 ° C. and a pressure of 3 MPa for 2 hours using a vacuum press, A molded body with a copper foil was produced in the same manner as in Example 1 except that the temperature was raised and maintained for another 2 hours.

<Example 12>
A molded body with a copper foil was prepared in the same manner as in Example 6 except that DecNB (5-decyl-2-norbornene) was used as the monomer (A) in preparing the polymerizable reaction solution.

<Example 13>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that BuNB (5-butyl-2-norbornene) was used as the monomer (A) in preparing the polymerizable reaction solution.

<Example 14>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that PENB (5-phenylethyl-2-norbornene) was used as the monomer (A) in preparing the polymerizable reaction solution.

<Example 15>
A molded article with a copper foil was prepared in the same manner as in Example 1 above, except that in the preparation of the polymerizable reaction solution, a mixture of HexNB and PENB having a weight ratio of 50:50 was used as the monomer (A).

<Example 16>
Molded product with copper foil in the same manner as in Example 6 except that a mixture of HexNB and TD (tetracyclododecene) in a weight ratio of 50:50 was used as the monomer (A) in preparing the polymerizable reaction solution. Was made.

<Example 17>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that p-styryltrimethoxysilane was used as the compound (B) in preparing the polymerizable reaction solution.

<Example 18>
In the preparation of the polymerizable reaction solution, a molded article with a copper foil was produced in the same manner as in Example 1 except that vinyltriethoxysilane was used as the compound (B).

<Comparative Example 1>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that the compound (B) was not used in the preparation of the polymerizable reaction solution.

<Comparative Example 2> Comparative Example Using Ring-Opening Norbornene Resin In the preparation of the polymerizable reaction liquid, benzylidene (1,3-dimethylimidazolid-2-ylidene) (in place of Pd catalyst 1 as catalyst (C)) ( A molded article with a copper foil was obtained in the same manner as in Comparative Example 1 described above except that tricyclohexylphosphine) ruthenium dichloride (Ru catalyst 1) was used and triphenylphosphine was used as the cocatalyst (D).

<Comparative Example 3>
In the preparation of the polymerizable reaction solution, a molded article with a copper foil was prepared in the same manner as in Example 1 except that methyltrimethoxysilane was used as the compound (B).

<Comparative example 4>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that decyltrimethoxysilane was used as the compound (B) in preparing the polymerizable reaction solution.

<Comparative Example 5>
In the preparation of the polymerizable reaction solution, a molded article with a copper foil was prepared in the same manner as in Example 1 except that 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was used as the compound (B). .

<Comparative Example 6>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was used as the compound (B) in the preparation of the polymerizable reaction solution.

<Comparative Example 7>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that 3-methacryloxypropylmethyldimethoxysilane was used as the compound (B) in preparing the polymerizable reaction solution.

<Comparative Example 8>
A molded article with a copper foil was prepared in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was used as the compound (B) in preparing the polymerizable reaction solution.

<Comparative Example 9>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that 3-methacryloxypropyltriethoxysilane was used as the compound (B) in preparing the polymerizable reaction solution.

<Comparative Example 10>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that 5-trimethoxysilyl-2-norbornene was used as the compound (B) in the preparation of the polymerizable reaction solution.

<Comparative Example 11>
In the preparation of the polymerizable reaction solution, the same as in Comparative Example 10 except that the weight ratio of the monomer (A) and the compound (B) was set to a ratio of (A) :( B) = 4: 1. Thus, a molded body with a copper foil was produced.

<Comparative Example 12>
A molded body with a copper foil was prepared in the same manner as in Example 1 except that 1-hexene was used as the compound (B) in the preparation of the polymerizable reaction solution.

<Comparative Example 13>
The adjustment of the polymerizable reaction solution was performed in the same manner as in Example 1 except that 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine was used as the compound (B). Since the reaction did not proceed and the monomer was volatilized, a molded body with copper foil could not be obtained.

<Comparative example 14>
The adjustment of the polymerizable reaction solution was carried out in the same manner as in Example 1 except that trimethoxyhydrosilane was used as the compound (B). However, since the reaction did not proceed and the monomer was volatilized, a molded article with copper foil was obtained. I couldn't.
<Comparative example 15> Comparative example tried with solution polymerization product (solution polymerization of 5-hexylnorbornene)
In a stainless steel reactor, hexyl norbornene (180.0 g) and 1-hexene (12.2 mL) were mixed with toluene (1170 mL) and set to stir at 80 ° C. under a nitrogen atmosphere. A solution of Pd catalyst 1 (0.038 g) in toluene (10 mL) was added and the solution was stirred for 3 hours. The resulting viscous polymer solution was then precipitated by gradually adding methanol. The resulting white solid polymer was washed with methanol and dried in vacuo. Yield: 144.8 g (80%), Mw = 477,000, PDI = 3.2.

