JP2006328174A - Cyclic olefin resin composition and its molded item - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic olefin resin composition that retains desirable transparency, heat resistance and mechanical properties inherent in a specific cyclic olefin addition (co)polymer and exhibits excellent flame retardancy by compounding the cyclic olefin addition (co)polymer and a specific flame-retardant into a composite. <P>SOLUTION: The cyclic olefin resin composition comprises 100 pts.wt. of the cyclic olefin addition (co)polymer [I] obtained by addition polymerization of a monomer containing the specific cyclic olefin compound and 2-40 pts.wt. of the specific condensed phosphate ester compound [II]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cyclic olefin resin composition. More specifically, in the present invention, the preferable transparency, heat resistance and mechanical properties inherent to the cyclic olefin addition polymer are maintained by combining a specific cyclic olefin addition polymer and a specific flame retardant. Further, the present invention relates to a cyclic olefin resin composition having excellent flame retardancy.

In recent years, cyclic olefin addition polymers are excellent in transparency, heat resistance, and the like, and therefore are increasingly used as materials for electrical and electronic parts including optical materials.
However, since the cyclic olefin addition polymer is easily combusted, its use as a sealing material, protective film material, insulating material, etc. for electric / electronic parts has been restricted from the viewpoint of safety.

  In order to impart flame retardancy to this cyclic olefin addition polymer, a resin composition in which a cyclic olefin addition polymer and one or more flame retardants are combined and combined has been proposed.

  For example, halogen flame retardants such as halogen flame retardants, antimony flame retardants, magnesium hydroxide (see Patent Document 1), ammonium polyphosphate (see Patent Document 2), halogenated epoxy resin flame retardants, phosphate ester series There has been proposed a resin composition combined with a flame retardant, an antimony oxide-based flame retardant (see Patent Document 3), and the like.

However, the above-described composition has a problem that flame retardancy is improved, but properties such as preferable transparency inherent in the cyclic olefin addition polymer are impaired.
In addition, due to increased concern about environmental problems and safety to the human body, there has also been a problem that the use of halogen-based and antimony-based flame retardants that generate harmful gases during the combustion of the resin composition is not preferred.
JP-A-2-255848 JP-A-5-239284 JP-A-11-106597

  The object of the present invention is to solve the problems associated with the prior art as described above, and this cyclic olefin addition (co) polymer and a specific flame retardant are combined to form this cyclic compound. An object of the present invention is to provide a cyclic olefin-based resin composition excellent in flame retardancy while maintaining preferable transparency, heat resistance and mechanical properties inherent to an olefin addition (co) polymer.

As a result of earnest research to solve the above problems, the present inventors,
Transparency and heat resistance by compounding a cyclic olefin addition (co) polymer having a structural unit derived from a specific cyclic olefin compound and a condensed phosphate ester compound having a specific structure at a specific ratio In addition, the inventors have found that a cyclic olefin-based resin composition having excellent mechanical properties and excellent flame retardancy can be obtained, and has completed the present invention.

That is, the cyclic olefin-based resin composition according to the present invention is
Cyclic olefin addition (co) polymer [I] having a structural unit represented by the following general formula (1)
100 parts by weight,
It contains 2 to 40 parts by weight of a condensed phosphate ester compound [II] represented by the following general formula (2).

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, further a ¹ and a ² as in the alkylidene group having 1 to 15 carbon atoms, alicyclic structure, cyclic aromatic structure, cyclic May form an acid anhydride group or a cyclic imido group, an alicyclic structure having 1 to 15 carbon atoms formed by the A ¹ and A ^3, aromatic cyclic structure, cyclic anhydride groups, or (A cyclic imide group may be formed, and m represents an integer of 0 or 1.)

(In the formula ^{(2), R 1, R} 2, R 4 ~R 6 each independently represent an aryl group having 5 to 20 carbon atoms, R ³ represents an arylene group having 6 to 25 carbon atoms, n Represents an integer of 0 to 3.)
The cyclic olefin addition (co) polymer [I] is a bicyclo [2.2.1] hepta-2-
Preferably, the structural unit derived from ene contains 40 mol% or more of all structural units, or
In the formula (1), at least one of A ^{1 to} A ⁴ is selected from the group consisting of hydrolyzable silyl group, alkoxycarbonyl group, oxetanyl group, carbonimide group, carbonate group, glycidyl group and acid anhydride group. It is preferable that 1 mol%-20 mol% of the structural unit which is a substituent to be included is included in all the structural units.

