JP2017149898A - Flame-retardant resin composition and resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition which is excellent in flame retardancy and has low dielectric constant and dielectric loss tangent, and to provide a resin molding formed by molding the flame-retardant resin composition.SOLUTION: There are provided a flame-retardant resin composition which contains a hydrogenated cyclic olefin ring-opened polymer, a specific condensed phosphate flame retardant, and a specific organic phosphinate flame retardant; and a resin molding formed by molding the flame-retardant resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant resin composition that is excellent in flame retardancy and has a low dielectric constant and dielectric loss tangent, and a resin molded body formed by molding this flame retardant resin composition.

  Conventionally, cyclic olefin polymers have been widely used as molding materials and the like because they are excellent in transparency, low moisture absorption, heat resistance, insulation, chemical resistance, impact resistance, and the like. However, when a resin composition is prepared by adding a flame retardant in order to improve the flame retardancy of a resin composition containing a cyclic olefin polymer, the above properties inherent to the cyclic olefin polymer may be impaired. there were.

  As a resin composition that can solve this problem, Patent Document 1 describes a flame retardant resin composition containing a specific norbornene polymer and a halogen-containing flame retardant. This resin composition maintains the mechanical strength and chemical resistance inherent in norbornene-based polymers and is excellent in flame retardancy.

However, like the resin composition described in Patent Document 1, a resin composition containing a norbornene-based polymer and a halogen-containing flame retardant provides an excellent flame retardant effect, but a halogen-containing flame retardant during resin molding. Since hydrogen halide is generated by thermal decomposition, problems such as contamination of the working environment, corrosion of the mold, coloring of the resin, and gelation may occur. Furthermore, resin compositions containing these halogen-containing flame retardants may cause harmful dioxin-based compounds during combustion, and substances regulated by the European Union (EU) RoHS directive In particular, there are many demands for halogen-free flame retardant in electrical and electronic applications, and they are not necessarily suitable as molding materials for high-frequency circuit boards.
For this reason, a flame retardant resin composition having excellent flame retardancy and low dielectric constant and dielectric loss tangent has been demanded.

JP-A-11-140282

  The present invention has been made in view of the above circumstances, and has a flame retardant resin composition having excellent flame retardancy and low dielectric constant and dielectric loss tangent, and molding the flame retardant resin composition. It aims at providing the resin molding which becomes.

In order to solve the above problems, the present inventor has intensively studied a resin composition containing a cyclic olefin ring-opening polymer hydrogenated product and a flame retardant. As a result, it was found that a resin composition having a low dielectric constant and dielectric loss tangent can be obtained by using a condensed phosphate ester flame retardant as the flame retardant.
However, condensed phosphate ester flame retardants tend to be inferior in compatibility with the cyclic olefin ring-opening polymer hydrogenated product and in dispersibility in the cyclic olefin ring-opened polymer hydrogenated product. The acid ester flame retardant sometimes separated. Moreover, when the addition amount was reduced in order to suppress the separation of the condensed phosphate ester-based flame retardant, there was a problem that it was difficult to obtain a resin composition having excellent flame retardancy.
As a result of further studies by the inventor, by using an organic phosphinate flame retardant in addition to the condensed phosphate ester flame retardant, separation of the condensed phosphate ester flame retardant can be suppressed. Thus, it was found that a flame retardant resin composition having excellent flame retardancy and low dielectric constant and dielectric loss tangent can be obtained. The present invention has been made based on such findings.

Thus, according to the present invention, the following flame-retardant resin composition [1] to [5] and the resin molded product [6] are provided.
[1] A flame retardant resin composition containing a hydrogenated cyclic olefin ring-opening polymer, a condensed phosphate ester flame retardant, and an organic phosphinate flame retardant, the condensed phosphate ester flame retardant Is the following formula (1)

(Wherein R ^{1 to} R ⁴ each independently represents an unsubstituted or substituted aryl group, X represents a divalent group having an arylene structure, and a is an integer of 2 or more. )
The organic phosphinate flame retardant is a compound represented by the following formula (2):

(Wherein R ⁵ and R ⁶ each independently represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, M ^{b +} represents a b-valent metal ion, b Is 1, 2 or 3.)
Or the following formula (3)

(Wherein R ⁷ and R ⁸ each independently represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, Y represents a divalent group, and M ^{c +} represents C, d and e are each independently 1, 2 or 3, which satisfy the formula: c × d = 2 × e.)
The flame retardant resin composition characterized by being the compound shown by these.
[2] The flame retardant resin composition according to [1], wherein the condensed phosphate ester flame retardant has a melting point of 150 ° C. or lower.
[3] The content of the condensed phosphate ester flame retardant is 1 to 30 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product, according to [1] or [2]. Flame retardant resin composition.
[4] The flame retardant resin composition according to any one of [1] to [3], wherein the organic phosphinate flame retardant has a melting point of 300 ° C. or higher.
[5] Any of [1] to [4], wherein the content of the organic phosphinate flame retardant is 1 to 30 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product. The flame-retardant resin composition as described in 2.
[6] A resin molded body obtained by molding the flame retardant resin composition according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the flame-retardant resin composition which is excellent in a flame retardance and whose dielectric constant and dielectric loss tangent are low, and the resin molded object formed by shape | molding this flame-retardant resin composition are provided.

