Circuit board resin composition, and method for producing resin powder particles

Abstract

The purpose of the present invention is to provide a circuit board resin composition that can reduce environmental load and that can be used as a material for manufacturing circuit boards in which the dielectric constant is reduced. The present invention pertains to a circuit board resin composition containing resin powder particles having a halogen content of 3 mass% or less.

Description

Resin composition for substrates and method for producing resin powder particles

[0001] The present invention relates to a resin composition for substrates and a method for producing resin powder particles, and more particularly to a resin composition for substrates and a method for producing resin powder particles used in the resin composition for substrates.

[0002] As electronic devices become faster and more functional, substrates used in various electronic devices are required to have low dielectric constants, low dielectric loss tangents, etc. As a material for such substrates, for example, Patent Document 1 proposes a fluororesin-containing polyimide precursor composition containing a fluororesin micropowder, a predetermined compound, and a polyimide precursor solution. According to Patent Document 1, the use of the fluororesin-containing polyimide precursor composition can improve electrical properties (low dielectric constant, low dielectric loss tangent), physical properties, etc.

[0003] JP 2017-008209 A

[0004] In recent years, regulations on perfluoroalkyl substances and polyfluoroalkyl compounds (PFAS) have been tightened worldwide. Under these circumstances, the fluorine-based resin-containing polyimide precursor composition disclosed in Patent Document 1 is undesirable because it contains a fluorine-based resin. Therefore, there is a demand for the development of substrate materials that can reduce environmental impact.

[0005] Therefore, an object of the present invention is to provide a resin composition for substrates that can reduce the environmental load and can be used as a material for producing substrates with a reduced dielectric constant, and a method for producing resin powder particles used in the resin composition for substrates.

[0006] The present inventors have conducted extensive research to achieve the above object, and have newly discovered that a composition containing resin powder particles having a halogen content of 3 mass % or less can reduce the environmental impact and can be used as a material for producing a substrate having a reduced dielectric constant, thereby completing the present invention.

[0007] That is, the present invention aims to advantageously solve the above-mentioned problems, and [1] the resin composition for substrates of the present invention is a resin composition for substrates containing resin powder particles having a halogen content of 3 mass% or less. The above resin composition for substrates can reduce environmental impact and can be used as a material for producing substrates with a reduced dielectric constant. In the present invention, the "halogen content" can be measured using the method described in the examples.

[0008] [2] In the resin composition for a substrate according to [1] above, it is preferable that the resin powder particles have an average particle diameter of 30 μm or less, and that the ratio of the volume of resin powder particles having a particle diameter of 70 μm or more to the total volume of the resin powder particles in the resin composition for a substrate is 15% or less. By using the resin composition for a substrate, a substrate with an even lower dielectric constant can be produced.

[0009] [3] In the resin composition for substrates according to [1] above, it is preferred that the resin powder particles have an average particle diameter of 20 μm or less, and that the proportion of the volume of resin powder particles having a particle diameter of 70 μm or more to the total volume of the resin powder particles in the resin composition for substrates is 15% or less. By using the resin composition for substrates described above, it is possible to manufacture a substrate with an even lower dielectric constant. In the present invention, "average particle diameter" means the volume-weighted average diameter, and "particle diameter" means the volume-weighted diameter. In the present invention, the "average particle diameter" and "the proportion of the volume of resin powder particles having a particle diameter of 70 μm or more to the total volume of resin powder particles in the resin composition for substrates" can be determined by the method described in the Examples.

[0010] [4] In the resin composition for a substrate according to any one of the above [1] to [3], the resin powder particles are preferably particles of a cyclic olefin resin. If the resin powder particles are particles of a cyclic olefin resin, the heat resistance of a substrate produced using the resin composition for a substrate of the present invention can be improved.

[0011] [5] In the resin composition for a substrate according to any one of the above [1] to [4], the resin powder particles are preferably particles of a crystalline cyclic olefin resin. If the resin powder particles are particles of a crystalline cyclic olefin resin, the heat resistance of a substrate produced using the resin composition for a substrate of the present invention can be further improved.

[0012] Another object of the present invention is to advantageously solve the above-mentioned problems, and [6] the method for producing resin powder particles of the present invention is a method for producing resin powder particles, which comprises subjecting a solution containing a cyclic olefin ring-opening polymer at a solids concentration of 10 mass% or more to a hydrogenation reaction, to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass% or less. According to the method for producing resin powder particles, it is possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention.

[0013] Another object of the present invention is to advantageously solve the above-mentioned problems, and [7] the present invention provides a method for producing resin powder particles, which comprises pulverizing a hydrogenated crystalline cyclic olefin ring-opening polymer in a solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass% or less. According to the above-mentioned method for producing resin powder particles, it is possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention.

[0014] According to the present invention, it is possible to provide a resin composition for substrates that can reduce environmental impact and can be used as a material for producing substrates with a reduced dielectric constant. Also, according to the present invention, it is possible to provide a method for producing resin powder particles used in the resin composition for substrates of the present invention.

[0015] Hereinafter, embodiments of the present invention will be described in detail. The resin composition for substrates of the present invention is used as a material for forming substrates and contains resin powder particles having a halogen content of 3% by mass or less. Furthermore, substrates manufactured using the resin composition for substrates of the present invention have a reduced environmental impact and a reduced dielectric constant, and therefore can be used for various purposes, and are particularly suitable for use as high-frequency substrates. The resin powder particles contained in the resin composition for substrates of the present invention can be manufactured, for example, by the method for manufacturing resin powder particles of the present invention.

[0016] (Resin Composition for Substrates) The resin composition for substrates of the present invention contains resin powder particles having a halogen content of 3% by mass or less, and may optionally contain other components such as additives.

