JPH05239284A - Flame-retardant cycloolefinic resin composition - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. which neither corrodes a processing machine nor generates a toxic gas when burned by compounding a specific cycloolefin resin component with a specified amts. of ammonium polyphosphate, pentaerythritol, and a silicone. CONSTITUTION:100 pts.wt. cycloolefinic resin component is compounded with 1-40 pts.wt. ammonium pholyphosphate, 1-20 pts.wt. pentaerythritol, and 1-10 pts.wt. silicone. The resin component comprises at least one cycloolefin resin selected from the group consisting of a random copolymer of ethylene with a cycloolefin of formula I (wherein(n) and (q) are each 0 or 1; (m) is or higher; and R<1> to R<18> R1, and R<b> are each H, halogen, a hydrocarbon group, etc.) or formula II (wherein (p) and (g) are each 0 or higher; (m) and (n) are each 0-2; and R<1> to R<19> are each H, halogen, an aliph., alicyclic, or arom. hydrocarbon group, alkoxy, etc.), a ring-opening (co)polymer obtd. from the cycloolefin of formula I, a hydrogenation product of the ring-opening (co)polymer, and a graft coplymer obtd. by grafting an unsatd. carboxylic acid (deriv.) onto one of the foregoing polymers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin resin composition which is excellent in heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, dimensional stability, impact resistance and flame retardancy. Regarding

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin random copolymer obtained by using a specific cyclic olefin as a bulky monomer and copolymerizing this cyclic olefin with ethylene has heat resistance, heat aging resistance and solvent resistance. The present applicant has already filed an application for a random copolymer using a specific cyclic olefin based on the finding that it has excellent dielectric properties and rigidity (Japanese Patent Application Laid-Open No. 60-168,708,
JP-A-61-098,780 and JP-A-61-11
5,912, JP 61-115,916, JP 61-120,816, and JP 6
2-252,407).

The cyclic olefin random copolymer described in the above publication is considered to be one of the resins suitable as a molding material for automobiles, home appliances, OA equipment, sundries, etc. However, it is easily combusted, so that it can be used for electric parts and the like. The use was restricted from the viewpoint of safety in applications where flame retardancy is strongly required. Further, JP-A 2-255848 discloses a flame-retardant cyclic olefin polymer composition in which a halogen-based flame retardant, an antimony flame retardant, and polytetrafluoroethylene are mixed with a cyclic olefin polymer. Has been done.

However, blending a halogen-based flame retardant and an antimony-based flame retardant causes corrosion of equipment during resin processing and generation of harmful gas during resin combustion. There has been a demand for the development of flame retardant formulations using flame retardants.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and does not use a halogen-based flame retardant or an antimony-based flame retardant, that is, an apparatus for processing a resin. It is an object of the present invention to provide a novel flame-retardant cyclic olefin-based resin composition that is free from corrosion and generation of harmful gas during resin combustion.

[0006]

SUMMARY OF THE INVENTION A flame-retardant cyclic olefin resin composition according to the present invention comprises (a) ethylene and the following formula [I] or [I]:
Random copolymer (a-1) with a cyclic olefin represented by the formula [I], a ring-opening polymer or ring-opening copolymer (a-2) of the cyclic olefin represented by the following formula [I], and a ring-opening weight thereof. At least one cyclic olefin selected from the group consisting of a hydrogenated product (a-3) of a polymer or a ring-opening copolymer, and a graft modified product (a-4) obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof. 100 parts by weight of resin, (b) ammonium polyphosphate; 1 to 40 parts by weight, (c) pentaerythritol; 1 to 20 parts by weight,
(D) Silicone; 1 to 20 parts by weight.

[0007]

[Chemical 3]

However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are ,
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group,
R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group.

[0009]

[Chemical 4]

However, in the above formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0,
1 or 2 and R ^{1 to} R ¹⁹ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. Or represents a group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or C 1-3 alkylene. May be bonded via a group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be.

The above random copolymer (a-1) comprises ethylene, the above cyclic olefin, and 3 to 2 carbon atoms.
It may be a copolymer with 0 α-olefin. The cyclic olefin-based resin (a) constituting the flame-retardant cyclic olefin-based resin composition according to the present invention has a softening temperature of 70 ° C. or higher and an intrinsic viscosity measured in decalin at 130 ° C. [ The cycloolefin resin (a) having an η] of 0.05 to 10 dl / g is preferable.

Further, the flame-retardant cyclic olefin resin composition according to the present invention comprises the above cyclic olefin resin (a),
In addition to ammonium polyphosphate (b), pentaerythritol (c), and silicone (d), (e) an amorphous to low crystalline α-olefin system formed from at least two α-olefin components Elastic copolymer (e-1), at least two α-olefins,
Α-formed from at least one non-conjugated diene component
At least one soft copolymer selected from the group consisting of an olefin / diene elastic copolymer (e-2) and an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof (e-3). The coalescence can be contained in a ratio of 5 to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin (a).

Further, the flame-retardant cyclic olefin resin composition according to the present invention comprises the above cyclic olefin resin (a), ammonium polyphosphate (b), pentaerythritol (c) and silicone (d), or the above. In addition to the cyclic olefin resin (a), ammonium polyphosphate (b), pentaerythritol (c), silicone (d) and soft copolymer (e), the crystalline polyolefin (f) is added to the cyclic olefin. It can be contained in a proportion of 2 to 60 parts by weight with respect to 100 parts by weight of the resin (a).

Since the flame-retardant cyclic olefin resin composition according to the present invention is composed of the above-mentioned components, it is excellent in flame retardancy and, at the same time, the equipment is corroded during resin processing and the resin is burned. No harmful gas is generated.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The flame-retardant cyclic olefin resin composition according to the present invention will be specifically described below. The flame-retardant cyclic olefin resin composition according to the present invention comprises a specific cyclic olefin resin (a), ammonium polyphosphate (b), pentaerythritol (c), and silicone (d). It is contained in proportion. The flame-retardant cyclic olefin resin composition according to the present invention may further contain a specific soft copolymer (e) and / or crystalline polyolefin (f) in addition to these components. ..