The glass transition temperature of the cyclic olefin addition (co) polymer [I] is 200 ° C to 400 ° C.
It is preferable to be within the range.
The condensed phosphate ester compound [II] is preferably represented by the following general formula (3).

(In the formula (3), A ⁵ to A ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
The cyclic olefin-based resin composition is preferably capable of forming a film having a film thickness of 100 μm and a light transmittance (ASTM-D1003) with respect to light having a wavelength of 500 nm of 80% or more.

  The molded body of the present invention is characterized by comprising the above cyclic olefin-based resin composition, and the molded body is particularly preferably a film or a sheet.

The cyclic olefin-based resin composition according to the present invention is excellent in transparency, heat resistance and mechanical properties, and is excellent in flame retardancy.
Therefore, a molded body such as a film formed from the cyclic olefin-based resin composition according to the present invention is useful as a material for electrical and electronic parts including optical materials.

Hereinafter, the cyclic olefin resin composition of the present invention will be described in detail.
The cyclic olefin resin composition of the present invention contains a cyclic olefin addition (co) polymer [I] and a condensed phosphate ester compound [II].
<Cyclic olefin addition (co) polymer [I]>
The cyclic olefin addition (co) polymer [I] used in the present invention can be obtained by addition polymerization of a monomer containing a cyclic olefin compound represented by the following general formula (4). The structural unit represented by the above formula (1) is formed by addition polymerization of the cyclic olefin compound.

(In formula (4), A ^{1 to} A ⁴ and m are as defined in the above formula (1).)
In the present invention, the cyclic olefin addition (co) polymer is a homopolymer of one kind of cyclic olefin compound, a copolymer of two or more kinds of cyclic olefin compounds, or at least one kind of cyclic olefin compound. It represents a copolymer with a monomer other than the cyclic olefin compound.

Specific examples of the monomer of the cyclic olefin compound represented by the above formula (4) include the following compounds, but the present invention is not limited to these specific examples.
As a monomer having no polar group and no functional group as a substituent, for example,
Bicyclo [2.2.1] hept-2-ene,
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5- (1-butenyl) bicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-ene,
5-octylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-dodecylbicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-vinylbicyclo [2.2.1] hept-2-ene,
5-allylbicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5- (ethylphenyl) bicyclo [2.2.1] hept-2-ene,
5,6-benzobicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenylbicyclo [2.2.1] hept-2-ene,
5-benzylbicyclo [2.2.1] hept-2-ene,
5,6-dimethylbicyclo [2.2.1] hept-2-ene,
5-methyl-6-ethylbicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
3,4-benzotricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
4,5-benzotricyclo [6.2.1.0 ^2,7 ] nonadeca-9-ene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-4-ene and the like.

As a monomer having an alkoxycarbonyl group as a substituent, for example,
Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
Methyl bicyclo [2.2.1] hept-5-ene-2-methylcarboxylate-2-methyl carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] ethyl dodeca-9-ene-4-carboxylate.

As a monomer having a trialkylsiloxycarbonyl group or a dialkylaluminoxycarbonyl group as a substituent, for example,
Triethylsilyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Dicyclobutyl [2.2.1] hept-5-ene-2-carboxylate,
Bicyclo [2.2.1] hept-5-ene-2-carboxylate diisobutylaluminum, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate triethylsilyl,
Tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodeca-9-ene-4-carboxylate diisobutylaluminum.

As a monomer having an acid anhydride group as a substituent, for example,
Bicyclo [2.2.1] hept-5-ene-2,3-carboxylic anhydride,
Bicyclo [2.2.1] hept-5-ene-2-spiro-3'-exo-succinic anhydride,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4,5-carboxylic anhydride.

As a monomer having a carbonimido group as a substituent, for example,
Bicyclo [2.2.1] hept-5-ene-N-cyclohexyl-2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-N-phenyl-2,3-carbonimide,
Bicyclo [2.2.1] hept-5-ene-2-spiro-N-cyclohexyl-succinimide,
Bicyclo [2.2.1] hept-5-ene-2-spiro-N-phenyl-succinimide and the like.

As a monomer having an oxetanyl group as a substituent, for example,
5-[(3-ethyl-3-octacenyl) methoxy] bicyclo [2.2.1] hept-2-ene,
5-[(3-oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene,
And bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl.

As a monomer having a hydrolyzable alkoxysilyl group as a substituent, for example,
5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilylbicyclo [2.2.1] hept-2-ene,
9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-triethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-cyclohexyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-phenyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dimethylmethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-trichlorosilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dichloromethylsilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethylsilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chlorodimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dichloromethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-chloromethylmethoxysilyltetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-4-ene and the like.