[0017] <Resin Powder Particles> The resin powder particles contained in the resin composition for substrates of the present invention are resin powder particles having a halogen content of 3 mass % or less. Note that, in the present invention, "resin powder particles" refers to resin particles having an average particle diameter of 500 μm or less.

[0018] Here, from the viewpoint of further reducing the environmental load, the resin powder particles of the present invention preferably have a halogen content of 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0019] In order to effectively achieve a thin substrate, the average particle size of the resin powder particles is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. The average particle size of the resin powder particles is usually 0.3 μm or more.

[0020] Furthermore, from the viewpoint of further reducing the dielectric constant of the obtained substrate, the proportion of the volume of resin powder particles having a particle diameter of 70 μm or more to the total volume of resin powder particles in the resin composition for substrates is preferably 15% or less, more preferably 1% or less, and even more preferably 0% (i.e., the resin powder particles in the resin composition for substrates do not include resin powder particles having a particle diameter of 70 μm or more).

[0021] From the viewpoint of further reducing the dielectric constant of the resulting substrate, it is preferable that the average particle size of the resin powder particles is 30 μm or less, and the proportion of the volume of resin powder particles having a particle size of 70 μm or more to the total volume of resin powder particles in the resin composition for substrates is 15% or less, and more preferably that the average particle size of the resin powder particles is 20 μm or less, and the proportion of the volume of resin powder particles having a particle size of 70 μm or more to the total volume of resin powder particles in the resin composition for substrates is 15% or less.

[0022] The resin powder particles having a halogen content of 3% by mass or less are not particularly limited, but from the viewpoint of improving the heat resistance of the resulting substrate, particles of a cyclic olefin resin are preferred, and particles of a crystalline cyclic olefin resin are more preferred. In the present invention, the term "cyclic olefin resin" refers to a polymer having an alicyclic structure in the molecule, which is obtained by polymerizing a cyclic olefin monomer, or a hydrogenated product thereof. In the present invention, the term "crystalline cyclic olefin resin" refers to a cyclic olefin resin whose melting point can be observed by differential scanning calorimetry (DSC).

[0023] Examples of the cyclic olefin resin include a ring-opening polymer of a cyclic olefin monomer (hereinafter also referred to as "polymer (α)") and its hydrogenated product, and an addition polymer using at least one cyclic olefin monomer (hereinafter also referred to as "polymer (β)") and its hydrogenated product. The cyclic olefin resin may be used alone or in combination of two or more.

[0024] Here, the hydrogenation rate of the hydrogenated product is preferably 95% or more. If the hydrogenation rate is 95% or more, the resin composition for substrates will have excellent resistance to heat yellowing and heat degradation. In the present invention, the "hydrogenation rate" refers to the hydrogenation rate relative to all carbon-carbon unsaturated bonds contained in the hydrogenated polymer (including double bonds in the aromatic rings, if the polymer has an aromatic ring), and can be measured using nuclear magnetic resonance (NMR) spectroscopy.

[0025] The cyclic olefin monomer used in producing the polymer (α) and its hydrogenated product is a compound having a ring structure formed by carbon atoms and having a carbon-carbon double bond in the ring. Examples of such compounds include norbornene-based monomers. Furthermore, when the polymer (α) is a copolymer, a monocyclic olefin can also be used as the cyclic olefin monomer.

[0026] The norbornene-based monomer is a monomer containing a norbornene ring. Examples of the norbornene-based monomer include bicyclic monomers such as bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: ethylidenenorbornene) and derivatives thereof (having a substituent on the ring); tricyclo[4.3.0.1 ２，５ ]deca-3,7-diene (common name: dicyclopentadiene) and tricyclic monomers such as its derivatives; 7,8-benzotricyclo[4.3.0.1 ２，５ ]dec-3-ene (common name: methanotetrahydrofluorene, tetracyclo[7.4.0.0 ２，７ .1 １０，１３ ]trideca-2,4,6,11-tetraene) and its derivatives, tetracyclo[4.4.0.1 ２，５ .1 ７，１０ ] dodec-3-ene (common name: tetracyclododecene), 8-ethylidenetetracyclo[4.4.0.1 ２，５ .1 ７，１０ ]-3-dodecene and its derivatives; and the like.

[0027] These monomers may have a substituent at any position, such as an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group, an alkylidene group such as an ethylidene group or a propan-2-ylidene group, an aryl group such as a phenyl group, a hydroxy group, an acid anhydride group, a carboxyl group, or an alkoxycarbonyl group such as a methoxycarbonyl group.

[0028] Examples of monocyclic olefins include cyclic monoolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; and cyclic diolefins such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, and phenylcyclooctadiene.

[0029] These cyclic olefin monomers can be used alone or in combination of two or more. When two or more cyclic olefin monomers are used, the polymer (α) may be a block copolymer or a random copolymer.

[0030] The polymer (α) can be produced according to a known method using a metathesis polymerization catalyst. There are no particular limitations on the metathesis polymerization catalyst, and known catalysts can be used. Examples of metathesis polymerization catalysts include catalyst systems comprising a halide, nitrate, or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and a reducing agent; catalyst systems comprising a halide or acetylacetone compound of a metal selected from titanium, vanadium, zirconium, tungsten, and molybdenum, and an organoaluminum compound as a co-catalyst; and Schrock-type or Grubbs-type living ring-opening metathesis polymerization catalysts (JP-A-7-179575; J. Am. Chem. Soc., 1986, 108, p. 733; J. Am. Chem. Soc., 1993, 115, p. 9858; and J. Am. Chem. Soc., 1996, 118, p. 100). These metathesis polymerization catalysts can be used alone or in combination of two or more.