Cyclic olefin resin (a) The cyclic olefin resin (a) used in the present invention is a random copolymer (a-1) of ethylene and a specific cyclic olefin, a ring-opening weight of a specific cyclic olefin. Polymer or ring-opening copolymer (a-2), hydrogenated product (a-3) of the ring-opening polymer or ring-opening copolymer, and graft modification by modifying these with unsaturated carboxylic acid or its derivative It is at least one type of cyclic olefin resin selected from the group consisting of the products (a-4). The random copolymer (a-1) is ethylene, a specific cyclic olefin,
It may be a copolymer with an α-olefin having 3 to 20 carbon atoms.

First, the random copolymer (a-1) of ethylene and a specific cyclic olefin will be described. The cyclic olefin constituting this random copolymer (a-1) is represented by the following general formula [I] or [II].

[0018]

[Chemical 5]

However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, the ring formed here is a 6-membered ring, and when q is 0, it is a 5-membered ring. In the above formula [I], R ^{1 to} R ^18, R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, each independently, usually, an alkyl group having 1 to 20 carbon atoms,
Examples thereof include halogenated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group.
Specific examples of the alkyl halide include a group in which at least a part of hydrogen atoms forming the alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .. Further, specific examples of the cycloalkyl group include a cyclohexyl group, specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and these groups include a lower alkyl group. It may have a group.

Further, in the above formula [I], R¹⁵And R
¹⁶And R¹⁷And R¹⁸And R¹⁵And R ¹⁷And R¹⁶And R¹⁸
And R¹⁵And R¹⁸Or, or R¹⁶And R¹⁷That's it
Combined (jointly with each other) to form a monocyclic or polycyclic group
May be formed, and formed in this way
The monocyclic or polycyclic group may have a double bond. This
Here, examples of the monocyclic or polycyclic group are described below.
A group can be mentioned.

[0022]

[Chemical 6]

In the above-exemplified groups, carbon atoms numbered 1 and 2 are the same as R in the formula [I].
It represents a carbon atom of an alicyclic structure to which the group represented by ^{15 to} R ¹⁸ is bonded. R ¹⁵ and R ¹⁶ or R ¹⁷ and R
¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0024]

[Chemical 7]

However, in the formula [II], p and q
Is 0 or an integer of 1 or more, and m and n are 0, 1 or 2. In addition, R ^{1 to} R ¹⁹ are each independently
It represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. Where R ⁹
And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. May be. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other to form methylene. Group (-CH _2- ), ethylene group (-CH ₂ CH _2- ) or trimethylene group (-C
H ₂ CH ₂ CH ₂ —) forms any alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, examples of the monocyclic or polycyclic aromatic ring include R ¹⁵ and R when n = m = 0.
^The groups described below in which ¹² and ¹² further form an aromatic ring can be mentioned.

[0027]

[Chemical 8]

In the above formula, q is the above general formula [I
It has the same meaning as q in I]. In the general formula [II], the halogen atom has the same meaning as the halogen atom in the general formula [I]. The aliphatic hydrocarbon group here is an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group. Specific examples of the halogenated alkyl group include a group in which at least a part of hydrogen atoms forming the alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. it can.

Specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, and specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. .. These groups may have a lower alkyl group. The above formulas [I] and [I
Examples of the cyclic olefin represented by I] include bicyclo [2.2.1] hept-2-ene derivative and tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene derivatives, hexacyclo [6.
6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4 Heputadensen derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13, ^{16.0
3,8 12,17} ] -5-dococene derivative, pentacyclo [6.6.
1.1 ^3,6 .0 ^2,7 .0 ^9,14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.0.1 ^{2, 5]-3-decene} derivative, tricyclo [4.3.0.1 ^{2, 5]-3-undecene} derivative, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [7.4 .0.1 ^{2 5} .1 ^9,12 .0 ^8,13] -3-pentadecene derivatives, pentacyclo [8.7.0.1.3.6.1 ^10,17 .1
^12,15 .0 ^2,7 .0 ^11,16] -4-eicosene derivatives, Nonashikuro ^{[10.9.1.1 4,7 .1 13,20 1 15,18 .0} 3,8 .0 2,10 .0 12 ^{, 21} .0
^14,19] -5-pentacosene derivatives, pentacyclo [8.4.
0.1 ^2,3 .1 ^9,12 .0 ^8,13] -3-hexadecene derivative, pentacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] -Five-
Heneicosene derivatives, Nonashikuro [10.10.1.1 ^5,8 .1
^14,21 .1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives, bicyclo [2.2.1] hept-2-ene derivative,
Examples include 1.4-methano-1.4.4a.9a-tetrahydrofluorene derivative, 1.4-methano-1.4.4a.5.10.10a-hexahydroanthracene derivative and cyclopentadiene-acenaphthylene adduct.

In the following, the above formula [I] or [I
Specific examples of the cyclic olefin represented by [I] are shown below.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

[0051]

[Chemical 28]

[0052]

[Chemical 29]

[0053]

[Chemical 30]

The above-mentioned general formula [I] or [II]
The cyclic olefin represented by can be produced by subjecting cyclopentadiene and olefins having a structure corresponding to cyclopentadiene to a Diels-Alder reaction. These cyclic olefins can be used alone or in combination of two or more kinds.