As a monomer having a hydrolyzable silacycloalkyl group in the side chain substituent, for example, 5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2 .1] hept-2-ene,
5- [1′-methyl-2 ′, 5′-dioxa-3 ′, 4′-dimethyl-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 5′-dioxa-3′-methyl-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-4 ′, 4′-dimethyl-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
9- [1′-Methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-4-ene and the like.

Among these, as a monomer having no functional group and polar group as a substituent, bicyclo [2.2.1] hept-2-ene or 5-butylbicyclo [2.2.1] hepta-2 is used. -Ene can be preferably used, and a monomer having a polar group as a substituent includes 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene or 4-methyltetracyclo [6]. 2.1.1 ^3,6 . ^0,7 ] methyl dodeca-9-ene-4-carboxylate can be preferably used.

The said monomer may be used individually by 1 type, or may be used in combination of 2 or more type.
As monomers other than the above cyclic olefin compounds, α-olefin compounds such as ethene, prop-1-ene, but-1-ene, hexa-1-ene, octa-1-ene; styrene, methyl acrylate, N- Compounds such as alkylmaleimide and N-arylmaleimide can be used.

The cyclic olefin addition (co) polymer [I] is a bicyclo [2.2.1] hepta-2-
It is preferable to have a structural unit derived from ene. The above cyclic olefin addition (co) polymer [I
However, by having such a structural unit, a polymer having excellent rigidity can be obtained, and compatibility between the cyclic olefin addition (co) polymer [I] and the condensed phosphate compound [II] can be improved. improves. Moreover, the composition excellent in transparency and a flame retardance can be obtained.

However, bicyclo [2.2] in the above cyclic olefin addition (co) polymer [I].
. 1] If the content of hepta-2-ene is too high, the solubility of the addition (co) polymer [I] in various solvents may decrease.

In order to improve the solubility of the cyclic olefin addition (co) polymer [I] in various solvents,
The addition (co) polymer [I] has a structural unit derived from bicyclo [2.2.1] hept-2-ene and 5-butylbicyclo [2.2.1] hept-2-ene or 4- Methyltetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] more preferably having a structural unit derived from methyl dodeca-9-ene-4-carboxylate.

Furthermore, the cyclic olefin addition (co) polymer [I] has a structural unit derived from bicyclo [2.2.1] hept-2-ene in a total structural unit of 40 mol% or more, more preferably 40 mol% to 95 mol%. , More preferably 50 mol% to 90 mol%, and 5-butylbicyclo [2.2.1] hept-2-ene or 4-methyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] methyl dodeca-9-ene-4-carboxylate is derived from 45 mol% or less, more preferably 5 mol% to 40 mol%, and even more preferably 10 mol% to 30 mol% of all structural units. Thus, it is desirable to use the above monomer. Thereby, a composition excellent in the balance between solubility in various solvents and rigidity can be obtained.

The cyclic olefin addition (co) polymer [I] has a hydrolyzable silyl group, alkoxycarbonyl group, oxetanyl group, carbonimide group, at least one of A ^{1 to} A ⁴ in the formula (1), 1 mol% to 20 mol%, more preferably 2 mol% to 15 mol%, more preferably 3 mol% to 10 mol% of a structural unit having a substituent selected from the group consisting of a carbonate group, a glycidyl group and an acid anhydride group. Thus, it is desirable to use a monomer having these polar substituents. When the cyclic olefin addition (co) polymer [I] has such a structural unit, the compatibility between the cyclic olefin addition (co) polymer [I] and the condensed phosphate ester compound [II] is improved. improves. Moreover, the composition excellent in transparency and a flame retardance can be obtained.