[0031] The amount of the metathesis polymerization catalyst used may be appropriately selected depending on the polymerization conditions, etc., but is usually 0.000001 to 0.1 mole, preferably 0.00001 to 0.01 mole, per mole of the cyclic olefin monomer.

[0032] When ring-opening polymerization of a cyclic olefin monomer is carried out, a linear α-olefin having 4 to 40 carbon atoms, such as 1-butene, 1-hexene, or 1-decene, can be used as a molecular weight modifier. The amount of the linear α-olefin added is usually 0.01 to 0.50 mol, preferably 0.03 to 0.30 mol, and more preferably 0.05 to 0.15 mol, per 1 mol of the cyclic olefin monomer.

[0033] The ring-opening polymerization of the cyclic olefin monomer can be carried out in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the polymerization reaction. Examples of the organic solvent include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane, methylnorbornane, and ethylnorbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; and halogenated alkanes and aryl compounds such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, and tetrachloroethylene. These organic solvents can be used alone or in combination of two or more.

[0034] The polymerization temperature is not particularly limited, but is usually −50 to 250° C., preferably −30 to 200° C., and more preferably −20 to 150° C. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, and preferably 1 to 10 hours.

[0035] The polymer (α) obtained by the above method can be subjected to a hydrogenation reaction to obtain a hydrogenated product of the polymer (α). The hydrogenation reaction of the polymer (α) can be carried out by a conventional method, by contacting the polymer (α) with hydrogen in the presence of a hydrogenation catalyst.

[0036] The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst. Homogeneous catalysts are easily dispersed in the hydrogenation reaction liquid, allowing the amount of catalyst to be reduced. In addition, they have sufficient activity even without high temperature and high pressure, making decomposition and gelation of the polymer (α) and its hydrogenated product less likely to occur. For this reason, from the viewpoints of cost and product quality, it is preferable to use a homogeneous catalyst. On the other hand, heterogeneous catalysts exhibit particularly excellent activity under high temperature and high pressure, allowing the polymer (α) to be hydrogenated in a short time.

[0037] Examples of homogeneous catalysts include Wilkinson's complex [chlorotris(triphenylphosphine)rhodium(I)], dichlorobis(triphenylphosphine)palladium, chlorohydridocarbonyltris(triphenylphosphine)ruthenium, bis(tricyclohexylphosphine)benzylidineruthenium(IV) dichloride; and catalysts comprising a combination of a transition metal compound and an alkyl metal compound, such as combinations of cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, and tetrabutoxytitanate / dimethylmagnesium.

[0038] Examples of heterogeneous catalysts include those in which a metal such as Ni, Pd, Pt, Ru, or Rh is supported on a carrier. In particular, when the amount of impurities in the resulting hydride is to be reduced, it is preferable to use an adsorbent such as alumina or diatomaceous earth as the carrier.

[0039] The hydrogenation reaction is usually carried out in an organic solvent. There are no particular limitations on the organic solvent as long as it is inert to the hydrogenation reaction. Specific examples include the same organic solvents as those previously mentioned as being used in the ring-opening polymerization of cyclic olefin monomers. In addition, since the solvent used in the ring-opening polymerization reaction is usually also suitable as a solvent for the hydrogenation reaction, a hydrogenation catalyst can be added to the ring-opening polymerization reaction solution, and then the solution can be subjected to the hydrogenation reaction.

[0040] The hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature. Therefore, when the polymer (α) has an aromatic ring, the remaining rate of the aromatic ring can be controlled by selecting the hydrogenation catalyst, adjusting the reaction temperature, etc. For example, in order to leave the unsaturated bond of the aromatic ring to a certain extent or more, it is sufficient to control the reaction temperature, reduce the hydrogen pressure, shorten the reaction time, etc.

[0041] Examples of cyclic olefin monomers used in the synthesis of polymer (β) and its hydrogenated product include the same cyclic olefin monomers as those used in the synthesis of polymer (α). In the synthesis of polymer (β), other monomers copolymerizable with the cyclic olefin monomers can also be used as monomers. Examples of other monomers include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; aromatic vinyl compounds, such as styrene and α-methylstyrene; and non-conjugated dienes, such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. Among these, α-olefins are preferred, and ethylene is more preferred. The other monomers can be used alone or in combination of two or more.

[0042] When a cyclic olefin monomer and another monomer are addition copolymerized, the ratio of the amounts of the cyclic olefin monomer to the other monomer used is usually 30:70 to 99:1, preferably 50:50 to 97:3, and more preferably 70:30 to 95:5 by weight (cyclic olefin monomer:other monomer).

[0043] When two or more types of cyclic olefin monomers are used, or when a cyclic olefin monomer and another monomer are used, the polymer (β) may be a block copolymer or a random copolymer.

[0044] The polymer (β) can be synthesized according to a known method using an addition polymerization catalyst. Examples of the addition polymerization catalyst include vanadium catalysts formed from a vanadium compound and an organoaluminum compound, titanium catalysts formed from a titanium compound and an organoaluminum compound, and zirconium catalysts formed from a zirconium complex and an aluminoxane. These addition polymerization catalysts can be used alone or in combination of two or more. The amount of the addition polymerization catalyst used can be appropriately selected depending on the polymerization conditions, etc., but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol, per mol of monomer.

[0045] The addition polymerization of cyclic olefin monomers is usually carried out in an organic solvent. There are no particular limitations on the organic solvent as long as it is inert to the polymerization reaction. Specific examples thereof include the same organic solvents as those listed above as being used in the ring-opening polymerization of cyclic olefin monomers.

[0046] The polymerization temperature is usually −50 to 250° C., preferably −30 to 200° C., and more preferably −20 to 150° C. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, and preferably 1 to 10 hours.