  Hereinafter, the present invention will be described in detail by dividing into 1) a flame retardant resin composition and 2) a resin molded product.

1) Flame Retardant Resin Composition The flame retardant resin composition of the present invention may be referred to as a cyclic olefin ring-opening polymer hydrogenated product, a condensed phosphate ester flame retardant (hereinafter referred to as “flame retardant (α)”). ), And an organic phosphinate salt flame retardant (hereinafter sometimes referred to as “flame retardant (β)”), wherein the flame retardant (α) is represented by the formula ( The compound represented by 1), wherein the flame retardant (β) is a compound represented by the formula (2) or the formula (3).

[Cyclic olefin ring-opening polymer hydrogenated product]
The cyclic olefin ring-opened polymer hydrogenated product used in the present invention is obtained by subjecting the cyclic olefin ring-opened polymer to a hydrogenation reaction.
The cyclic olefin ring-opening polymer is a polymer obtained by performing a ring-opening polymerization reaction using a cyclic olefin as a monomer. In particular, in the present invention, it means a polymer obtained using at least a norbornene monomer as a monomer.
Here, the “cyclic olefin” refers to a compound having an alicyclic structure in the molecule and a carbon-carbon double bond in the alicyclic structure. The “norbornene monomer” means a monomer having a norbornene ring structure in the molecule.
In the present invention, a flame retardant resin composition having a low dielectric constant can be efficiently obtained by using a cyclic olefin ring-opening polymer hydrogenated product as the polymer component.

  Examples of the norbornene-based monomer include compounds represented by the following formula (4).

In formula (4), R ^{9 to} R ¹² each independently include a hydrogen atom; a halogen atom; an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, an oxygen atom, or a nitrogen atom. Represents a substituent. Two groups selected from R ^{9 to} R ¹² may be bonded to form a ring. m is 0, 1 or 2.

Examples of the halogen atom for R ^{9 to} R ¹² include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the unsubstituted hydrocarbon group having 1 to 20 carbon atoms of R ^{9 to} R ¹² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t- Alkyl groups such as butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, A cycloalkyl group such as a cyclohexyl group and a cycloheptyl group; an alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group; an ethynyl group; Alkynyl groups such as 1-propynyl group, 2-propynyl (propargyl) group, 3-butynyl group, pentynyl group, hexynyl group; phenyl group Aryl groups such as tolyl group, xylyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, anthryl group and phenanthryl group; aralkyl groups such as benzyl group and phenethyl group; alkylidene such as methylidene group, ethylidene group and propylidene group Group; etc. are mentioned.
Examples of these substituents include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group;
R ⁹ and R ¹⁰ , R ¹¹ and R ^12, or R ⁹ and R ¹¹ may be combined to form a ring.

Specific examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common) Name: ethylidene norbornene) and derivatives thereof (meaning those having a substituent in the ring; the same shall apply hereinafter);
Tricyclo [4.3.0 ^1,6 . 1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and tricyclic monomers such as derivatives thereof;
7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene: also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) ) 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 tetracyclic monomers such as derivatives thereof; and the like.

These norbornene monomers can be used singly or in combination of two or more.
When the cyclic olefin ring-opening polymer is a copolymer, the copolymer may be a block copolymer or a random copolymer.

The cyclic olefin ring-opening polymer may be a copolymer obtained by using the norbornene-based monomer and the monocyclic cyclic olefin monomer.
Examples of the monocyclic olefin monomer include cyclic monoolefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and derivatives thereof; cyclic diolefins such as cyclohexadiene and cyclooctadiene and derivatives thereof; It is done.

Examples of the substituent of the monocyclic olefin monomer include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group; alkylidene groups such as propane-2-ylidene group; aryl groups such as phenyl group; Group; acid anhydride group; carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group; and the like.
Monocyclic olefin monomers can be used singly or in combination of two or more.

  Although the usage-amount of a monocyclic olefin monomer is not specifically limited, 20 weight% or less is preferable with respect to the whole cyclic olefin monomer, 10 weight% or less is more preferable, and it is still more preferable not to use.

The cyclic olefin ring-opening polymer can be produced according to a known method using a metathesis polymerization catalyst.
There is no limitation in particular as a metathesis polymerization catalyst, A well-known thing is used. As a metathesis polymerization catalyst, a catalyst system comprising a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a metal halide or acetylacetone compound selected from the group consisting of a co-catalyst and an organoaluminum compound; a Schrock type or Grubbs type living ring-opening metathesis polymerization catalyst (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) And the like.

  These metathesis polymerization catalysts can be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 with respect to 1 mol of the cyclic olefin monomer. Is a mole.

When performing ring-opening polymerization of a cyclic olefin monomer, a linear α-olefin having 4 to 40 carbon atoms such as 1-butene, 1-hexene, 1-decene and the like can be used as a molecular weight regulator.
The addition amount of the linear α-olefin is usually 0.001 to 0.030 mol, preferably 0.003 to 0.020 mol, more preferably 0.005 to 0, per 1 mol of the cyclic olefin monomer. .015 mole.

  The ring-opening polymerization of the cyclic olefin monomer can be performed 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 aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; fats such as cyclohexane, methylcyclohexane, decalin, and bicyclononane. And cyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene;

  Although superposition | polymerization temperature is not specifically limited, Usually, -50-250 degreeC, Preferably it is -30-200 degreeC, More preferably, it is -20-150 degreeC. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, preferably 1 to 10 hours.