Examples of the catalyst that can be used for the addition (co) polymerization include nickel-based catalysts, palladium-based catalysts, cobalt-based catalysts, titanium-based catalysts, zirconium-based catalysts, and the like.
Nickel-based catalyst:
Ni (octoate) ₂ / (Ph) ₃ C · B (C ₆ F ₅ ) ₄ / Et ₃ Al
Ni (acetylacetonate) ₂ / MAO,
Ni (octoate) ₂ -HSbF ₆ / BF ₃ .Et ₂ O / Et ₃ Al,
Palladium catalyst:
[Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ ,
Pd (acetate) ₂ / PCy ₃ / (Ph) ₃ C · B (C ₆ F ₅ ) ₄ ,
Pd (octoate) ₂ / PCy ₃ / (Ph) ₃ C · B (C ₆ F ₅ ) ₄ ,
Pd (octoate) ₂ / PPh ₃ / (Ph) ₃ C · B (C ₆ F ₅ ) ₄ / Et ₃ Al,
(η ³ -allyl) Pd (triflate) (P (o-tolyl) ₃ ) / Li [B (C ₆ F ₅ ) ₄ ],
Cobalt catalyst:
Co (dodecanoate) ₂ / MAO,
Titanium catalyst:
(T-BuNSiMe ₂ Flu) TiMe ₂ / (Ph) ₃ C · B (C ₆ F ₅ ) ₄ / i-Bu ₃ Al,
Me ₅ CpTiCl ₃ / MAO,
Zirconium-based catalyst:
Et (Ind) ₂ ZrCl ₂ / MAO,
Me ₂ Si (Ind) ₂ ZrCl ₂ / MAO,
Ph ₂ C (Cp) (Flu) ZrCl ₂ / MAO,
(1,3-Me ₂ Cp) Zr (S ₂ CNMe ₂ ) ₃ / MAO
(Ph: phenyl, MAO: methylaluminoxane, Cy: cyclohexyl, Ind: indenyl, Flu: fluorenyl, Cp: cyclopentadienyl, respectively).

Examples of the solvent that can be used for the addition (co) polymerization include hydrocarbon solvents and halogenated hydrocarbon solvents.
A copolymer of the monomer of the cyclic olefin compound represented by the formula (4) and the α-olefin compound can be polymerized using a titanium catalyst, a zirconium catalyst, or the like. The copolymer of the cyclic olefin compound and styrene can be polymerized using a nickel-based catalyst, and the copolymer of the cyclic olefin and methyl acrylate can be polymerized using a palladium-based catalyst. it can.

Glass transition temperature (Tg) of cyclic olefin addition (co) polymer [I] used in the present invention
Is usually 150 ° C. to 450 ° C., but in order to have high heat resistance, it is preferably 200 ° C. to 400 ° C., more preferably 230 ° C. to 380 ° C. If the glass transition temperature is lower than the above range, there may be a problem in terms of heat resistance. On the other hand, if it exceeds the above range, the toughness of the addition (co) polymer tends to decrease.

The molecular weight of the cyclic olefin addition (co) polymer [I] used in the present invention is measured by gel permeation chromatography (GPC) method, and the polystyrene-equivalent number average molecular weight (Mn) is 10,000 to 200. It is desirable that the weight average molecular weight (Mw) is 30,000 to 500,000, preferably 100,000 to 300,000. When Mn and Mw are lower than the above ranges, the mechanical strength and elongation are small, and the film or sheet tends to be easily broken. On the other hand, when the above range is exceeded, the solution viscosity of the polymer becomes too high, so that it tends to be difficult to handle when producing a film or sheet by the solution casting method (casting method).

<Condensed Phosphate Ester Compound [II]>
The condensed phosphate ester compound [II] used in the present invention is represented by the above formula (2). The condensed phosphate ester compound [II] having such a structure is preferable because it has a high compatibility with the cyclic olefin addition (co) polymer [I] and a composition having excellent transparency can be obtained.

Specific examples of the condensed phosphate ester compound [II] represented by the above formula (2) include the following compounds, but the present invention is not limited to these specific examples.
1,3-bis (phenylphosphoryl) benzene 1,3-bis (diphenylphosphoryl) benzene,
1,3-bis [di (alkylphenyl) phosphoryl] benzene,
1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene,
1,3-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene,
1,3-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] benzene,
1,3-bis [di (2 ′, 6′-dibutylphenyl) phosphoryl] benzene,
1,3-bis [di (2′-t-butylphenyl) phosphoryl] benzene,
1,3-bis [di (2′-isopropylphenyl) phosphoryl] benzene 1,3-bis [di (2′-methylphenyl) phosphoryl] benzene,
1,4-bis (diphenylphosphoryl) benzene,
1,4-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene,
1,4-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene,
1,4-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] benzene,
1,4-bis [di (2′-t-butylphenyl) phosphoryl] benzene,
1,4-bis [di (2′-isopropylphenyl) phosphoryl] benzene,
1,4-bis [di (2′-methylphenyl) phosphoryl] benzene,
4,4′-bis [di (2 ″, 6 ″ -dimethylphenyl) phosphorylphenyl] dimethylmethane and the like.

Among these, the condensed phosphate ester compound [II] represented by the above formula (3) is highly compatible with the cyclic olefin addition (co) polymer [I] and has excellent transparency. It is more preferable because heat resistance and mechanical properties are hardly lowered.