[0047] The polymer (β) obtained by the above method can be subjected to a hydrogenation reaction to obtain a hydrogenated product of the polymer (β). The hydrogenation reaction of the polymer (β) can be carried out by the same method as the method for hydrogenating the polymer (α) described above.

[0048] Among these, a crystalline hydrogenated cyclic olefin polymer (hereinafter also referred to as "polymer (γ)") is preferred as the cyclic olefin resin. Polymer (γ) is a hydrogenated polymer obtained by polymerizing a cyclic olefin monomer, and has crystallinity. That is, polymer (γ) is a polymer whose melting point can be observed by differential scanning calorimetry (DSC). Use of polymer (γ) makes it possible to produce a substrate with even better heat resistance. The melting point of polymer (γ) is preferably 200°C or higher, more preferably 230 to 290°C.

[0049] The polymer (γ) may be a ring-opening polymer or an addition polymer, but is preferably a ring-opening polymer (i.e., a crystalline hydrogenated product of the polymer (α)) because it has better crystallinity.

[0050] The cyclic olefin monomer used in the production of polymer (γ) is not particularly limited, and those exemplified above as the cyclic olefin monomers used in the production of polymer (α) can be used. Among them, it is preferable to use dicyclopentadiene as at least one of the cyclic olefin monomers, since this results in polymer (γ) with better crystallinity. The content of dicyclopentadiene-derived repeating units in all repeating units of polymer (γ) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass.

[0051] Some cyclic olefin monomers exist as endo and exo stereoisomers, and either can be used as a monomer when producing polymer (γ). Alternatively, one isomer may be used alone, or an isomer mixture in which the endo and exo isomers are present in any desired ratio may be used. It is preferable to increase the ratio of one stereoisomer, as this results in a polymer (γ) with better crystallinity. When the ratio of the endo isomer is high in the isomer mixture, the ratio of the endo isomer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on 100% by mass of the entire isomer mixture. When the ratio of the exo isomer is high in the isomer mixture, the ratio of the exo isomer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on 100% by mass of the entire isomer mixture. It is preferable that the ratio of the endo isomer is high in the isomer mixture, based on 100% by mass of the entire isomer mixture.

[0052] In polymer (γ), generally, as the degree of syndiotactic stereoregularity (ratio of racemo-dyads) increases, the crystallinity tends to increase. The degree of stereoregularity of polymer (γ) is not particularly limited, but the ratio of racemo-dyads to the repeating units is preferably 60% or more, more preferably 70% or more, and particularly preferably 88% or more.

[0053] The proportion of racemo-dyads is １３ Specifically, the inverse-gated decoupling method was applied at 200°C using a mixed solvent of 1,3,5-trichlorobenzene-d3 / 1,2-dichlorobenzene-d4 (volume ratio 2:1). １３ By performing C-NMR measurement, the ratio of the racemo dyads can be determined from the intensity ratio of the signal at 43.35 ppm derived from the meso dyad and the signal at 43.43 ppm derived from the racemo dyad, with the peak at 127.5 ppm of 1,2-dichlorobenzene-d4 as the reference shift.

[0054] The stereoregularity of the polymer usually does not change before and after the hydrogenation reaction. Therefore, a polymer (γ) having high syndiotactic stereoregularity can be obtained, for example, by ring-opening polymerization of a cyclic olefin monomer to obtain a polymer having high syndiotactic stereoregularity, and then subjecting the polymer to a hydrogenation reaction. For example, a polymer (γ) having high syndiotactic stereoregularity can be synthesized according to the methods described in WO 2012 / 033076, JP 2014-118475, etc.

[0055] The weight average molecular weight (Mw) of the cyclic olefin resin is not particularly limited, but is preferably 10,000 or more and 100,000 or less, and the number average molecular weight (Mn) is preferably 3,000 or more and 800,000 or less.

[0056] (Method for Producing Resin Powder Particles) The method for producing resin powder particles having a halogen content of 3% by mass or less contained in the resin composition for substrates of the present invention is not particularly limited, and the following methods 1) to 3) can be used, for example. 1) A method for producing resin powder particles, comprising subjecting a solution containing a cyclic olefin ring-opening polymer at a solids concentration of 10% by mass or more to a hydrogenation reaction to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less. 2) A method for producing resin powder particles, comprising pulverizing a hydrogenated crystalline cyclic olefin ring-opening polymer in a solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less. 3) A method for producing resin powder particles, comprising dry-pulverizing a cyclic olefin resin having a halogen content of 3% by mass or less to obtain resin powder particles of a cyclic olefin resin having a halogen content of 3% by mass or less. Methods 1) to 3) will be described in detail below.

[0057] <Method 1)> In method 1), a solution containing a cyclic olefin ring-opening polymer at a solids concentration of 10% by mass or more is subjected to a hydrogenation reaction to hydrogenate the cyclic olefin ring-opening polymer in the solution, thereby obtaining resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less.

[0058] As the cyclic olefin ring-opening polymer, for example, the polymer (α) described above can be used. Furthermore, as a solution containing a cyclic olefin ring-opening polymer at a solids concentration of 10% by mass or more, for example, a solution containing the polymer (α), an organic solvent, a polymerization catalyst, etc. can be used. As the organic solvent and the polymerization catalyst, the organic solvent and the polymerization catalyst used in the hydrogenation reaction of the polymer (α) described above can be used. Furthermore, the method for hydrogenating the polymer (α) can be the same as the method described above.