Although the weight average molecular weight (Mw) of a cyclic olefin ring-opening polymer is not specifically limited, Preferably it is 15,000-150,000, More preferably, it is 20,000-100,000, More preferably, it is 23,000-50,000. 000.
The molecular weight distribution (Mw / Mn) of the cyclic olefin ring-opening polymer is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 4.
When the weight average molecular weight and molecular weight distribution of the cyclic olefin ring-opening polymer are within the above ranges, a resin molded product having sufficient mechanical strength can be easily obtained.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclic olefin ring-opening polymer are standard polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

As will be described later, since the stereoregularity is usually maintained in the hydrogenation reaction, a crystalline cyclic olefin ring-opening polymer hydrogen is obtained by subjecting a cyclic olefin ring-opening polymer having a high stereoregularity to the hydrogenation reaction. An additive can be obtained efficiently. The crystalline cyclic olefin ring-opening polymer hydrogenated product is excellent in heat resistance and chemical resistance. Further, the crystalline cyclic olefin ring-opening polymer hydrogenated product has a remarkable reinforcing effect when used in combination with a reinforcing material, and the mechanical strength and heat resistance are greatly improved by using it together with the reinforcing material. Because of these characteristics, the flame retardant resin composition containing a crystalline cyclic olefin ring-opening polymer hydrogenated product is suitable as a molding material for electric / electronic parts.
Here, the “crystalline cyclic olefin ring-opening polymer hydrogenated product” is a polymer whose melting point is observed when differential scanning calorimetry is performed.

  When synthesizing a cyclic olefin ring-opening polymer having high stereoregularity, the norbornene-based monomer used is preferably dicyclopentadiene. The amount of dicyclopentadiene used is preferably 50% by weight or more, more preferably 80% by weight or more, and still more preferably 100% by weight, based on the entire cyclic olefin monomer.

  Some norbornene-based monomers have endo and exo stereoisomers. When synthesizing a cyclic olefin ring-opening polymer having high stereoregularity, one of the stereoisomers of one stereoisomer is synthesized. It is preferable to increase the ratio. For example, the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

  A cyclic olefin ring-opening polymer having high stereoregularity can be synthesized, for example, according to the method described in JP-A No. 2014-162811.

The cyclic olefin ring-opened polymer hydrogenated product can be obtained by subjecting the cyclic olefin ring-opened polymer obtained by the above method to a hydrogenation reaction (hydrogenation reaction of main chain double bond).
The hydrogenation reaction of the cyclic olefin ring-opening polymer can be performed, for example, by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and a homogeneous catalyst or a heterogeneous catalyst generally used for a hydrogenation reaction of an olefin compound can be appropriately used.

  As homogeneous catalysts, transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / s-butyllithium, tetrabutoxytitanate / dimethylmagnesium and alkali Catalyst system consisting of a combination of metal compounds, dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, chlorotris (triphenylphosphine) rhodium And a noble metal complex catalyst.

  As heterogeneous catalysts, metal catalysts such as nickel, palladium, platinum, rhodium, ruthenium; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, etc. And a solid catalyst in which the metal is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide or the like.

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like. The inert organic solvent is usually the same as the solvent used for the ring-opening polymerization reaction. Therefore, the hydrogenation reaction can also be carried out using the ring-opening polymerization reaction solution with the hydrogenation catalyst added as it is.

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

  The hydrogenation rate in the hydrogenation reaction (ratio of hydrogenated main chain carbon-carbon double bonds) is not particularly limited, but is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more, Particularly preferably, it is 99% or more. As the hydrogenation rate increases, the heat resistance of the cyclic olefin ring-opening polymer hydrogenated product is further improved.

The weight average molecular weight (Mw) of the cyclic olefin ring-opening polymer hydrogenated product is not particularly limited, but is preferably 15,000 to 150,000, more preferably 20,000 to 100,000, and still more preferably 23,000. ~ 50,000.
The molecular weight distribution (Mw / Mn) of the cyclic olefin ring-opening polymer hydrogenated product is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 4.
When the weight average molecular weight and molecular weight distribution of the cyclic olefin ring-opening polymer hydrogenated product are within the above ranges, a resin molded product having sufficient mechanical strength can be easily obtained.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclic olefin ring-opening polymer hydrogenated product can be measured by the same method as described above.

  In the cyclic olefin ring-opening polymer hydrogenated product, the stereoregularity of the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction is usually maintained. Therefore, for example, when the cyclic olefin ring-opening polymer is a polymer having syndiotactic stereoregularity, by subjecting it to a hydrogenation reaction, hydrogenation of the cyclic olefin ring-opening polymer having the same stereoregularity is achieved. A thing is obtained.

  The ratio of racemo dyad in the cyclic olefin ring-opening polymer hydrogenated product having syndiotactic stereoregularity is not particularly limited, but is usually 55% or more, preferably 60% or more, more preferably 65 to 99%. Since the cyclic olefin ring-opening polymer hydrogenated product having a ratio of racemo dyad within the above range has higher crystallinity, a flame retardant resin composition that is superior in heat resistance can be obtained by using this polymer. Can be obtained.