  Specific examples include 1,3-bis (phenylphosphoryl) benzene and 1,3-bis [di (alkylphenyl) phosphoryl] benzene. In addition, since it is widely used industrially, 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene, also known as resorcinol bis (dixylenyl phosphate), and 1,3-bis [Di (2 ′, 6′-dibutylphenyl) phosphoryl] benzene is particularly preferred.

<Cyclic olefin resin composition>
The cyclic olefin resin composition of the present invention comprises a cyclic olefin addition (co) polymer [I] 10.
It contains 2 to 40 parts by weight, preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight of the condensed phosphate ester compound [II] as a flame retardant with respect to 0 part by weight. desirable. If the amount of the condensed phosphate ester compound [II] is lower than the above range, sufficient flame retardancy tends not to be obtained. On the other hand, if the amount exceeds the above range, there is a problem in transparency. There is also a tendency for the mechanical properties to be greatly reduced.

When the cyclic olefin resin composition of the present invention is a film having a film thickness of about 100 μm, the total light transmittance measured in accordance with ASTM-D1003 is 80% or more, more preferably 85% or more. preferable. When the total light transmittance is less than 80%, there is a tendency that light loss is large and desired characteristics cannot be exhibited.

<Other ingredients>
Other flame retardants can be added to the above resin composition as needed within a range that does not impair various properties such as transparency of the above cyclic olefin resin composition. Examples of the other flame retardant include aluminum hydroxide, magnesium hydroxide, and 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10 represented by the following formula (5). -Phosphaphenanthrene-10-oxide etc. are mentioned.

For 100 parts by weight of the above cyclic olefin addition (co) polymer [I], phenolic,
By adding 0.01 to 5 parts by weight of an antioxidant such as a lactone, phosphorus or thioether, the heat deterioration resistance can be further improved.

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methyl-phenyl), and 1,1-bis. (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3-3,5-di-tert-butyl-4-hydroxyphenyl] propionate] methane 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-t-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di- (t-butyl-4-hydroxyphenyl)] propionate, phenolic antioxidants, hydroquinone antioxidants, bis- (2
, 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl phosphite, tetrakis (2,4-di-t-butyl-5-methyl) Phenyl) 4,4′-biphenylenediphosphonite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phos Phosphorous secondary antioxidants such as phyto, tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, dilauryl-3,3′-thiodipropionate, 2-mercaptobenz And sulfur-based secondary antioxidants such as imidazole.

  Further, for the cyclic olefin-based resin composition of the present invention, within the range not impairing the object of the present invention, for example, ultraviolet absorbers such as resorcinol, benzotriazole, benzophenone, lubricants, mold release materials, antistatic agents, etc. One or more usual additives can be added.

<Molded body>
The molded body formed from the cyclic olefin resin composition of the present invention is used as various materials.

  The shape of the molded body is not particularly limited, and examples thereof include films, sheets, thin films, and laminates. Among these, a film or a sheet is more preferable.

  The method for molding the resin composition is not particularly limited, and a solution casting method (casting method), an extrusion molding method, a compression molding method, an injection molding method, and the like can be used. In the solution casting method, a resin composition is dissolved in a solvent to prepare a solution of the composition, and then the solution is applied to a support, and then the solvent is dried to obtain a film or sheet. This is a method for obtaining a molded body. Among these, the solution casting method is preferable in that the deterioration of the polymer due to the thermal history can be suppressed.

As the solvent used in the solution casting method, the above resin composition containing the cyclic olefin addition (co) polymer [I] and the condensed phosphate ester [II] can be dissolved uniformly and transparently. It is preferable to use it. Thereby, the molded object excellent in transparency and mechanical characteristics can be obtained.

<Application>
The cyclic olefin-based resin composition of the present invention makes use of excellent transparency, heat resistance, mechanical properties and flame retardancy, sealing materials for electrical and electronic parts including optical materials, protective film materials, insulating materials It is useful as such.

Examples of the optical material include a light guide plate, a protective film, an adhesive film, a touch panel, a transparent electrode substrate, a TFT substrate, and a color filter substrate.
Examples of the electrical / electronic components include copper-clad laminates for printed wiring boards, interlayer insulation films for build-up multilayer wiring layers for high-density mounting boards, insulating materials for semiconductor package boards, and transfer molding materials for semiconductor parts. Examples thereof include a material, an underfill sealing material, a buffer coat film, a passivation film, and a solder resist protective film.