[0059] The resin powder particles of the hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3% by mass or less obtained by the above method 1) typically have an average particle size of 10 μm or less. Therefore, the above method 1) makes it possible to produce resin powder particles that can be suitably used in the resin composition for substrates of the present invention. Here, the reason why the resin powder particles of the hydrogenated crystalline cyclic olefin ring-opening polymer obtained by the above method 1) have a small particle size is not clear, but it is presumed that this is because, when a solution containing a cyclic olefin ring-opening polymer is subjected to a hydrogenation reaction, a hydrogenated crystalline cyclic olefin ring-opening polymer is produced in the solution. In this case, if the solids concentration of the cyclic olefin ring-opening polymer in the solution is 10% by mass or more, the solubility of the hydrogenated crystalline cyclic olefin ring-opening polymer in the solution decreases, resulting in more rapid precipitation of the hydrogenated crystalline cyclic olefin ring-opening polymer.

[0060] <Method 2)> In method 2), a hydrogenated crystalline cyclic olefin ring-opening polymer is pulverized in a solution to obtain resin powder particles of a hydrogenated crystalline cyclic olefin ring-opening polymer having a halogen content of 3 mass% or less.

[0061] The hydrogenated crystalline cyclic olefin ring-opening polymer may be, for example, the polymer (γ) described above. The method for pulverizing the hydrogenated crystalline cyclic olefin ring-opening polymer in solution is not particularly limited, and known wet pulverization methods can be used. From the viewpoint of efficiently producing resin powder particles suitable for use in the resin composition for substrates of the present invention, it is preferable to use method 2) above to spray a solution containing the hydrogenated crystalline cyclic olefin ring-opening polymer at high pressure and pulverize the hydrogenated crystalline cyclic olefin ring-opening polymers by causing them to collide with each other. The hydrogenated crystalline cyclic olefin ring-opening polymer particles obtained by such pulverization typically have an average particle size of 10 μm or less. Therefore, they can be suitably used as resin powder particles for the resin composition for substrates of the present invention. When spraying a solution containing the hydrogenated crystalline cyclic olefin ring-opening polymer at high pressure, the spray pressure is preferably 100 MPa or higher in order to ensure uniform particle size of the resulting resin powder particles.

[0062] The above methods 1) and 2) may be carried out alone or in combination. For example, by carrying out the above method 2) after the above method 1), resin powder particles having a smaller average particle size can be efficiently produced.

[0063] <Method 3)> The resin having a halogen content of 3% by mass or less used in method 3) is not particularly limited, and can be, for example, the cyclic olefin resin described above, polypropylene, etc. Furthermore, the dry grinding method is not particularly limited, and a known dry grinding method can be used.

[0064] <Other Components> The resin composition for substrates of the present invention may further contain components other than the resin powder particles described above. Examples of other components include known additives such as antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, colorants, plasticizers, flame retardants, and antistatic agents. The content of other components in the resin composition for substrates can be appropriately determined depending on the application of the composition for substrates, etc.

[0065] <Method for preparing resin composition for substrate> The method for preparing the resin composition for substrate of the present invention is not particularly limited, and can be prepared, for example, by mixing resin powder particles having a halogen content of 3 mass% or less with other components using a known method.

[0066] The content of the resin powder particles in the resin composition for substrates is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more, based on the total mass of the resin composition for substrates. When the content of the resin powder is equal to or more than the above lower limit, the resin composition for substrates of the present invention can be more suitably used as a material for producing substrates for various applications.

[0067] (Substrate) A substrate produced using the resin composition for substrates of the present invention usually has a dielectric constant of 2.5 or less at a frequency of 10 GHz. Therefore, the substrate produced using the resin composition for substrates of the present invention can be used for various applications, and is particularly suitable for use as a high-frequency substrate.

[0068] <Method for manufacturing substrate> Here, the method for manufacturing a substrate using the resin composition for substrates of the present invention is not particularly limited, and for example, a substrate can be manufactured by pressing the resin composition for substrates of the present invention. In this case, the pressing method is not particularly limited, and pressing can be performed by a known method. In addition, the pressing pressure is not particularly limited, and can be adjusted depending on the thickness of the substrate to be obtained.

[0069] The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the following, "%" and "parts" are based on mass unless otherwise specified. Measurements in the examples and comparative examples were carried out by the following methods.

[0070] <Weight-average molecular weight and number-average molecular weight> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers obtained in Examples 1, 3, 4, and 5 were determined as values ​​converted into standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent. The GPC measurements were performed at 40°C. The measurement apparatus used was a "System HLC-8320" manufactured by Tosoh Corporation, and the measurement column used was an "H-type column" manufactured by Tosoh Corporation.

[0071] <Hydrogenation rate> The hydrogenation rates of the hydrogenated products obtained in Examples 1, 3, and 4 were １ Calculation was performed by measuring H-NMR.

[0072] <Glass Transition Temperature and Melting Point> A sample was heated in a differential scanning calorimeter to completely melt it, then cooled to room temperature at a temperature drop rate of 10°C / min, and then differential scanning calorimetry was performed at a temperature rise rate of 10°C / min up to 350°C. The glass transition temperature (Tg) and melting point were measured from the peak at this time. The differential scanning calorimeter used was a "High Sensitivity Differential Scanning Calorimeter EXSTARX-DSC7000" manufactured by Hitachi High-Tech Science Corporation. The differential scanning calorimeter was calibrated using indium, tin, and lead as temperature and calorie standards.

[0073] <Halogen Content> A sample was placed in an aluminum ring, compressed with a press, and covered with a polypropylene (PP) film, and an X-ray fluorescence (XRF) analyzer (Rigaku Corporation, "Primus IV") was used to perform composition analysis of elements from carbon (C) to gallium (Ga). From the results of the XRF analysis, the ratio of the total mass of fluorine (F) and chlorine (Cl) to the total mass of elements from carbon (C) to gallium (Ga) (C to Ga) [(F + Cl) / (C to Ga) x 100] was calculated, and the obtained value was taken as the halogen content (mass%).