The ratio of the racemo dyad of the cyclic olefin ring-opening polymer hydrogenated product can be quantified based on the spectrum data obtained by measuring the ¹³ C-NMR spectrum. For example, ¹³ C-NMR measurement was performed at 200 ° C. using a mixed solvent of 1,3,5-trichlorobenzene-d3 / orthodichlorobenzene-d4 (volume ratio: 2/1) as a solvent, and 43 derived from meso-dyad. The ratio of racemo dyad can be determined from the intensity ratio of the .35 ppm signal and the 43.43 ppm signal from racemo dyad.

In the crystalline cyclic olefin ring-opened polymer hydrogenated product, the temperature range of the melting point is not particularly limited, but is usually 200 ° C. or higher, preferably 230 to 290 ° C.
The hydrogenated cyclic olefin ring-opening polymer having such a melting point is excellent due to a balance between moldability and heat resistance. The melting point of the cyclic olefin ring-opening polymer hydrogenated product is adjusted by adjusting the degree of syndiotactic stereoregularity (racemo dyad ratio) or by selecting the type of monomer used. can do.

  In the flame-retardant resin composition of the present invention, the cyclic olefin ring-opening polymer hydrogenated product can be used alone or in combination of two or more.

[Condensed phosphate ester flame retardant]
The flame retardant resin composition of the present invention contains a condensed phosphate ester flame retardant [flame retardant (α)] represented by the following formula (1).
In the flame retardant resin composition of the present invention, a flame retardant resin composition having a low dielectric constant and dielectric loss tangent can be efficiently obtained by using the flame retardant (α).

In formula (1), R ^{1 to} R ⁴ each independently represents an unsubstituted or substituted aryl group, and X represents a divalent group having an arylene structure. a represents an integer of 2 or more.

Examples of the aryl group represented by R ^{1 to} R ⁴ include aryl groups having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, such as phenyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, and phenanthryl group. Groups.
Examples of these substituents include halogen atoms such as fluorine atom and chlorine atom; alkyl groups such as methyl group and ethyl group; alkoxy groups such as methoxy group and ethoxy group;

Examples of the divalent group having an arylene structure of X include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 2,6-naphthylene group, and biphenylene group. Bisphenol A residue, bisphenol D residue, bisphenol AD residue, bisphenol S residue and the like.
a represents an integer of 2 or more, and is preferably an integer of 2 to 30. When a is an integer of 2 or more, a resin composition in which bleeding out of the condensed phosphate ester flame retardant hardly occurs can be obtained.

  Among these, the flame retardant (α) is preferably a compound represented by the following formula (1a) or (1b).

In the formulas (1a) and (1b), a represents the same meaning as described above. R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , R ⁱ , R ^j , R ^k , and R ^l are each independently an alkyl group having 1 to 6 carbon atoms. Represents.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, sec-butyl group and the like.

^{-R a, -R b, -R e} , -R f, -R g, -R h, -R k, -R l ( hereinafter. To - sometimes referred to as ^{"R a} and the like") is a phenyl group It represents that any hydrogen atom therein may be substituted with an alkyl group having 1 to 6 carbon atoms. The number of -R ^a or the like contained in one of the phenyl groups is 0-5. If multiple -R ^a like one of the phenyl groups are present, to which may be the same or different from each other.

—R ^c , —R ^d , —R ⁱ , —R ^j (hereinafter sometimes referred to as “—R ^c, etc.”) is an arbitrary hydrogen atom in the phenylene group having 1 to 6 carbon atoms. It represents that it may be substituted. The number of —R ^{c and the} like contained in one phenylene group is 0-4. When a plurality of —R ^{c and the} like are present in one phenylene group, they may be the same or different from each other.

The melting point of the flame retardant (α) is preferably 150 ° C. or less, and more preferably 100 ° C. or less. When the melting point of the flame retardant (α) is 150 ° C. or less, the flame retardant (α) can be dispersed in the resin in a melted state when the flame retardant resin composition is kneaded.
The 5% weight loss temperature of the flame retardant (α) is preferably 300 ° C. or higher, and more preferably 350 ° C. or higher. Since the kneading of the cyclic olefin ring-opening polymer hydrogenated product and the additive is performed at a relatively high temperature, a flame retardant (α) having a high 5% weight loss temperature is preferably used.

  The amount of the flame retardant (α) contained in the flame retardant resin composition is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product. It is. When there is too little quantity of a flame retardant ((alpha)), there exists a possibility that the resin composition excellent in a flame retardance may not be obtained. On the other hand, when there is too much quantity of a flame retardant ((alpha)), a flame retardant ((alpha)) does not mix well with a cyclic olefin polymer hydrogenated product, and there exists a possibility that a resin composition may not be obtained.

[Organic phosphinate flame retardant]
The flame retardant resin composition of the present invention contains an organic phosphinate flame retardant [flame retardant (β)] represented by the following formula (2) or (3).
In the flame retardant resin composition of the present invention, the flame retardant (β) is used as a flame retardant, and at the same time, the compatibilization for compatibilizing the flame retardant (α) with the cyclic olefin ring-opening polymer hydrogenated product. Also used as an agent.
That is, the flame retardant (α) tends to be inferior in compatibility with the cyclic olefin ring-opening polymer hydrogenated product and in dispersibility in the cyclic olefin ring-opened polymer hydrogenated product, and is sufficient in the resin composition. There was a problem that the amount of flame retardant (α) could not be included, but this problem can be solved by making the flame retardant (β) coexist. As a result, a flame retardant resin composition having excellent flame retardancy and low dielectric constant and dielectric loss tangent can be obtained.