Examples of the insulating material include a coating material for electric wires and cables, and an insulating material for office automation equipment such as a computer, a printer, and a copying machine.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, molecular weight (Mn, Mw) of cyclic olefin addition (co) polymer, glass transition temperature (Tg), composition analysis in copolymer, residual solvent amount of cyclic olefin-based resin composition, total light transmittance, Flame retardancy, breaking strength and breaking elongation were measured by the following methods.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw)
Using a 150C type gel permeation chromatography (GPC) apparatus manufactured by Waters (WATERS), an H-type column manufactured by Tosoh Corporation was used and measured at 120 ° C. using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.

(2) Glass transition temperature (Tg)
The glass transition temperature was measured at the peak temperature of temperature dispersion of Tanδ (ratio of storage elastic modulus E ′ and loss elastic modulus E ″ Tanδ = E ″ / E ′) measured by dynamic viscoelasticity. Measurement of dynamic viscoelasticity uses Leo Vibron DDV-01FP (manufactured by Orientec), measurement frequency: 10 Hz, heating rate: 4 ° C./min, excitation mode: single waveform, excitation amplitude: 2.5 μm The peak temperature of Tan δ was measured.

(3) Composition analysis in copolymer The monomer remaining in the polymer solution after the completion of polymerization was measured by gas chromatography (GC) to determine the composition in the copolymer.

(4) Residual solvent amount When measuring the residual solvent amount other than toluene in the cyclic olefin-based resin composition, 1 g of a film is dissolved or swollen in 20 mL of toluene, and the residual solvent in the film is extracted, followed by gas chromatography. A column Poraplot Q (manufactured by Hewlett Packard) was attached to an apparatus HP-5890 (manufactured by Hewlett Packard), and the amount of residual solvent was measured. When measuring the amount of residual toluene in the film, 1 g of the film was dissolved or swollen in 20 mL of cyclohexane or 20 mL of acetone, and measured and quantified by the same method.

(5) Total light transmittance
Based on ASTM-D1003, the cyclic olefin resin composition was formed into a film having a thickness of about 100 μm, and the total light transmittance was measured.

(6) Flame retardant measurement evaluation method (Flame retardant measurement evaluation method 1)
A film made of a cyclic olefin-based resin composition is cut into 50 mm × 200 mm, rounded into a cylindrical shape having a diameter of 12.7 mm and a length of 200 mm, and one end of the cylindrical film faces the ground, and its longitudinal direction Was held so that it was perpendicular to the ground. Next, the other end was exposed to a flame of about 20 mm for 3 seconds and then released. Observe the burned state of the film after flame-off and evaluate in four stages (◎: self-extinguish within 5 seconds, ○: self-extinguish within 7 seconds, Δ: self-extinguish within 10 seconds, x: 10 seconds Within self-extinguish or burn out). ◎, ○ and △ were judged as good.

(Flame retardance measurement evaluation method 2)
After the evaluation by the flame retardancy measurement evaluation method 1, immediately after extinguishing the fire, the end portion was again exposed to a flame of about 20 mm for 3 seconds and then released. Repeat this operation two more times, and evaluate the total time until the fire extinguishes after flame removal (◎: self-extinguish within 7 seconds, ○: self-extinguish within 10 seconds, x: within 10 seconds) Did not self-extinguish). ◎ and ○ were judged as good.

(7) Breaking strength / breaking elongation
According to JIS K7113, the test piece was measured at a pulling speed of 3 mm / min.
[Reference Example 1]
In a 100 mL glass pressure bottle, under nitrogen atmosphere, 47 mL of toluene with a water content of 20 ppm, 50 mmol of bicyclo [2.2.1] hept-2-ene, 40 mmol of 5-butylbicyclo [2.2.1] hept-2-ene The mouth of the pressure bottle was sealed with a rubber cap with a crown. 20 mL of 0.1 MPa gaseous ethylene was added to this through a rubber cap. Next, the pressure bottle was heated to 55 ° C., and 0.0002 mmol of palladium acetate, 0.0002 mmol of tricyclohexylphosphine and 0.0002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were charged to initiate polymerization. . After 1 hour and 2 hours from the start of polymerization, 5 mmol of bicyclo [2.2.1] hept-2-ene was added, and polymerization was performed for 4 hours from the start of polymerization. The conversion ratio of the monomer to the cyclic olefin addition copolymer was 99.8%. This polymer solution was coagulated and separated with isopropanol and dried to obtain a cyclic olefin addition copolymer A.

The Mn of addition copolymer A was 58,000, and Mw was 167,000. The Tg of addition copolymer A was 352 ° C. Moreover, the ratio of the structural unit derived from 5-butylbicyclo [2.2.1] hept-2-ene in the addition copolymer A was 39.5 mol%.