[0074] <Average particle size and proportion of resin powder particles with a particle size of 70 μm or more> A sample was dispersed in a dispersion medium (cyclohexane, isopropyl alcohol, or 3M's "Novec7300"), and the volume-weighted average diameter and particle size distribution of the sample were measured using a laser diffraction particle size distribution analyzer (Shimadzu Corporation's "SALD-3100"). The obtained volume-weighted average diameter was taken as the average particle size. Furthermore, in the above particle size distribution, the proportion of samples with a volume-weighted diameter of more than 70 μm relative to the entire sample was taken as the proportion of the volume of resin powder particles with a particle size of 70 μm or more relative to the total volume of resin powder particles in the resin composition for substrates.

[0075] <Dielectric Constant> A sheet was prepared by pressing the sample at a pressure of 20 MPa or more. The pressure during pressing was set to the glass transition temperature (Tg) or higher of the sample if the sample was amorphous, and set to the melting point or higher of the sample if the sample was crystalline. Next, the obtained sheet was cut to obtain a test piece. The dielectric constant of this test piece at a frequency of 10 GHz was measured by a cylindrical cavity resonator method using a network analyzer ("N5230A" manufactured by Keysight Technologies, Inc.).

[0076] Example 1 A glass pressure-resistant reactor that had been thoroughly dried and then purged with nitrogen was charged with 143 parts of a 70% cyclohexane solution of dicyclopentadiene (endo isomer content of 99% or more) (100 parts as dicyclopentadiene), 5.1 parts of 1-hexene, and 514 parts of cyclohexane, followed by the addition of 0.37 parts of a 19% n-hexane solution of diethylaluminum ethoxide. Next, a solution of 0.07 parts of tetrachlorotungsten phenylimide (tetrahydrofuran) complex in 3 parts of toluene was added, and the mixture was heated to 53°C to initiate a ring-opening polymerization reaction. After 2 hours, 1.3 parts of methanol was added to terminate the ring-opening polymerization reaction. The dicyclopentadiene ring-opening polymer (cyclic olefin ring-opening polymer) contained in the resulting polymerization reaction solution had a weight-average molecular weight (Mw) of 28,200 and a number-average molecular weight (Mn) of 8,900. To the obtained polymerization reaction solution, 0.5 parts of diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., "Radiolite #300") was added as a filter aid. This suspension was filtered using a leaf filter (manufactured by IHI Corporation, "CFR2") to obtain a solution containing a dicyclopentadiene ring-opening polymer. Next, the obtained solution containing the dicyclopentadiene ring-opening polymer was transferred to a reactor equipped with a stirrer and a temperature-controlled jacket (manufactured by Sumitomo Heavy Industries, Ltd.), and then 167 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyl tris(triphenylphosphine)ruthenium were added to prepare a solution containing a dicyclopentadiene ring-opening polymer at a solids concentration of 12%. Next, while stirring the entire volume at a rotation speed of 64 rpm, a hydrogenation reaction was carried out for 4 hours at a hydrogen pressure of 4 MPa and a temperature of 180 ° C., to obtain a slurry containing particles of hydrogenated dicyclopentadiene ring-opening polymer. The hydrogenation rate of the hydrogenated dicyclopentadiene ring-opening polymer was 99.5%. To 100 parts of the solid content of the slurry, 0.5 parts of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (manufactured by BASF Japan, "Irganox (registered trademark) 1010") was added as an antioxidant, and the solvent was removed using a freeze dryer (manufactured by Nippon Techno Service Co., Ltd., "FD0480-1601") to obtain particles of a hydrogenated dicyclopentadiene ring-opening polymer.The obtained particles of hydrogenated dicyclopentadiene ring-opening polymer were used as a sample and differential scanning calorimetry was performed. The results showed that the hydrogenated dicyclopentadiene ring-opening polymer particles were crystalline. Furthermore, the halogen content, average particle size, proportion of resin powder particles with a particle size of 70 μm or more, and dielectric constant were determined using the sample. The results are shown in Table 1.

[0077] Example 2 The slurry prepared in Example 1 after adding the antioxidant was passed through a ball chamber having a diameter of 14 mm 30 times, calculated from the circulation time, using a wet atomization apparatus (manufactured by Sugino Machine, "HJP-25005"). The spraying pressure was set to 200 MPa. The solvent was removed from the resulting slurry using a freeze dryer (manufactured by Nippon Techno Service, "FD0480-1601") to obtain particles of hydrogenated dicyclopentadiene ring-opening polymer. Differential scanning calorimetry was performed on the resulting particles of hydrogenated dicyclopentadiene ring-opening polymer, and the results showed that the particles were crystalline. The same measurements were performed on the sample as in Example 1. The results are shown in Table 1.