In formula (2), R ⁵ and R ⁶ each independently represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, and M ^{b +} represents a b-valent metal ion. , B is 1, 2 or 3.

In formula (3), R ⁷ and R ⁸ each independently represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, Y represents a divalent group, M ^{c +} represents a c-valent metal ion. c, d, and e are each independently 1, 2 or 3, and these satisfy the formula: c × d = 2 × e.

As an unsubstituted alkyl group of R ^{5 to} R ⁸ , carbon number 1 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, sec-butyl group, etc. -10, preferably an alkyl group having 1 to 6 carbon atoms.
The unsubstituted aryl group of R ^{5 to} R ⁸ has 6 to 20 carbon atoms such as phenyl group, tolyl group, xylyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, etc. Is an aryl group having 6 to 12 carbon atoms.
Examples of these substituents include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group;

Examples of M ^{b +} include monovalent metal ions such as sodium ion and potassium ion, divalent metal ions such as magnesium ion, calcium ion and zinc ion, and trivalent metal ions such as aluminum ion.
Examples of M ^{c +} include the same as those shown as M ^{b +} .

  Examples of the divalent group of Y include an alkylene group having 1 to 6 carbon atoms such as a methylene group, ethylene, and trimethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1, And a bivalent arylene group having 6 to 20 carbon atoms such as a 5-naphthylene group and a biphenylene group.

Among these, as the flame retardant (β), a compound represented by the formula (2) is preferable.
Examples of the compound represented by the formula (2) include bis (dimethylphosphinic acid) zinc, bis (diethylphosphinic acid) zinc, tris (dimethylphosphinic acid) aluminum, and tris (diethylphosphinic acid) aluminum.

The melting point of the flame retardant (β) is preferably 300 ° C. or higher, and more preferably 350 ° C. or higher. When the melting point of the flame retardant (β) is 300 ° C. or more, it becomes easy to disperse the flame retardant (β) in the resin in a solid state when the flame retardant resin composition is kneaded. When the flame retardant (β) is dispersed in the resin in a solid state, the effect as the compatibilizer is more exhibited.
The 5% weight loss temperature of the flame retardant (β) is preferably 300 ° C. or higher, and more preferably 350 ° C. or higher. Since the kneading of the cyclic olefin ring-opening polymer hydrogenated product and the additive is performed at a relatively high temperature, a flame retardant (β) having a high 5% weight loss temperature is preferably used.

  The amount of the flame retardant (β) contained in the flame retardant resin composition is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product. It is. When the amount of the flame retardant (β) is too small, the compatibility of the flame retardant (α) with the cyclic olefin ring-opening polymer hydrogenated product may not be improved. On the other hand, when the amount of the flame retardant (β) is too large, the dielectric loss tangent of the resin composition may be increased.

(Anti-drip agent)
The flame retardant resin composition of the present invention may contain an anti-drip agent.
An anti-drip agent is a compound that suppresses the drop (drip) of a droplet during combustion and increases the flame retardancy of a flame retardant resin composition when used in combination with a flame retardant (α) or a flame retardant (β). . Examples of the anti-drip agent include phenolic resins, silicone resins, and fluorine resins.
Among these, a fluororesin is preferable because it has a high anti-drip effect. Examples of fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropolypropylene) copolymer, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, and (tetrafluoroethylene / ethylene). Examples thereof include a copolymer, a (hexafluoropolypropylene / propylene) copolymer, a polyvinylidene fluoride, and a (vinylidene fluoride / ethylene) copolymer. Among these, polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer are preferable.
When the flame retardant resin composition of the present invention contains an anti-drip agent, the content of the anti-drip agent in the flame retardant resin composition is 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product, Usually 0.05 to 10 parts by weight, preferably 0.1 to 3 parts by weight.

[Other ingredients]
The flame retardant resin composition of the present invention may contain other known additives as long as the effects of the present invention are not hindered.
Such additives include fillers, antioxidants, mold release materials, flame retardants other than flame retardants (α) and flame retardants (β), antibacterial agents, coupling agents, plasticizers, colorants, lubricants, silicone oils, Foaming agent, surfactant, light stabilizer, dispersant, dispersion aid, heat stabilizer, UV absorber, antistatic agent, crystallization nucleating agent, antifogging agent, neutralizing agent, decomposing agent, metal deactivation Agent, antifouling material, thermoplastic elastomer, fibrous reinforcement (glass fiber, carbon fiber, synthetic fiber, ceramic fiber, whisker), plate reinforcement (mica, talc, clay, glass flake), granular reinforcement (metal) Oxide, carbonate, sulfate, glass beads, carbon black) and the like. These additives can be used alone or in combination of two or more.
The content of these additives is not particularly limited, and can be appropriately determined according to the purpose of addition within a range not impairing the effects of the present invention.