In the present invention, the cyclic olefin random copolymer (a-1) used as the cyclic olefin resin (a) is, for example, ethylene in the liquid phase in the presence of a catalyst and the above formula [I]. ] Or [II] or a cyclic olefin (unsaturated monomer) represented by [II]. In the present invention, the cyclic olefin compound represented by the above formula [I] or [II] is copolymerized to form a cyclic olefin random copolymer (a-
The monomer constituting 1) is ethylene. However, in the cyclic olefin random copolymer used in the present invention,
In addition to ethylene used as an olefin compound, another olefin compound may be copolymerized.

In the present invention, examples of other olefin compounds which can be copolymerized with ethylene and the cyclic olefin compound represented by the above formula [I] or [II] are propylene, 1-butene, and 4-methyl. -1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
Α-Olefins having 3 to 20 carbon atoms such as 1-octadecene and 1-eicosene; cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H -Cycloolefins such as indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene And non-conjugated dienes such as 5-vinyl-2-norbornene; norbornene-2,5-methylnorbornene-2,
5-Ethylnorbornene-2,5-isopropylnorbornene-2,5-n-butylnorbornene-2,5-i-
Butyl norbornene-2,5,6-dimethylnorbornene-2,5-chloronorbornene-2,2-fluoronorbornene-2 and 5,6-dichloronorbornene-
Norbornenes such as 2 can be mentioned.

The above ethylene and the formula [I] or [II]
The reaction with the cyclic olefin represented by is usually carried out in a hydrocarbon solvent. Examples of the hydrocarbon solvent used here include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene,
Aromatic hydrocarbons such as toluene and xylene may be mentioned.

Further, among the polymerizable unsaturated monomers which can be used in the preparation of the cyclic olefin random copolymer, compounds which are liquid at the reaction temperature can be used as the reaction solvent. These solvents can be used alone or in combination. The catalyst used in the reaction of the above olefin with the cyclic olefin represented by the formula [I] or [II] is a catalyst composed of a vanadium compound and an organoaluminum compound soluble in a hydrocarbon solvent used as a reaction solvent. Can be mentioned.

The vanadium compound used as the catalyst here has the formula VO (OR) _a V _b or the formula
The compound represented by V (OR) _c X _d may be mentioned. However, in the above formula, R is a hydrocarbon group, and a, b, c and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3,
2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d
It has a relationship of ≦ 4.

Further, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of these vanadium compounds include VOC
l ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ C
l, VO (O-iso- C 3 H 7) Cl 2, VO (O-n-C 4
H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ ,
VOCl ₂ , VO (O-n-C ₄ H ₉ ) ₃ and VCl ₃・ 2
Examples thereof include vanadium compounds such as (OC ₈ H ₁₇ OH). These vanadium compounds can be used alone or in combination.

Examples of the electron donor that forms an adduct with the above vanadium compound include 1 to 18 carbon atoms.
Alcohols, C6-C20 phenols (these phenols may have a lower alkyl group), C3-C15 ketones, C2-C2
15 aldehydes, carboxylic acids having 2 to 30 carbon atoms,
Esters of organic or inorganic acids, 2 to 15 carbon atoms
Examples of the acid halides, ethers having 2 to 20 carbon atoms, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate. You can These electron donors can be used alone or in combination.

As the organoaluminum compound used here, a compound having at least one Al-carbon bond in the molecule can be used. Here, as an example of the organic aluminum compound, (i) formula R ¹ _m Al (OR
² ) _n H _p X _q (wherein R ¹ and R ² are hydrocarbon groups having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. Is halogen, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ n <
3 and q are numbers 0 ≦ q <3, and m + n + p +
an organoaluminum compound represented by q = 3).

[0063] (ii) formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, a K, R ¹ is as defined above)
A complex alkyl compound of a Group 1 metal represented by and aluminum can be mentioned. Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below.

The formula R ¹ _m Al (OR ² ) _3-m (where R ¹
And R ² have the same meaning as described above, and m is preferably a number of 1.5 ≦ m <3). formula
R ¹ _m AlX _3-m (wherein R ¹ has the same meaning as described above, X is halogen, and m is preferably 0 <m <3)
The compound represented by. Formula R ¹ _m AlH _3-m (where R ¹
Has the same meaning as above, and m is preferably 2 ≦ m <3
Is a compound represented by the formula:

The formula R ¹ _m Al (OR ² ) _n X _q (where R ¹
And R ² have the same meaning as described above. X is halogen,
0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q =
3). Specific examples of the organoaluminum compound represented by the above formula (ii) include:
Trialkylaluminums, dialkylaluminum alkoxides, alkylaluminum sesquialkoxides, such as partially alkoxylated alkylaluminums, dialkylaluminum halides, alkylaluminum sesquihalides having an average composition of the formula R ¹ _2.5 Al (OR ² ) _0.5, etc. , Partially halogenated alkyl aluminum, such as alkyl aluminum dihalide, dialkyl aluminum hydride,
Mention may be made of partially hydrogenated alkylaluminium, such as alkylaluminium dihydride, and partially alkoxylated and halogenated alkylaluminium.

The organoaluminum compound may be a compound similar to the compound represented by the formula (ii), such as an organoaluminum compound in which two or more aluminum atoms are bound to each other via an oxygen atom or a nitrogen atom. .. Specific examples of such compounds include (C
_{2 H 5) 2 AlOAl (C} 2 H 5) 2, (C 4 H 9) 2 AlOA
_{l (C 4 H 9) 2} , (C 2 H 5) 2 AlN (C 6 H 5) Al (C
₂ H ₅ ) ₂ can be mentioned.

Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof. The amount of the vanadium compound used is usually 0.0
1-5 gram atom / liter, preferably 0.05-3
It is in the range of gram atom / liter. The amount of the organoaluminum compound used is usually in the range of 2 or more, preferably 2 to 50, particularly preferably 3 to 20, when expressed as the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (Al / V). It is in.