[Reference Example 2]
In a 5 L reactor, 2 L of toluene having a water content of 15 ppm at 25 ° C. in a nitrogen atmosphere, 493 g (5.24 mol) of bicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] 180 g (1.2 mol) of hepta-2-ene and 100.8 g (0.286 mol) of 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene were charged. To this, ethylene as a molecular weight regulator was added so that the pressure in the system was 0.013 MPa. Further, 0.0267 mmol of catalyst components (tricyclohexylphosphine) palladium dietanoate and 0.0267 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were charged. Next, the polymerization was started by heating to 55 ° C., and after 1.5 hours (conversion to polymer: 72%), 47 g of bicyclo [2.2.1] hept-2-ene and 5-trimethoxy 9.6 g of silylbicyclo [2.2.1] hept-2-ene was added to the reactor, and after another 3 hours (conversion to polymer: 92%), bicyclo [2.2.1] hepta- 4-7.0 g of 2-ene and 9.6 g of 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene were added to the reactor, and polymerization was carried out for 6 hours from the start of polymerization. The conversion ratio of the monomer to the cyclic olefin addition copolymer was 99.8%.

  The cyclic olefin addition copolymer B thus obtained had an Mn of 52,000 and an Mw of 167,000. The Tg of addition copolymer B was 315 ° C. Moreover, the ratio of the structural unit derived from 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene in the addition copolymer B was 7.1 mol%.

[Reference Example 3]
In a 100 mL glass pressure bottle, under a nitrogen atmosphere, 20 mL of 20 ppm toluene, 30 mL cyclohexane, 55 mmol bicyclo [2.2.1] hept-2-ene and 4-methyltetracyclo [6.2.1.1 ^{3 , 6} . ^0,7 ] methyl dodeca-9-ene-4-carboxylate 20 mmol, 0.002 mmol of tricyclohexyl palladium bis (2-ethylhexanoate) as a catalyst component, triphenylcarbenium tetrakis (pentafluorophenyl) aluminum 0.002 mmol of nato and 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were charged and sealed with a rubber cap with a crown. 20 mL of 0.1 MPa gaseous ethylene was added to this through a rubber cap. The pressure bottle was heated to 60 ° C. to start polymerization, and 5 mmol of bicyclo [2.2.1] hept-2-ene was added every 30 minutes, and polymerization was performed for 3 hours from the start of polymerization. . The conversion ratio of the monomer to the cyclic olefin addition copolymer was 99.8%.

The cyclic olefin addition copolymer C thus obtained had an Mn of 62,000 and an Mw of 173,000. The Tg of addition copolymer C was 323 ° C. In addition, 4-methyltetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 15 mol%.

[Example 1]
3 parts by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant with respect to 100 parts by weight of addition copolymer A , Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.3 parts by weight as an antioxidant, tris (2,6-di-t-butylphenyl) 0.3 parts by weight of phosphite and 1.0 parts by weight of cyclohexyl p-toluenesulfonate were added to prepare a 20% by weight toluene solution.

  This solution was formed on a polyester film by a solution casting method. It dried at 180 degreeC for 2 hours, the solvent was removed, and the film 1 with a film thickness of 100 micrometers was obtained. Film 1 had a Tg of 305 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Example 2]
In the same manner as in Example 1, except that 10 parts by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was added. A film 2 having a thickness of 102 μm was obtained. Film 2 had a Tg of 298 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Example 3]
Except for adding 30 parts by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.), the same method as in Example 1 was used. A film 3 having a film thickness of 101 μm was obtained. Film 3 had a Tg of 294 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Example 4]
10 parts by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant with respect to 100 parts by weight of addition copolymer B , Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.3 parts by weight as an antioxidant, tris (2,6-di-t-butylphenyl) 0.3 parts by weight of phosphite and 1.0 parts by weight of cyclohexyl p-toluenesulfonate were added to prepare a 20% by weight toluene solution.

  This solution was formed on a polyester film by a solution casting method. After drying at 180 ° C. for 2 hours to remove the solvent, this film was dried with 180 ° C. heated steam to obtain a film 4 having a thickness of 100 μm. The film 4 was excellent in solvent resistance, Tg was 320 ° C., and excellent in flame retardancy. Other results are shown in Table 1.