[Flame-retardant resin composition]
The method for producing the flame retardant resin composition of the present invention is not particularly limited, and a known method can be used. For example, the flame retardant resin composition of the present invention is mixed by mixing the hydrogenated cyclic olefin ring-opened polymer, the flame retardant (α), the flame retardant (β), and other additives blended as necessary. Can be obtained.
The mixing method is not particularly limited as long as each component is sufficiently mixed. Among these, when a crystalline cyclic olefin ring-opening polymer hydrogenated product is used, a sufficiently mixed flame-retardant resin composition is easily obtained, and therefore a method of kneading in a molten state is preferable.

When knead | mixing in a molten state, it is preferable to knead | mix at the temperature of the range of glass transition temperature +50 degreeC of a cyclic olefin ring-opening polymer hydrogenated product + glass transition temperature +150 degreeC. If the temperature is too low, the viscosity becomes high and kneading is difficult, and if the temperature is too high, the cyclic olefin ring-opening polymer hydrogenated product and other components tend to deteriorate.
After kneading, pellets of the flame retardant resin composition can be obtained by extruding into a rod shape in a molten state and cutting into an appropriate length with a strand cutter.

  The flame retardant resin composition of the present invention is excellent in flame retardancy. The flame retardant resin composition of the present invention is preferably V-2 grade or higher when a flammability test is performed based on UL94.

  The flame retardant resin composition of the present invention has a low dielectric constant and dielectric loss tangent. The flame retardant resin composition of the present invention preferably has a dielectric constant of less than 2.5 and a dielectric loss tangent of less than 0.002 when measured by the method described in the Examples.

2) Resin molded body The resin molded body of the present invention is formed by molding the flame retardant resin composition of the present invention.
The molding method is not particularly limited, and a known molding method such as an injection molding method, a compression molding method, or an extrusion molding method can be used.

  The resin molded product of the present invention is not particularly limited, but can fully utilize the characteristics of the flame retardant resin composition of the present invention, so that it can be applied to a power cable covering material (plastic insulated wire, power cable, city / outside) Cables, intra-office cables, broadband cables, high-frequency coaxial cables, high-frequency coaxial (tube) feeders and elliptical waveguides, communication wires and cables, etc.); general circuit boards (hard printed boards, flexible printed boards, multilayer printed wiring boards) Etc.); High-frequency circuit boards (circuit board for satellite communication equipment, etc.); Automotive exterior members (bonnets, trunk doors, doors, fenders, grills, etc.); Engine members such as air intakes and engine covers; Head lamp housings, rear lamps Vehicle lamp members such as housings, reflectors and extension reflectors; instrument panels, seat housings, etc. Vehicle interior parts; automotive parts such as automobile motor cases, sensor cases, module parts cases, fuel cell stack separators; bicycle parts such as power assist battery members; power assists, industrial robots, electric wheelchair members, etc. Robot parts housing; aircraft interior members; hull members; home appliances such as TVs, refrigerators, air conditioners, electric fans, humidifiers, dehumidifiers, drying washing machines, dishwashers, microwave ovens, rice cookers, electronic jar pots, dryers, etc. Parts: PCs, printers, copiers, telephones, fax machines, audio equipment, cameras, game machines, hard disk drives, mobile phones, smartphones and other electronic products; connectors, relays, capacitors, sensors, antennas, IC trays, chassis Coil sealing, motor case, Electronic components such as source boxes; backlight light source lighting equipment for liquid crystal displays of large liquid crystal display devices; backlight light source lighting equipment for liquid crystal displays of small electronic devices such as mobile phones, smartphones and tablets; road traffic display boards, etc. LED reflectors used as light sources for electric display boards; optical lens barrels; release films for laminated printed wiring boards; solar cell substrates; packaging and packaging films; LED molding materials; pump casings, impellers, piping joints Housing parts such as bathtubs, septic tanks, bathroom panels, exterior panels, window sash rails, window insulation, wash bowls, etc .; industrial products such as infusion containers, chemical layers, chemical piping, gas piping, containers, pallets, rack columns It can be used as a member.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The measurement in each example was performed by the following method.

[Glass transition temperature and melting point]
Using a differential scanning calorimeter (DSC), differential scanning calorimetry was carried out at a temperature rising rate of 10 ° C./min, and the glass transition temperature and melting point of the polymer were measured.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
Gel permeation chromatography (GPC) was performed at 40 ° C. using tetrahydrofuran as a solvent, and the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined as polystyrene equivalent values.
Measuring apparatus: Gel permeation chromatography (GPC) system “HLC-8220” (manufactured by Tosoh Corporation)
Column: “H type column” (manufactured by Tosoh Corporation)

[Hydrogenation rate of unsaturated bond]
^{Based on the 1} H-NMR measurement, the hydrogenation rate of the unsaturated bond in the polymer was determined.