[0078] (Example 3) A glass pressure-resistant reactor that had been thoroughly dried and then purged with nitrogen was charged with 2.0 parts of a monomer mixture consisting of 25% tetracyclododecene, 70% methanotetrahydrofluorene, and 25% norbornene (1% relative to the total amount of monomers used in polymerization), 1.2 parts of 1-hexene, 0.42 parts of diisopropyl ether, 0.11 parts of isobutyl alcohol, and 785 parts of cyclohexane, followed by the addition of 1.35 parts of a 20% concentration cyclohexane solution of triisobutylaluminum and stirring. Next, 13.4 parts of a 0.65% cyclohexane solution of tungsten hexachloride was added, and the mixture was heated to 53 ° C. to initiate a ring-opening polymerization reaction, followed by stirring for 10 minutes. Next, while maintaining the total volume at 53°C and stirring, 198 parts of the monomer mixture (99% based on the total amount of monomers used in polymerization) and 20.1 parts of a 0.65% tungsten hexachloride cyclohexane solution were each continuously added dropwise over 150 minutes into the polymerization reaction vessel. After the completion of the dropwise addition, stirring was continued for 30 minutes, and then 0.4 parts of isopropyl alcohol was added to terminate the ring-opening polymerization reaction. The ring-opening polymer (cyclic olefin ring-opening polymer) of the monomer mixture contained in the resulting polymerization reaction solution had a weight-average molecular weight (Mw) of 19,000 and a number-average molecular weight (Mn) of 10,700. Next, 300 parts of the resulting polymerization reaction solution were transferred to an autoclave equipped with a stirrer, and 32 parts of cyclohexane and 3.8 parts of a diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Industries, Ltd., "T8400RL", nickel loading: 58%) were added. The atmosphere in the autoclave was replaced with hydrogen, and the reaction was carried out at 190°C under a hydrogen pressure of 4.5 MPa for 6 hours. After completion of the hydrogenation reaction, the mixture was filtered at a pressure of 0.25 MPa using a pressure filter (Fundafilter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) with diatomaceous earth (Radiolite (registered trademark) #500, manufactured by Showa Chemical Industry Co., Ltd.) as a filter bed to obtain a colorless, transparent solution containing a hydrogenated cyclic olefin ring-opening polymer. The hydrogenation rate of the hydrogenated cyclic olefin ring-opening polymer was 99.7%. To the colorless, transparent solution, 0.5 parts of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (Irganox (registered trademark) 1010, manufactured by BASF Japan Ltd.) was added as an antioxidant per 100 parts of the hydrogenated cyclic olefin ring-opening polymer in the solution.Thereafter, foreign matter was removed by filtration using a filter (manufactured by Cuno Filter, "Zeta Plus (registered trademark) 30H", pore size 0.5 to 1 μm) and a metal fiber filter (manufactured by Nichidai Corporation, pore size 0.4 μm). The obtained filtrate was then placed in a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), and the solvent cyclohexane and other volatile components were removed at a temperature of 290°C and a pressure of 1 kPa or less. The filtrate was extruded in a molten state into strands from a die directly connected to the concentrator, water-cooled, and then cut into pellets using a pelletizer (manufactured by Nagata Manufacturing Co., Ltd., "OSP-2") to obtain pellets. The obtained pellets were placed together with liquid nitrogen in a rotor speed mill (manufactured by Fritsch, "P-14") and pulverized (dry pulverization) at a rotation speed of 10,000 rpm and a sieve ring mesh of 0.08 mm to 6.0 mm to obtain particles of a hydrogenated cyclic olefin ring-opening polymer. The obtained particles of hydrogenated cyclic olefin ring-opening polymer were used as a sample and subjected to differential scanning calorimetry. The results showed that the particles of hydrogenated cyclic olefin ring-opening polymer were amorphous. Furthermore, the same measurements as in Example 1 were performed using the above sample. The results are shown in Table 1.

[0079] Example 4: 100 parts of tetracyclododecene, 0.42 parts of 1-hexene, and 388 parts of cyclohexane were added to a glass pressure-resistant reactor that had been thoroughly dried and then purged with nitrogen. Subsequently, 0.40 parts of a 20% triisobutylaluminum cyclohexane solution, 0.16 parts of n-dibutyl ether, and 0.31 parts of a 10% isobutyl alcohol cyclohexane solution were added and stirred. Next, 9.70 parts of a 0.65% tungsten hexachloride cyclohexane solution were added, and the mixture was heated to 50°C to initiate a ring-opening polymerization reaction. After 2 hours, 0.11 parts of isopropyl alcohol were added to terminate the ring-opening polymerization reaction. The weight-average molecular weight (Mw) of the tetracyclododecene ring-opening polymer (cyclic olefin ring-opening polymer) contained in the resulting polymerization reaction solution was 36,200, and the number-average molecular weight (Mn) was 23,200. To the obtained polymerization reaction solution, 0.5 parts of diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., "Radiolite #300") was added as a filter aid. This suspension was filtered using a leaf filter (manufactured by IHI Corporation, "CFR2") to obtain a solution containing a tetracyclododecene ring-opening polymer. Next, the obtained solution containing the tetracyclododecene ring-opening polymer was transferred to a reactor equipped with a stirrer and a temperature-controlled jacket (manufactured by Sumitomo Heavy Industries, Ltd.), and then 600 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyl tris(triphenylphosphine)ruthenium were added to obtain a solution containing a tetracyclododecene ring-opening polymer at a solids concentration of 12%. Next, while stirring the entire volume at a rotation speed of 64 rpm, a hydrogenation reaction was carried out for 4 hours at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. to obtain a slurry containing particles of hydrogenated tetracyclododecene ring-opening polymer. The hydrogenation rate of the hydrogenated tetracyclododecene ring-opening polymer was 99.3%. To 100 parts of the solid content of the slurry, 0.5 parts of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (manufactured by BASF Japan, "Irganox (registered trademark) 1010") was added as an antioxidant, and the solvent was removed using a freeze dryer (manufactured by Nippon Techno Service Co., Ltd., "FD0480-1601") to obtain particles of hydrogenated tetracyclododecene ring-opening polymer.The obtained particles of hydrogenated tetracyclododecene ring-opening polymer were subjected to differential scanning calorimetry, which revealed that the particles of hydrogenated tetracyclododecene ring-opening polymer were crystalline. Furthermore, the same measurements as in Example 1 were performed using the above sample. The results are shown in Table 1.