The cyclic olefin random polymer (a-1) obtained by using the above catalyst usually has a repeating unit derived from ethylene in the range of 52 to 90 mol%, preferably 55 to 80 mol%. The amount of the repeating unit derived from a cyclic olefin is 10 to 48 mol%, preferably 20 to 45 mol%. When the cyclic olefin random copolymer contains a repeating unit derived from an α-olefin other than ethylene, the content of the repeating unit derived from the α-olefin in the cyclic olefin random copolymer is usually 20 It is at most mol%, preferably at most 10 mol%.

In the cyclic olefin random copolymer (a-1) used in the present invention, the repeating units derived from ethylene and the repeating units derived from cyclic olefin are arranged substantially linearly. Moreover, these repeating units are randomly arranged. The cyclic olefin random copolymer (a
It is considered that at least a part of the cyclic olefin represented by the formula [I] in -1) has a structure represented by the following formula [III].

[0070]

[Chemical 31]

However, in the above formula [III], n,
m, q, R ^{1 to} R ^18, and R ^a and R ^b have the same meaning as in the above formula [I]. Further, in the cyclic olefin random copolymer (a-1) used in the present invention, at least a part of the cyclic olefin represented by the formula [II] has a structure represented by the following formula [IV]. Conceivable.

[0072]

[Chemical 32]

However, in the above formula [IV], n,
m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the above formula [II]. Next, the cyclic olefin ring-opening polymer and the cyclic olefin ring-opening polymer (a-2) used as the cyclic olefin resin (a) in the present invention, and the cyclic olefin ring-opening polymer and the cyclic olefin ring-opening weight. The combined hydrogenated product (a-3) will be described.

Among the cyclic olefin resin (a), the cyclic olefin ring-opening polymer and the cyclic olefin ring-opening copolymer (a-2) are, for example, those represented by the above formula [I] or [II].
A cyclic olefin represented by the following formula: in the presence of a catalyst consisting of a halide, nitrate or acetylacetone compound of a metal such as ruthenium, rhodium, palladium, osmium, indium or platinum and a reducing agent, or titanium, palladium, zirconium or molybdenum. It can be produced by (co) polymerization while ring-opening in the presence of a catalyst composed of a metal halide such as acetylacetone compound or the like and organoaluminum.

This cyclic olefin ring-opening (co) polymer (a
It is considered that at least a part of the cyclic olefin represented by the formula [I] in -2) has a structure represented by the following formula [V].

[0076]

[Chemical 33]

In the above formula [V], R ¹ to
R ¹⁸ , R ^a and R ^b , and m, n and q have the same meanings as in formula [I]. The hydrogenated product of the cyclic olefin ring-opening (co) polymer [hydrogenated ring-opening (co) polymer] (a-3) is a cyclic olefin ring-opening (co) polymer obtained as described above. The coalesced product can be prepared by reduction with hydrogen in the presence of a hydrogenation catalyst.

In the hydrogenated ring-opening (co) polymer (a-3), at least a part of the cyclic olefin represented by the formula [I] is considered to have the structure represented by [VI].

[0079]

[Chemical 34]

In the above formula [VI], R ^{1 to} R
¹⁸ , R ^a and R ^b , and m, n and q have the same meanings as in the above formula [I]. In the present invention, the cyclic olefin resin (a) further includes the cyclic olefin random copolymer (a-1), a cyclic olefin ring-opening polymer or a ring-opening copolymer (a-2),
Hydrogenated product of the ring-opening polymer or ring-opening copolymer (a-
The graft modified product (a-4) of 3) is used.

An unsaturated carboxylic acid or its derivative is preferably used as the graft-modified product used in the present invention, that is, as the graft monomer used for producing the graft-modified cyclic olefin resin (a-4). .. Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid ^TM (endocis-bicyclo [2,2,1 ] Hept-5-ene-2,3-dicarboxylic acid)
Can be mentioned.

Further, examples of the above unsaturated carboxylic acid derivatives include unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and ester compounds of unsaturated carboxylic acids. be able to. Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, glycidyl acrylate and glycidyl methacrylate.

These grafting monomers can be used alone or in combination. Among the above graft monomers, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof, or glycidyl methacrylate and glycidyl acrylate are particularly preferable.

The graft-modified cyclic olefin resin (a-4) used in the present invention is, for example, the above-mentioned cyclic olefin resin with the above-mentioned graft monomer,
It can be produced by adopting various known methods and modifying them. For example, there is a method in which the unmodified cyclic olefin resin is melted and a graft monomer is added to perform graft polymerization, or a method in which the unmodified cyclic olefin resin and graft monomer are dissolved in a solvent to perform graft copolymerization. Further, as a method for producing a graft-modified cyclic olefin resin, a method of modifying an unmodified cyclic olefin resin by incorporating a graft monomer so as to have a desired graft modification rate,
A graft-modified cycloolefin resin having a high graft modification rate is prepared in advance, and the graft-modified cycloolefin resin having a high modification rate is diluted with an unmodified cycloolefin resin to obtain a graft-modified cycloolefin resin having a desired modification rate. There is a manufacturing method. In the present invention, a graft-modified cycloolefin resin produced by any method can also be used. And, the modification ratio of the graft-modified cycloolefin resin used in the present invention is usually
It is in the range of 0.01 to 5% by weight, preferably 0.1 to 4% by weight.

In order to efficiently graft-copolymerize the above-mentioned graft monomer, it is preferable to carry out such a reaction in the presence of a radical initiator. The graft reaction is usually performed at a temperature of 60 to 350 ° C. The radical initiator is usually used in an amount within the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the unmodified cyclic olefin resin.

As the radical initiator, organic peroxides and organic peresters are preferably used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5
-Dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert
-Butyl peracetate, 2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexyne-3,2,5-
Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate , Cumyl perpivalate and tert-
Butyl perdiethyl acetate can be mentioned.

Further, in the present invention, an azo compound can be used as a radical initiator. Specific examples of this azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Among these, radical initiators such as benzoyl peroxide, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (te
rt-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane,
1,4-bis (tert-butylperoxyisopropyl)
Dialkyl peroxide such as benzene is preferably used.