〔Additive〕
The flame retardant used is as follows.
Condensed phosphate ester flame retardant (B1): ADEKA, trade name: FP-800, melting point 65-85 ° C., compound represented by the following formula (5)

Condensed phosphate ester flame retardant (B2): manufactured by ADEKA, trade name: FP-600, liquid at 25 ° C., compound represented by the following formula (6)

Condensed phosphate ester flame retardant (B3): manufactured by Daihachi Chemical Industry Co., Ltd., trade name: PX-200, melting point 95 ° C., compound represented by the following formula (7)

Organic phosphinate flame retardant (C1): manufactured by Clariant Co., Ltd., trade name: Exolit OP 935, melting point over 300 ° C., compound represented by the following formula (8)

メラミン系難燃剤（Ｄ１）：ＢＡＳＦ社製、商品名：ＭＥＬＡＰＵＲ２００／７０、融点４００℃超、下記式（９）で示される化合物

Melamine flame retardant (D1): manufactured by BASF, trade name: MELAPUR 200/70, melting point over 400 ° C., compound represented by the following formula (9)

[Production Example 1] [Synthesis of hydrogenated dicyclopentadiene ring-opening polymer]
In a metal pressure-resistant reaction vessel purged with nitrogen inside, 154.5 parts of cyclohexane, 42.8 parts of cyclohexane solution (concentration 70%) of dicyclopentadiene (end content 99% or more) (30 parts as dicyclopentadiene) 1-hexene 1.9 parts was added and the whole was heated to 53 ° C.
On the other hand, in a solution obtained by dissolving 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene, 0.061 part of n-hexane solution of diethylaluminum ethoxide (concentration 19%). And stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was added to the reactor and a ring-opening polymerization reaction was performed at 53 ° C. for 4 hours to obtain a solution containing a dicyclopentadiene ring-opening polymer.

To 200 parts of the solution containing the obtained dicyclopentadiene ring-opened polymer, 0.037 part of 1,2-ethanediol was added as a terminator and stirred at 60 ° C. for 1 hour to stop the polymerization reaction. Thereafter, 1 part of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts of filter aid (product name “Radiolite (registered trademark) # 1500” manufactured by Showa Chemical Industry Co., Ltd.) is added, and PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo Co., Ltd.) is used. The adsorbent was filtered off to obtain a solution containing a dicyclopentadiene ring-opening polymer.
A part of this solution was used to measure the molecular weight of the dicyclopentadiene ring-opened polymer. The weight average molecular weight (Mw) was 28,100, the number average molecular weight (Mn) was 8,750, the molecular weight distribution (Mw / Mn) was 3.21.

100 parts cyclohexane and 0.0043 parts chlorohydridocarbonyltris (triphenylphosphine) ruthenium are added to 200 parts solution (polymer content 30 parts) containing dicyclopentadiene ring-opening polymer after purification treatment, and hydrogen Hydrogenation reaction was performed at 6 MPa and 180 ° C. for 4 hours. The reaction liquid was a slurry liquid in which a solid content was deposited.
The reaction solution is centrifuged to separate the solid and the solution, and the solid is dried under reduced pressure at 60 ° C. for 24 hours to obtain 28.5 parts of a dicyclopentadiene ring-opening polymer hydrogenated product (A1). It was.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product (A1) was 99% or more, the glass transition temperature was 98 ° C., and the melting point was 262 ° C.

[Example 1]
100 parts of dicyclopentadiene ring-opening polymer hydrogenated product (A1) obtained in Production Example 1, 10 parts of condensed phosphate ester flame retardant (B1), 10 parts of organic phosphinate flame retardant (C1) After kneading with a twin-screw kneading extruder (Technobel KZW15-30MG) to obtain a strand (rod-like molten resin), this was cut with a strand cutter to obtain a pellet-like (granular) resin composition. .
The operating conditions of the small twin-screw kneader are shown below.
・ Barrel set temperature: 270-290 ° C
・ Screw rotation speed: 90-100rpm
・ Screw diameter: 15mm
・ L / D: 40

  Next, the pellet-shaped resin composition obtained by the above method was filled in a mold having a predetermined shape subjected to a release treatment, and then hot-pressed at a temperature of 280 ° C. and a pressure of 3 MPa to obtain a thickness of 1. A 5 mm resin molded body was obtained.

[Example 2]
A resin molded body was obtained in the same manner as in Example 1 except that 20 parts of the organic phosphinate flame retardant (C1) was used.

Example 3
A resin molded body was obtained in the same manner as in Example 1 except that 20 parts of the condensed phosphate ester flame retardant (B1) was used.

Example 4
A resin molded body was obtained in the same manner as in Example 1 except that 10 parts of the condensed phosphate ester flame retardant (B2) was used instead of the condensed phosphate ester flame retardant (B1).

[Comparative Example 1]
A resin molded body was obtained in the same manner as in Example 1 except that only 100 parts of dicyclopentadiene ring-opening polymer hydrogenated product (A1) was used without adding a flame retardant.

[Comparative Example 2]
A resin molded body was obtained in the same manner as in Example 1 except that the organic phosphinate flame retardant (C1) was not added.

[Comparative Example 3]
Biaxial kneading was performed in the same manner as in Example 1 except that 20 parts of the condensed phosphate ester flame retardant (B1) was added and the organic phosphinate flame retardant (C1) was not added. Since the flame retardant and the resin were separated, a pellet-like (granular) resin composition could not be obtained.

[Comparative Example 4]
A resin molded body was obtained in the same manner as in Example 1 except that the condensed phosphate ester flame retardant (B1) was not added and 30 parts of the organic phosphinate flame retardant (C1) was added.

[Comparative Example 5]
A resin molded body was obtained in the same manner as in Example 1, except that 10 parts of the melamine flame retardant (D1) was used instead of the organic phosphinate flame retardant (C1).