(Production of molded body)
The 5-hexylnorbornene polymer (30 g) and vinyltrimethoxysilane (1.5 g) obtained above were dissolved in mesitylene (70 g) to prepare a polymer solution.

  Silicone rubber with a center line average roughness Ra of 0.06 μm, punched out to a thickness of 1.7 mm, 200 mm × 200 mm and a central portion of 160 mm × 160 mm on a Mitsui Metal Foil Manufacturing Co., Ltd. DFF-NA 12 μm thickness And set to be horizontal.

40 mL of the polymer solution was poured into the produced mold, heated at 80 ° C. for 5 hours using an oven in the atmosphere, and further heated at 150 ° C. for 5 hours. After cooling the mold at room temperature, the molded body with copper foil was taken out, and the resin layer was so brittle that it could not be evaluated.

  The adhesiveness between the copper foil and the molded body of the molded body with copper foil obtained in Examples 1 to 18 and Comparative Examples 1 to 12 was evaluated as 90 ° C. peel strength according to JIS-C-6481.

  In addition, after the copper foil was immersed in a ferric chloride solution at room temperature for 30 minutes and the copper foil was etched, the dielectric properties, molecular weight, silicon atom content, and glass transition temperature of the molded body washed with pure water were measured. It was measured.

<Example 19>
In the preparation of the polymerizable reaction solution, the monomer (A) and the following filler (E) were mixed at a weight ratio (A) :( E) = 80: 20, and the composition stirred for 1 hour at room temperature was mixed with the monomer (A). A molded body with a copper foil was produced in the same manner as in Example 1 except that it was used instead. In addition, the ratio with respect to the monomer component in a mixture was used like the above-mentioned Example 1 at the time of preparation of a catalyst etc.
Monomer (A): HexNB
Filler (E): fused silica treated with decylsilane (manufactured by Admatechs Co., Ltd .: Admafine SO-E2: average particle size 0.5 μm)

<Example 20>
In the preparation of the polymerizable reaction liquid, the above Example 19 was used except that fused silica (manufactured by Admatechs Co., Ltd .: Admafine SO-E2: average particle size 0.5 μm) treated with vinylsilane was used as the filler (E) In the same manner, a molded body with a copper foil was produced.

<Example 21>
Molding with copper foil in the same manner as in Example 19 except that the weight ratio of the monomer (A) to the filler (E) was (A) :( E) = 60: 40 in the preparation of the polymerizable reaction solution. The body was made.

<Comparative Example 16>
In the preparation of the polymerizable reaction solution, the monomer (A) and the following filler (E) were mixed at a weight ratio (A) :( E) = 80: 20, and the composition stirred for 1 hour at room temperature was mixed with the monomer (A). A molded body with a copper foil was produced in the same manner as in Comparative Example 1 except that it was used instead. In addition, the ratio with respect to the monomer component in a mixture was used like the above-mentioned comparative example 1 at the time of preparation of a catalyst etc.

  The adhesiveness between the copper foil and the molded body of the molded body with copper foil obtained in Examples 19 to 21 and Comparative Example 16 was evaluated as a peel strength at 90 ° C. according to JIS-C-6481.

  Moreover, after the copper foil was immersed in a ferric chloride solution at room temperature for 30 minutes and the copper foil was etched, the dielectric properties and glass transition temperature of the molded body washed with pure water were measured.

<Example 22>
In the production of the molded body, a molded body with a stainless steel plate was produced in the same manner as in Example 1 except that a stainless steel plate was used instead of the stainless steel plate with a copper foil.

<Example 23>
In the production of the molded body, a molded body with a glass plate was produced in the same manner as in Example 1 except that a glass plate was used instead of the stainless steel plate with copper foil.

<Comparative Example 17>
In the production of the molded body, a molded body with a stainless steel plate was produced in the same manner as in Comparative Example 1 except that a stainless steel plate was used instead of the stainless steel plate with a copper foil.

<Comparative Example 18>
In the production of the molded body, a molded body with a glass plate was produced in the same manner as in Comparative Example 1 except that a glass plate was used instead of the stainless steel plate with copper foil.

  The adhesiveness of the molded product surfaces of the molded products obtained in Examples 22 and 23 and Comparative Examples 17 and 18 was evaluated by a tape test according to JIS-K-5400 adhesion (cross-cut method). That is, 100 square squares of 1 mm square were formed on the insulating film with a cutter knife, and cello tape (registered trademark) was stretched thereon. One minute later, the cellulosic tape was peeled off while suppressing the inorganic base material, and the number of resin moldings peeled off from the inorganic base material was counted.