In the present invention, the cyclic olefin resin (a) used in the flame-retardant cyclic olefin resin composition.
Has a softening temperature (TMA) of usually 70 ° C. or higher, preferably 70 to 200 ° C., more preferably 100 to 180 ° C., and a glass transition temperature (Tg) of usually 50 to 190 ° C., preferably It is in the range of 80 to 170 ° C.

The cyclic olefin resin (a)
Is the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is usually 0.05 to 10 dl / g, preferably 0.3 to
2.0 dl / g, more preferably 0.4 to 1.2 dl
Within the range of / g. The cyclic olefin resin (a) has a crystallinity of usually 0 to 20%, preferably 0 to 2% as measured by an X-ray diffraction method.

Ammonium Polyphosphate The ammonium polyphosphate (b) forming the flame-retardant cyclic olefin resin composition according to the present invention is obtained by thermally condensing ammonium orthophosphate and urea. Pentaerythritol The pentaerythritol (c) forming the flame-retardant cyclic olefin resin composition according to the present invention is monopentaerythritol, dipentaerythritol, tripentaerythritol, or the like, or a mixture thereof.

[0091] The silicone to form a flame retardant cyclic olefinic resin composition according to the silicone (d) according to the invention is an organopolysiloxane consisting of a chemical bond units substantially expressed by the following equation.

[0092]

[Chemical 35]

Here, R in the above formula represents a saturated or unsaturated monovalent hydrocarbon group, or a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl group, an allyl group or the like. Soft Copolymer (e) The soft copolymer (e) forming the flame-retardant cyclic olefin resin composition according to the present invention is an amorphous or low crystalline product formed from at least two α-olefin components. Sexual α-
An olefin elastic copolymer (e-1), an α-olefin / diene elastic copolymer (e-2) formed from at least two α-olefins and at least one non-conjugated diene component, and It is at least one soft copolymer selected from the group consisting of aromatic vinyl hydrocarbon / conjugated diene copolymers or hydrides thereof (e-3).

The above α-olefin elastic copolymer (e-
Specific examples of 1) include (a) ethylene / α-olefin copolymer rubber and (b) propylene / α-olefin copolymer rubber. The α-olefin constituting the ethylene / α-olefin copolymer rubber (a) is usually an α-olefin having 3 to 20 carbon atoms,
Examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. Of these, propylene or 1-butene is particularly preferable.

The α-olefin constituting the propylene / α-olefin copolymer rubber (b) is usually an α-olefin having 4 to 20 carbon atoms, such as 1-olefin.
Examples thereof include butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. Of these, 1-butene is particularly preferable.

In the above ethylene / α-olefin copolymer rubber (a), the molar ratio of ethylene and α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin. Generally 30/70
˜95 / 5, preferably 50/50 to 95/5. The above-mentioned molar ratio in the ethylene / α-olefin copolymer rubber (a) is preferably 50/50 to 90/10 when the α-olefin is propylene, and the α-olefin has 4 carbon atoms. In the above case, it is preferably 80/20 to 95/5.

In the propylene / α-olefin copolymer rubber (b) as described above, propylene and α
The molar ratio with the olefin (propylene / α-olefin) varies depending on the type of the α-olefin, but is generally preferably 50/50 to 95/5. The above molar ratio in the propylene / α-olefin copolymer rubber (b) is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and α
-80 if the olefin has 5 or more carbon atoms
It is preferably / 20 to 95/5.

The α-olefin-based elastic copolymer (e-1) has a crystallinity of 0 as measured by X-ray diffractometry.
It is desirable that it is -50%, preferably 0-25%. The intrinsic viscosity [η] of the α-olefin elastic copolymer (e-1) measured in decalin at 135 ° C. is
It is desired to be 0.2 to 10 dl / g, preferably 1 to 5 dl / g.

Furthermore, the density is 0.82 to 0.
96 g / cm ³ , preferably 0.84 to 0.92 g / c
It is preferably m ³ . The α-olefin-based elastic copolymer (e-1) used in the present invention is a graft monomer selected from unsaturated carboxylic acids or derivatives thereof in an amount of 0.01 to 5% by weight, preferably 0.1 to 4%. weight%
It may be a copolymer graft-modified with.

The unsaturated carboxylic acid or its derivative used for modifying the α-olefin elastic copolymer (e-1) in the present invention includes acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid and itacone. acid,
Citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^TM (endocis-bicyclo [2,2,1] hept-5
Unsaturated carboxylic acids such as -ene-2,3-dicarboxylic acid) or derivatives thereof such as acid halides, amides,
Examples thereof include imides, anhydrides, esters, and the like. Specific examples include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable. To produce a modified α-olefin-based elastic copolymer by graft-copolymerizing a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof with the α-olefin-based elastic copolymer (e-1) Various conventionally known methods can be adopted.

For example, the α-olefin elastic copolymer is melted and a graft monomer is added to carry out graft polymerization, or the α-olefin elastic copolymer is dissolved in a solvent and the graft monomer is added. There is a method of graft copolymerization. In either case,
In order to efficiently graft-copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator.

The graft reaction is usually carried out at a temperature of 60 to 350 ° C. The use ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the ethylene / α-olefin random copolymer. Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-
2,5-Di (tert-butylperoxy) hexyne-3,2,5-
Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate , Cumylpen pivalate and tert-
Butyl perdiethyl acetate and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate.

Among these, dicumyl peroxide, di-tert-butyl peroxide and 2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,4-
Dialkyl peroxides such as bis (tert-butylperoxyisopropyl) benzene are preferably used.
Among the α-olefin-based elastic copolymer (e-1), the ethylene content is 35 to 50 mol% and the crystallinity is 5
% Or less ethylene / propylene random copolymer or ethylene / α-olefin random copolymer unsaturated carboxylic acid or a copolymer graft-modified with a graft monomer selected from its derivative is most effective in improving impact strength. It is preferable because it is excellent.