[Comparative Example 6]
A resin molded body was obtained in the same manner as in Example 1 except that 10 parts of the condensed phosphate ester flame retardant (B3) was used instead of the condensed phosphate ester flame retardant (B1).

  About the resin molding obtained in each example, the following methods evaluated the bleedout of a flame retardant, a flame retardance, a dielectric constant, and a dielectric loss tangent. These results are shown in Table 1.

[Bleed out of flame retardant]
The resin molded body having a thickness of 1.5 mm obtained in Examples and Comparative Examples was cut into a square having a side of 100 mm with a hot cutter, and this was used as a test piece. The test piece was left in an oven at 150 ° C. for 12 hours, and then cooled to room temperature. Appearance observation and tactile sensation evaluation were performed on this test piece, and the presence or absence of a flame retardant bleed out was examined.

〔Flame retardance〕
The resin molded bodies having a thickness of 1.5 mm obtained in Examples and Comparative Examples were cut into strips having a width of 13 mm and a length of 125 mm using a hot cutter, and this was used as a test piece. The test piece was fixed vertically with a clamp, and cotton was placed under it. After the flame of the burner was indirect flame for 10 seconds at the lower end of the test piece, the flame was removed, and the time until the fire that ignited the test piece disappeared was measured. Next, at the same time when the fire was extinguished, the second flame contact was performed for 10 seconds, and the time until the fire was ignited was measured in the same manner as the first time. In addition, it was also evaluated whether or not the cotton placed under the test piece ignites due to the fire type falling during combustion.
The combustion rank was given according to UL-94V specification from the 1st and 2nd combustion time, the presence or absence of cotton ignition, etc. The flame rank increases in the order of non-standard, V-2, V-1, and V-0.

[Dielectric constant / dielectric loss tangent]
The resin molded body having a thickness of 1.5 mm obtained in the examples and comparative examples was cut into a square having a side of 50 mm with a hot cutter, and this was used as a test piece. About this test piece, the dielectric constant and dielectric loss tangent of a 10-70 GHz band were measured with the balanced disk resonator method using the vector network analyzer (PNA made from Agilent Technologies), and the following reference | standard evaluated.
Dielectric constant ◯: Less than 2.5 at all measurement points x: Measurement points of 2.5 or more exist.
Dielectric loss tangent ◯: Less than 0.002 at all measurement points x: Measurement points of 0.002 or more exist.

The following can be seen from Table 1.
The resin compositions obtained in Examples 1 to 4 have an evaluation in a flammability test based on UL94 of V-2, and are excellent in flame retardancy. In addition, these resin compositions all have low dielectric constant and dielectric loss tangent, and are excellent in electrical characteristics.
On the other hand, Comparative Example 1 is a result of the hydrogenated dicyclopentadiene ring-opening polymer alone, and it can be seen that this polymer has insufficient flame retardancy.
Moreover, when an organic phosphinate flame retardant is not used, a resin composition inferior in flame retardancy can be obtained (Comparative Example 2), or the condensed phosphate ester flame retardant is separated during kneading, and the desired resin composition No product is obtained (Comparative Example 3).
The resin composition obtained in Comparative Example 4 contains only an organic phosphinate flame retardant as a flame retardant. This resin composition is inferior in flame retardancy and has a high dielectric loss tangent.
The resin composition obtained in Comparative Example 5 contains a melamine flame retardant which is a similar high melting point flame retardant instead of the organic phosphinate flame retardant. This resin composition has a high dielectric constant and dielectric loss tangent, and is inferior in electrical characteristics.
The resin composition obtained in Comparative Example 6 contains a compound having a low molecular weight as a condensed phosphate ester flame retardant. In this resin composition, a bleedout phenomenon of the flame retardant is observed.

Claims (6)

A flame retardant resin composition containing a cyclic olefin ring-opening polymer hydrogenated product, a condensed phosphate ester flame retardant, and an organic phosphinate salt flame retardant,
The condensed phosphate ester flame retardant is represented by the following formula (1):

(Wherein R ^{1 to} R ⁴ each independently represents an unsubstituted or substituted aryl group, X represents a divalent group having an arylene structure, and a is an integer of 2 or more. )
A compound represented by
The organic phosphinate flame retardant is represented by the following formula (2)

(Wherein R ⁵ and R ⁶ each independently represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, M ^{b +} represents a b-valent metal ion, b Is 1, 2 or 3.)
Or the following formula (3)

(Wherein R ⁷ and R ⁸ each independently represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group, Y represents a divalent group, and M ^{c +} represents C, d and e are independently 1, 2 or 3, which satisfy the formula: c × d = 2 × e.)
The flame retardant resin composition characterized by being the compound shown by these.   The flame-retardant resin composition according to claim 1, wherein the condensed phosphate ester flame retardant has a melting point of 150 ° C or lower.   The flame-retardant resin composition according to claim 1 or 2, wherein the content of the condensed phosphate ester flame retardant is 1 to 30 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product. object.   The flame-retardant resin composition according to claim 1, wherein the organic phosphinate flame retardant has a melting point of 300 ° C. or higher.   The flame retardant according to any one of claims 1 to 4, wherein the content of the organic phosphinate flame retardant is 1 to 30 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydrogenated product. Resin composition.   The resin molding formed by shape | molding the flame-retardant resin composition in any one of Claims 1-5.