[Example 5]
A film 5 having a thickness of 105 μm was obtained in the same manner as in Example 2 except that the addition copolymer C was used. The film 5 had a Tg of 315 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Example 6]
1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) 5 parts by weight, and 10- (2,5-dihydroxyphenyl) -9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added in the same manner as in Example 1 to obtain a film 6 having a thickness of 103 μm, except that 5 parts by weight were added. The film 6 had a Tg of 301 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Example 7]
A film 7 having a thickness of 101 μm was obtained in the same manner as in Example 1 except that 10 parts by weight of 1,3-bis [di (2 ′, 6′-dibutylphenyl) phosphoryl] benzene was added. The film 7 had a Tg of 297 ° C. and was excellent in flame retardancy. Other results are shown in Table 1.

[Comparative Example 1]
In the same manner as in Example 1, except that 1 part by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was added. A film 8 having a thickness of 101 μm was obtained. Film 8 did not self-extinguish after ignition. Other results are shown in Table 1.

[Comparative Example 2]
In the same manner as in Example 1 except that 50 parts by weight of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) was added. A film 9 having a thickness of 101 μm was obtained. Although the film 9 had no problem in flame retardancy, it was cloudy and very brittle. Other results are shown in Table 1.

[Comparative Example 3]
Implemented except that 20 parts by weight of trioctyl phosphate was added instead of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) A film 10 having a thickness of 101 μm was obtained in the same manner as in Example 1. Film 10 did not self-extinguish after ignition. Other results are shown in Table 1.

[Comparative Example 4]
Except that 20 parts by weight of aluminum hydroxide was added instead of 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] benzene (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) A film 11 having a thickness of 100 μm was obtained in the same manner as in Example 1. Film 11 did not self-extinguish after ignition and was cloudy. Other results are shown in Table 1.

  From the results shown in Table 1, when the amount of the flame retardant with respect to the addition copolymer A is too small, the desired flame retardancy cannot be obtained. On the other hand, when the amount of the flame retardant is too large, there is a problem with the flame retardancy. Although not, it turns out that transparency and a mechanical characteristic fall (Examples 1-3, Comparative Examples 1 and 2). Moreover, when not adding the specific flame retardant used for this application to the addition copolymer A, it turns out that transparency, a flame retardance, and a mechanical characteristic are all inferior (Examples 1-3, the comparative example 3, and 4).

Claims (8)

Cyclic olefin addition (co) polymer [I] having a structural unit represented by the following general formula (1)
100 parts by weight,
A cyclic olefin-based resin composition comprising 2 to 40 parts by weight of a condensed phosphate ester compound [II] represented by the following general formula (2).

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, further a ¹ and a ² as in the alkylidene group having 1 to 15 carbon atoms, alicyclic structure, cyclic aromatic structure, cyclic May form an acid anhydride group or a cyclic imido group, an alicyclic structure having 1 to 15 carbon atoms formed by the A ¹ and A ^3, aromatic cyclic structure, cyclic anhydride groups, or (A cyclic imide group may be formed, and m represents an integer of 0 or 1.)

(In the formula ^{(2), R 1, R} 2, R 4 ~R 6 each independently represent an aryl group having 5 to 20 carbon atoms, R ³ represents an arylene group having 6 to 25 carbon atoms, n Represents an integer of 0 to 3.) The cyclic olefin addition (co) polymer [I] is a bicyclo [2.2.1] hept-2-
The cyclic olefin-based resin composition according to claim 1, wherein the structural unit derived from ene is contained in an amount of 40 mol% or more in all structural units. In the cyclic olefin addition (co) polymer [I], at least one of A ^{1 to} A ⁴ in the formula (1) is hydrolyzable silyl group, alkoxycarbonyl group, oxetanyl group, carbonimido group, carbonate The cyclic olefin-based resin according to claim 1, wherein the structural unit is a substituent selected from the group consisting of a group, a glycidyl group, and an acid anhydride group, and includes 1 mol% to 20 mol% of all structural units. Composition. The glass transition temperature of the cyclic olefin addition (co) polymer [I] is 200 ° C. to 400 ° C.
The cyclic olefin-based resin composition according to claim 1, wherein the cyclic olefin-based resin composition is in the range of The cyclic olefin-based resin composition according to any one of claims 1 to 4, wherein the condensed phosphate ester compound [II] is represented by the following general formula (3).

(In the formula (3), A ⁵ to A ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)   The cyclic olefin resin according to any one of claims 1 to 5, wherein a film having a film thickness of 100 µm and a light transmittance (ASTM-D1003) with respect to a light beam having a wavelength of 500 nm of 80% or more can be formed. Composition.   A molded article comprising the cyclic olefin-based resin composition according to any one of claims 1 to 6.   The molded body according to claim 7, wherein the molded body is a film or a sheet.