Specific examples of the above-mentioned α-olefin / diene-based elastic copolymer (e-2) include ethylene / α-
Olefin / diene copolymer rubber (a), propylene /
An α-olefin / diene copolymer rubber (B) is used. The α-olefin constituting the ethylene / α-olefin / diene copolymer rubber (a) is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene. , 4-methyl-1-
Examples include pentene, 1-octene, 1-decene, and mixtures thereof. Of these, propylene or 1-butene is particularly preferable.

The α-olefin constituting the propylene / α-olefin / diene copolymer rubber (b) is usually an α-olefin having 4 to 20 carbon atoms, such as 1-butene or 1-pentene, 1-hexene, 4-methyl-1-
Examples include pentene, 1-octene, 1-decene, and mixtures thereof. Of these, 1-butene is particularly preferable.

The diene component in the ethylene / α-olefin / diene copolymer rubber (a) or the propylene / α-olefin / diene copolymer rubber (b) is 1,4-hexadiene, 1,6 -Octadiene, 2-methyl-
1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-
Chain non-conjugated dienes such as methyl-1,6-octadiene,
Cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene,
5-isopropylidene-2-norbornene, 6-chloromethyl
-5-isopropenyl-2-norbornene cyclic non-conjugated dienes such as 2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene,
2-propenyl-2,2-norbornadiene can be exemplified.

Of these, 1,4-hexadiene and cyclic non-conjugated dienes, especially dicyclopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 1,4- Hexadiene,
1,4-octadiene is preferred. Ethylene as above
In the α-olefin / diene copolymer rubber (a), the molar ratio of ethylene and α-olefin (ethylene /
The α-olefin) varies depending on the type of the α-olefin, but is generally preferably 50/50 to 95/5.

The above molar ratio in the ethylene / α-olefin / diene copolymer rubber (a) is 50/50 to 90/1 when the α-olefin is propylene.
It is preferably 0, and when the α-olefin has 4 or more carbon atoms, it is preferably 80/20 to 95/5. Also, this ethylene / α-olefin /
The content of the diene component in the diene copolymer rubber (a) is 0.5 to 10 mol%, preferably 0.5 to 5 mol%.
Is desirable.

In the propylene / α-olefin / diene copolymer rubber (B) as described above, the molar ratio of propylene and α-olefin (propylene / α-olefin) varies depending on the type of α-olefin. Is generally preferably 50/50 to 95/5. The molar ratio of the propylene / α-olefin / diene copolymer rubber (B) is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and the α-olefin is Is preferably from 20/20 to 95/5 when it has 5 or more carbon atoms.

In addition, this propylene / α-olefin /
The content of the diene component in the diene copolymer rubber (b) is 0.5 to 10 mol%, preferably 0.5 to 5 mol%
Is desirable. The α-olefin / diene-based elastic copolymer (e-2) has a crystallinity of 0 to 10%, preferably 0 to 5%, as measured by an X-ray diffraction method.

The intrinsic viscosity [η] of the α-olefin / diene type elastic copolymer (e-2) measured in decalin at 135 ° C. is 0.1 to 10 dl / g, preferably 1 to
It is preferably 5 dl / g. Further, it is desirable that its iodine value is 1 to 30, preferably 5 to 25.

Furthermore, the density is 0.82 to 1.0.
0 g / cm ³ , preferably 0.85-0.90 g / cm
³ is desirable. Specific examples of the aromatic vinyl hydrocarbon / conjugated diene copolymer or its hydride (e-3) include (a) styrene / butadiene copolymer rubber and (ii) styrene / butadiene / styrene copolymer. Polymer rubber, (c) styrene / isoprene block copolymer rubber, (d) styrene / isoprene / styrene block copolymer rubber, (e) hydrogenated styrene / butadiene / styrene block copolymer rubber, (f) water Styrene / isoprene / styrene block copolymer rubber or the like is used.

Styrene-butadiene copolymer rubber (a)
In general, the molar ratio of styrene to butadiene (styrene / butadiene) is preferably 0/100 to 60/40. In the styrene / butadiene / styrene block copolymer rubber (b), the molar ratio of styrene and butadiene (styrene / butadiene) is 0 /
100-60 / 40 is preferable, and the degree of polymerization of each block is about 0-5,000 for styrene,
For butadiene, it is preferably about 10 to 20,000.

In the styrene / isoprene block copolymer rubber (c), the molar ratio of styrene to isoprene (styrene / isoprene) is generally 0/100 to 60.
It is preferably / 40. Styrene / isoprene /
In the styrene block copolymer rubber (d), the molar ratio of styrene and isoprene (styrene / isoprene)
Is preferably 0/100 to 60/40, and the degree of polymerization of each block is preferably about 0 to 5,000 for styrene and about 10 to 20,000 for isoprene.

The hydrogenated styrene / butadiene / styrene block copolymer rubber (e) means the styrene / butadiene as described above.
A copolymer rubber in which a double bond remaining in a butadiene / styrene block copolymer rubber is partially hydrogenated, and a weight ratio of styrene and a rubber portion (styrene / rubber portion) is 0/100 to 50 /. It is preferably 50. Hydrogenated styrene / isoprene / styrene block copolymer rubber (f) is a copolymer rubber in which the double bond remaining in the styrene / isoprene / styrene block copolymer is partially hydrogenated. Therefore, the weight ratio of styrene to the rubber part (styrene / rubber part) is 0/100 to 50/50.
Is preferred.