[0080] Example 5 A polymerization reactor whose interior had been dried and purged with nitrogen was charged with 960 parts of toluene, 220 parts of tetracyclododecene, and 0.166 parts of 1-hexene, and the solvent temperature was raised to 40°C while stirring at a rotation speed of 300 to 350 rpm. Meanwhile, 23.5 parts of toluene, 0.044 parts of rac-ethylenebis(1-indenyl)zirconium dichloride, and 6.22 parts of a 9.0% toluene solution of methylaluminoxane (manufactured by Tosoh Finechem Corporation, "TMAO-200 series") were mixed in a glass container to obtain a catalyst solution. When the solvent temperature in the reactor reached 40°C, the catalyst solution was added to the reactor, and then ethylene gas at 0.08 MPa was immediately introduced into the liquid phase to initiate polymerization. The ethylene outlet was positioned such that the ratio (B) / (A) of the distance (A) between the bottom of the reactor and the liquid level to the distance (B) between the ethylene outlet and the liquid level was 0.60. Ethylene gas was automatically supplied as ethylene gas was consumed, maintaining a constant ethylene gas pressure. After 30 minutes, the introduction of ethylene gas was stopped, the pressure was released, and 5 parts of methanol were added to terminate the polymerization reaction. The resulting reaction solution was filtered through diatomaceous earth ("Radiolite (registered trademark) #800" manufactured by Showa Chemical Industry Co., Ltd.) and poured into isopropanol containing 0.05% hydrochloric acid to precipitate a polymer. The precipitated polymer was separated, washed, and dried under reduced pressure at 100°C for 15 hours to obtain an ethylene-tetracyclododecene copolymer. The resulting ethylene-tetracyclododecene copolymer had a weight-average molecular weight (Mw) of 56,000 and a number-average molecular weight (Mn) of 22,000. To the obtained ethylene-tetracyclododecene copolymer, 1.0 part of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (manufactured by BASF Japan, "Irganox (registered trademark) 1010") as an antioxidant and 300 parts of cyclohexane were added, and the solvent was removed using a freeze dryer (manufactured by Nippon Techno Service Co., Ltd., "FD0480-1601").The material obtained after solvent removal was finely crushed and placed in a rotor speed mill (manufactured by Fritsch, model number "P-14") together with liquid nitrogen, and crushed (dry crushed) at a rotation speed of 10,000 rpm with a sieve ring mesh of 0.08 mm to 6.0 mm to obtain particles of ethylene-tetracyclododecene copolymer. The obtained particles of ethylene-tetracyclododecene copolymer were used as samples and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0081] (Example 6) Polypropylene (Prime Polypro, manufactured by Prime Polypro) pellets were placed in a rotor speed mill (Fritsch, P-14) together with liquid nitrogen. The rotation speed was set to 10,000 rpm, and the pellets were pulverized using a sieve ring mesh condition of 0.08 to 6.0 mm to obtain polypropylene particles. The obtained polypropylene particles were used as a sample and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0082] Comparative Example 1 A commercially available polytetrafluoroethylene powder (manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., "6-J") was used as a sample and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0083] (Comparative Example 2) Pellets of perfluoroalkoxyalkane (440HP-J, manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.) were placed in a rotor speed mill (P-14, manufactured by Fritsch) together with liquid nitrogen. The perfluoroalkoxyalkane pellets were then pulverized (dry pulverized) at a rotation speed of 10,000 rpm and with a sieve ring mesh of 0.08 mm to 6.0 mm to obtain a perfluoroalkoxyalkane powder. The obtained powder was used as a sample and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0084]

[0085] In Table 1, "crystalline DCPD" indicates a crystalline hydrogenated dicyclopentadiene ring-opening polymer, "amorphous COP" indicates a hydrogenated amorphous cyclic olefin ring-opening polymer, "crystalline TCD" indicates a crystalline hydrogenated tetracyclododecene ring-opening polymer, "PP" indicates polypropylene, "PTFE" indicates polytetrafluoroethylene, and "PFA" indicates perfluoroalkoxyalkane.

[0086] From Table 1, it can be seen that the particles obtained in Examples 1 to 6 are resin powder particles having a halogen content of 3 mass% or less and a low dielectric constant, and therefore, by using a resin composition for substrates containing these particles, it is possible to reduce the environmental load and produce substrates with a reduced dielectric constant.

[0087] According to the present invention, it is possible to provide a resin composition for substrates that can reduce the environmental load and can be used as a material for producing substrates with a reduced dielectric constant. Also, according to the present invention, it is possible to provide a method for producing resin powder particles that can be suitably used in the resin composition for substrates of the present invention.

Claims

1. A resin composition for substrates containing resin powder particles with a halogen content of 3% by mass or less.

2. The resin composition for a substrate according to claim 1, wherein the resin powder particles have an average particle diameter of 30 μm or less, and the proportion of the volume of resin powder particles with a particle diameter of 70 μm or more to the total volume of the resin powder particles in the resin composition for the substrate is 15% or less.

3. The resin composition for a substrate according to claim 1, wherein the resin powder particles have an average particle diameter of 20 μm or less, and the proportion of the volume of resin powder particles with a particle diameter of 70 μm or more to the total volume of the resin powder particles in the substrate resin composition is 15% or less.

4. The resin composition for substrates according to claim 1, wherein the resin powder particles are particles of a cyclic olefin resin.

5. The resin composition for substrates according to any one of claims 1 to 4, wherein the resin powder particles are particles of a crystalline cyclic olefin resin.

6. A method for producing resin powder particles, comprising the step of subjecting a solution containing a cyclic olefin ring-opening polymer at a solid content concentration of 10% by mass or more to a hydrogenation reaction, thereby obtaining resin powder particles of a crystalline cyclic olefin ring-opening polymer hydride having a halogen content of 3% by mass or less.

7. A method for producing resin powder particles, comprising the step of pulverizing a crystalline cyclic olefin ring-opening polymer hydride in a solution to obtain resin powder particles of a crystalline cyclic olefin ring-opening polymer hydride having a halogen content of 3% by mass or less.