As is apparent from Table 1, the molded bodies of the respective examples according to the present invention were superior to the molded bodies of the respective comparative examples with respect to evaluation of adhesion, heat resistance and dielectric loss tangent. Since the molded bodies produced in Comparative Examples 1 to 10 and Comparative Example 12 did not use the silane compound represented by the formula (1), the adhesion with the copper foil was inferior. Furthermore, since the molded body produced in Comparative Example 2 was a ring-opening norbornene resin, the result was inferior in heat resistance. Moreover, since the molded object produced in Comparative Example 11 uses a large amount of a silane compound other than the silane compound represented by the formula (1), the adhesion is a value similar to that of the example, but the dielectric loss tangent is high. The dielectric properties were inferior. In Comparative Examples 13 to 15, the sample could not be evaluated because it was brittle.
As is apparent from Table 2, the molded bodies of the respective examples according to the present invention were superior to the molded bodies of the respective comparative examples with respect to evaluation of adhesion, heat resistance, and dielectric loss tangent. Since the molded body produced in Comparative Example 16 did not use the silane compound represented by the formula (1), the adhesion with the copper foil was inferior.
As is apparent from Table 3, the molded bodies of the respective examples according to the present invention were superior to the molded bodies of the respective comparative examples in terms of adhesion evaluation. Since the molded body produced in Comparative Examples 17 and 18 did not use the silane compound represented by the formula (1), it was inferior in adhesion to the stainless steel plate and the glass plate.
Thus, it is clear that the molded body of each example according to the present invention gives excellent results regarding the evaluation of adhesion, heat resistance, and dielectric loss tangent.

Claims (14)

It is obtained by bulk polymerization of a reaction solution containing a norbornene-based monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1), and the silicon atom content is 0.01% by mass or more and 2.0%. Addition-type norbornene resins having a mass average molecular weight of 50,000 to 10,000,000.


(In the formula, R ¹ is a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin, R ² is a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ is a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, p is an integer of 1 to 3, q is an integer of 1 to 3, and r is 0 An integer of ˜2 and p + q + r = 4.)   The addition type norbornene resin according to claim 1, wherein the addition type norbornene resin has a number average molecular weight of 100,000 to 1,000,000.   The addition type norbornene resin according to claim 1 or 2, wherein the addition type norbornene resin has a dispersity of 10 or less. The addition-type norbornene-based resin according to any one of claims 1 to 3, wherein the norbornene-based monomer includes a compound represented by the formula (2).


(In the formula, R represents any one of a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, and an aralkyl group having 1 to 30 carbon atoms; n represents an integer of 0 to 2.)   The addition type norbornene resin according to any one of claims 1 to 4, wherein the addition type norbornene resin has a dielectric constant of less than 4.0 at a frequency of 45 GHz and a dielectric loss tangent of less than 0.005.   The addition-type norbornene-based resin according to any one of claims 1 to 5, wherein a glass transition temperature of the addition-type norbornene-based resin is 250 ° C or higher. By carrying out bulk polymerization of a reaction solution containing a norbornene-based monomer, a group 10 transition metal catalyst, and a silane compound represented by the formula (1), the silicon atom content is 0.01% by mass or more and 2.0% by mass. A method for producing an addition-type norbornene-based resin, which is an addition-type norbornene-based resin having a number average molecular weight of 50,000 to 10,000,000.


(In the formula, R ¹ is a hydrocarbon group having 2 to 30 carbon atoms having a terminal olefin, R ² is a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkyloxy group, and an aryloxy group. R ³ is a group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group, and an aralkyl group, p is an integer of 1 to 3, q is an integer of 1 to 3, and r is 0 An integer of ˜2 and p + q + r = 4.)   The method for producing an addition-type norbornene resin according to claim 7, wherein a molar ratio of the norbornene monomer to the Group 10 transition metal catalyst is 1: 1,000 or more and 1: 500,000 or less.   The method for producing an addition type norbornene resin according to claim 7 or 8, wherein a mass ratio of the norbornene monomer to the silane compound represented by the formula (1) is 1: 5 or more and 1: 1000 or less.   The method for producing an addition-type norbornene-based resin according to any one of claims 7 to 9, wherein the reaction solution is subjected to bulk polymerization in a temperature range of 30 to 250 ° C.   The method for producing an addition-type norbornene resin according to any one of claims 7 to 10, wherein the reaction solution is subjected to bulk polymerization in an inert gas atmosphere or in a vacuum.   A resin composition comprising the addition-type norbornene-based resin according to any one of claims 1 to 6.   The molded object containing the addition type norbornene-type resin of any one of Claim 1 thru | or 6. A composite member comprising a molded body containing the addition-type norbornene-based resin according to claim 13.