The weight average molecular weight Mw of such an aromatic vinyl hydrocarbon / conjugated diene block copolymer measured by GPC (gel permeation chromatography, solvent ortho-dichlorobenzene, 140 ° C.) is 5
00-2,000,000, preferably 10,000
It is desirable that it is ˜1,000,000. further,
The density is preferably 0.80 to 1.10 g / cm ³ , and preferably 0.88 to 0.96 g / cm ³ .

In the present invention, the above soft copolymers (e-1) to (e-3) can be contained in the cyclic olefin resin composition either individually or in combination of two or more. .. When such soft copolymers are used in combination, the soft copolymers (e-1) to (e-3) are
It can be used in any combination.

In the present invention, the soft copolymer (e)
Is 5 to 100 parts by weight, preferably 7 to 70 parts by weight, relative to 100 parts by weight of the cyclic olefin resin (a).
It is more preferably 10 to 50 parts by weight. The crystalline polyolefin (f) forming the flame-retardant cyclic olefin resin composition according to the present invention has a crystallinity of more than 30%, preferably a crystallinity of 40, measured by X-ray diffraction.
% Or more, more preferably 50% or more of polyolefin is used. At the same time, the crystalline polyolefin (f) has a tensile modulus at 23 ° C. of 2,
Polyolefins above 000 kg / cm ² are used, in particular this tensile modulus is preferably 2,000.
kg / cm ^2, greater 30,000 / cm ² or less, still more preferably greater than 2,000 kg / cm ² 20,0
Polyolefins in the range of less than 00 kg / cm ² are used.

Polyethylene or polypropylene can be used as the crystalline polyolefin (f). Here, as the polyethylene, a repeating unit derived from ethylene is usually 50 mol% or more,
Polyethylene containing 90 mol% or more is preferably used. As the polypropylene, polypropylene containing 70 mol% or more, preferably 80 mol% or more of repeating units derived from propylene is used.

That is, the crystalline polyethylene may be a homopolymer of ethylene or a copolymer with a small amount of other α-olefin. Examples of other α-olefins that copolymerize with ethylene include propylene,
3 to 20 carbon atoms such as butene-1, pentene-1, 4-methylpentene-1, 3-methylbutene-1 and hexene-1
The α-olefins can be mentioned. Specific examples of the crystalline polyethylene that can be used in the present invention include high density polyethylene, low density polyethylene and linear low density polyethylene (LLDPE). Such crystalline polyethylene is usually less than 0.
It has a density of 82 to 0.96 g / cm ³ , and has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is usually in the range of 1-5 dl / g.

When polypropylene is used as the crystalline polyolefin (f), a homopolymer of propylene and a copolymer of propylene and another α-olefin can be used. Examples of other α-olefins that copolymerize with propylene include ethylene and butene.
-1, pentene-1, 4-methylpentene-1, 3-methylbutene
-1 and hexene-1 α- with 2 to 20 carbon atoms
Olefins (excluding propylene) can be mentioned. Such crystalline polypropylene is usually 0.8
It has a density of about 8 to 0.92 g / cm ³ , and the intrinsic viscosity [η] measured in decalin at 135 ° C. is
It is usually in the range of 1 to 10 dl / g.

The crystalline polyolefin (f)
May have a repeating unit derived from a chain non-conjugated diene and / or a repeating unit derived from a cyclic non-conjugated diene within a range that does not impair the crystallinity.
The content of the repeating unit derived from such a non-conjugated diene in the crystalline polyolefin (f) used in the present invention is usually 5 mol% or less, preferably 3 mol%
It is below.

In the present invention, the crystalline polyolefin (f) is 2 to 60 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 100 parts by weight of the cyclic olefin resin (a). 20 parts by weight. The flame-retardant cyclic olefin resin composition according to the present invention further includes, in addition to the above components, an inorganic filler, an organic filler, a heat stabilizer, a weather resistance stabilizer, an antistatic agent, an antislip agent, Additives such as antiblocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be added.

[0125]

INDUSTRIAL APPLICABILITY The flame-retardant cyclic olefin resin composition according to the present invention is an apparatus for resin processing as compared with a cyclic olefin resin composition using a conventional halogen flame retardant and antimony flame retardant. There is an effect that it is possible to prevent the corrosion of the resin and the generation of harmful gas at the time of burning the resin.

Therefore, the flame-retardant cyclic olefin resin composition according to the present invention can be extremely advantageously used as a flame-retardant molding material for automobiles, home appliances, OA equipment, sundries and the like.

[0127]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. [Evaluation Method] The properties of the cyclic olefin random copolymer and soft copolymer used in the present invention, the crystalline polyolefin, and the flame-retardant cyclic olefin resin composition according to the present invention are measured as follows. did. (1) Intrinsic viscosity [η] Measured in decalin at 135 ° C. (2) Softening temperature (TMA) The temperature at which a temperature rising rate of 5 ° C./min, a load of 50 g, and a flat-bottom needle with a diameter of 1 mm inserted into 100 μm were taken as TMA. (3) Tensile Strength and Elongation Measured at 23 ° C. according to ASTM D-638 using a 2 mm thick injection test piece. (4) Crystallinity Measured by an X-ray diffraction method at 23 ° C. (5) Izod (IZ) Impact Strength Measured at 23 ° C. according to ASTM D-256 using an injection test piece with a 1/8 inch thickness and notch. (6) Flexural Modulus (FM) According to ASTM D-790, using a 1/8 inch thick injection test piece, cross head speed 20 mm / min, 23 ° C.
It was measured at. (7) Bending Strength According to ASTM D-790, it was measured at 23 ° C. using an injection test piece having a thickness of 1/8 inch. (8) Combustion test Judgment was made by a UL94 method with a thickness of 1/16 inch. [Test For Flammability of Plastic Materials (UL94)] UL94V-0 (Effective January 28, 1980) After burning for 10 seconds, do not continue to burn for more than 10 seconds.

B. 5 sets of test pieces shall be one set, and the total burning time shall be within 50 seconds after 10 flame contact. C. Do not Flaming or Glowing until the clamp. D. There is no Drip. Do not burn absorbent cotton under 12 inches even if there is a drip.

E. For each test piece, the Growing Time after the second flame contact should not exceed 30 seconds. (9) Oxygen index According to JIS K-7201, with a thickness of 1/16 inch,
The minimum oxygen concentration (%) necessary for the combustion time of the test piece to continue to burn for 3 minutes or more, or for the burning length after flame to continue burning of 50 mm or more was measured.

[0130]

Example 1 Ethylene / tetracyclodecene copolymer (intrinsic viscosity [η] measured in decalin at 135 ° C .:
0.6 dl / g, TMA: 115 ° C.) 100 parts by weight,
Ammonium polyphosphate [Sumitomo Chemical Co., Ltd., Sumisafe P] 30 parts by weight, pentaerythritol [Wako Pure Chemical Industries, Ltd.] 8 parts by weight, dimethyl silicone gum [Silicone, Torre Silicone Co., Ltd.], BY16
-140] 4 parts by weight and methyl hydrogen polysiloxane [Toray Silicone Co., Ltd., BY16-80
1] 1 part by weight was melt-kneaded at 230 ° C. using a twin-screw extruder with a diameter of 30 mm to prepare pellets of a cyclic olefin resin composition.

After this resin composition was dried at 100 ° C. for 8 hours, an injection molding machine [manufactured by Toshiba IS, 30EP
N] was used to set 230 ° C. and the mold temperature to 70 ° C. to prepare a test piece for measuring physical properties, and the above evaluation was performed. The results are shown in Table 1.

[0132]

Example 2 Ethylene / tetracyclodecene copolymer
(Intrinsic viscosity [η] measured in decalin at 135 ° C .:
0.6 dl / g, TMA: 135 ° C.) 100 parts by weight,
Ethylene / propylene copolymer (tensile modulus: 150k
g / cm² , Load 2.16Kg / cm² , Temperature 230 ℃
Melt flow rate at: 0.41 g / 10 minutes
Crystallinity: 0%, ultimate viscosity measured in decalin at 135 ° C
[Η]: 2.55 dl / g) 12 parts by weight and polyethylene
Len (linear low density polyethylene, tensile modulus: 5,000
0 kg / cm ² , Load 2.16 kg / cm² , Temperature 19
Melt flow rate at 0 ° C .: 20 g / 10 minutes, binding
Crystallinity: 40%, Density: 0.920 g / cm³ ) 11 layers
100 parts by weight of the mixture with 100 parts by weight of peroxide [perhex
25B, manufactured by NOF CORPORATION] 0.1 part by weight and Jibi
Add 0.3 parts by weight of nylbenzene, and add to the twin-screw extruder.
Partially crosslinked.

Pellets and test pieces for measuring physical properties were prepared in the same manner as in Example 1 except that this resin mixture was used in place of the ethylene / tetracyclodecene copolymer, and the above evaluation was carried out. The results are shown in Table 1.

[0134]

Comparative Examples 1 and 2 In Examples 1 and 2, ammonium polyphosphate, pentaerythritol, and
Without using silicone, only cyclic olefin copolymer (ethylene / tetracyclodecene copolymer), cyclic olefin copolymer (ethylene / tetracyclodecene copolymer) / elastic copolymer (ethylene / propylene copolymer) Combined) A test piece for measuring physical properties was prepared using a partially crosslinked polyethylene, and the above evaluation was performed.

The results are shown in Table 1.

[0136]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 51/06 LLE 7142-4J 65/00 LNY 8215-4J // (C08L 23/08 83:04 )

Claims (5)

[Claims] 1. (a) Ethylene and the following formula [I] or [I]
[I] a random copolymer with a cyclic olefin (a-1), a ring-opening polymer or ring-opening copolymer (a-2) of a cyclic olefin represented by the following formula [I], Hydrogenated compound (a-
3), and at least one cyclic olefin resin selected from the group consisting of graft modified products (a-4) obtained by modifying these with unsaturated carboxylic acids or their derivatives; 1
00 parts by weight, (b) ammonium polyphosphate; 1 to 40 parts by weight, (c) pentaerythritol; 1 to 20 parts by weight, and (d) silicone; 1 to 20 parts by weight. Flame-retardant cyclic olefin resin composition; (However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are respectively Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and represents R ^{15 to} R
¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ And with, or R ¹⁷ and R
¹⁸ may form an alkylidene group), and (However, in the above formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2
And R ^{1 to} R ¹⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. The carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or through an alkylene group having 1 to 3 carbon atoms. R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring when n = m = 0. ). 2. The random copolymer (a-1) comprises ethylene, the cyclic olefin, and α- having 3 to 20 carbon atoms.
The flame-retardant cyclic olefin resin composition according to claim 1, which is a random copolymer with an olefin. 3. The softening temperature of the cyclic olefin resin (a) is in the range of 70 ° C. or higher, and the intrinsic viscosity [η] measured in decalin at 130 ° C. is 0.05 to 10 dl /.
It is in the range of g, The flame-retardant cyclic olefin resin composition of Claim 1 or 2 characterized by the above-mentioned. 4. (e) An amorphous to low crystalline α-olefin elastic copolymer (e-1) formed from at least two α-olefin components, and at least two α-olefins. An α-olefin / diene elastic copolymer (e-2) formed from at least one non-conjugated diene component, and an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof (e-3) And at least one soft copolymer selected from the group consisting of 5) to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin (a). The flame-retardant cyclic olefin resin composition according to any one of claims 1, 2 and 3. 5. The crystalline polyolefin (f) is added in an amount of 2 to 6 with respect to 100 parts by weight of the cyclic olefin resin (a).
The flame-retardant cyclic olefin-based resin composition according to any one of claims 1, 2, 3 and 4, further containing 0 part by weight.