JP2002179875A - Heat-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-resistant resin composition having excellent thermal aging resistance and especially suitable as a liquid crystal substrate material, a semiconductor coating material and an adhesive for lens by compounding a cyclic olefin (co)polymer with a combination of specific antioxidants. SOLUTION: The heat-resistant resin composition contains (A) a specific cyclic olefin (co)polymer and (B) at least one kind of antioxidant selected from (b-1) a phenolic antioxidant, (b-2) a phosphorus-based antioxidant and (b-3) a thioether-based antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat resistance obtained by combining a specific cyclic olefin (co) polymer with a specific antioxidant.

[0002]

2. Description of the Related Art Conventionally, transparent resins such as polymethyl methacrylate, polycarbonate, polystyrene,
Methylpentene resins and the like are known. These resins are also produced in large quantities industrially, and are utilized in large quantities in various fields, taking advantage of their good transparency. However,
These resins do not always have sufficient heat resistance. For example, even in polycarbonate which is the resin having the highest heat resistance among the above resins, the glass transition temperature which is an index of the heat resistance is about 150 ° C., which is higher. Development of a resin having heat resistance is desired.

As a resin having excellent transparency and higher heat resistance, a ring-opened polymer of a norbornene derivative having a polar substituent has been proposed. However, since ring-opened polymers of norbornene derivatives have carbon-carbon double bonds in their main chains, they undergo severe oxidative degradation at high temperatures, and are practically used as heat-resistant polymers regardless of their high glass transition temperatures. Had not been converted. For this reason, an attempt to improve the oxidative deterioration of the ring-opened polymer by hydrogenation has been proposed (Japanese Patent Publication No. 57-8815). The improvement of the oxidative deterioration by hydrogenation can greatly improve the oxidative deterioration resistance as compared with the conventional unhydrogenated polymer, but in the case of a high heat-resistant resin having a high glass transition temperature, it is inevitable. Therefore, it is necessary to raise the processing temperature, and deterioration during processing, particularly yellowing, is still a problem.

In recent years, cyclic olefin (co) polymers obtained by addition polymerization of norbornene derivatives have been proposed (JP-A-4-63807, JP-A-8-1).
No. 98919, Japanese Patent Publication No. 9-508649, Japanese Patent Publication No. 11-505880, etc.). This cyclic olefin (co) polymer has excellent heat resistance and transparency, and is useful for optical materials, semiconductor coating materials, adhesives, and the like.
However, like the ring-opened polymer of the norbornene derivative described above, it is a high heat-resistant resin having a high glass transition temperature, and it is necessary to necessarily increase the processing temperature, so that deterioration during processing, particularly yellowing Coloring is still a problem.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a heat resistance by combining a cyclic olefin (co) polymer with a specific antioxidant. An object of the present invention is to provide a heat-resistant resin composition which is excellent in deterioration property and is particularly suitable for a liquid crystal substrate material, a semiconductor coating material, and a lens adhesive.

[0006]

The present invention provides (A) a cyclic olefin (co) polymer containing a repeating unit (a-1) represented by the following general formula (1), and (B) thermogravimetric analysis. (TGA)
(B-1) a phenolic antioxidant, (b-2) a phosphorus-based antioxidant, and (b-3) The present invention relates to a heat-resistant resin composition containing at least one antioxidant selected from the group of sulfur-based antioxidants.

[0007]

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[In the general formula (1), A ^{1 to} A ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkenyl group, a halogen atom, a halogenated carbon atom. hydrogen radical, or - indicates a (CH ₂₎ a polar group represented by _k X. Where X is —C (O) OR ¹ ,
—OC (O) R ² , wherein R ^{1 to} R ² are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group and a halogen substituent thereof, and k is 0.
Represents an integer of 1 to 3. A ^{1 to} A ⁴ each represent a vinylidenyl group formed of A ¹ and A ² or A ³ and A ⁴ ; A ¹ and A ² ;
Also included are imide groups formed by ¹ and A ³ or A ³ and A ⁴ , and A ² and A ⁴ . l is an integer of 0 or 1. The (A) cyclic olefin (co) polymer preferably further contains a repeating unit (a-2) represented by the following general formula (2).

[0009]

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[In the general formula (2), B ^{1 to} B ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and-(CR ⁴ R ⁵ ) _n Si (OR ³ ) _m R ⁶ _(3-m) ,-(C
^{R 4 R 5) Si (R} 7 R 8) OSi (OR 3) m R 6 (3-m), -
_{C (O) O (CH 2} ) n Si (OR 3) m R 6 (3-m) indicates an alkoxysilyl group or Arirokishishiriru group or hydrolysis-Chijimigozanmoto these represented by, B ¹ ~ At least one of B ⁴ contains an alkoxysilyl group or an allyloxysilyl group or a hydrolyzed / condensed residue thereof. Here, R ³ represents an alkyl group or an aryl group having 1 to 10, and R ^{4 to} R ⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 0 to 3, n is an integer of 0 to 5, and r is 0 or 1. Further, the (A) cyclic olefin-based (co) polymer comprises 5 units of the repeating unit (a-1) represented by the general formula (1).
0 to 99.9 mol%, and 50 to 0.1 mol% of the repeating unit (a-2) represented by the general formula (2) [(a-1) +
(a-2) = 100 mol%].

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Cyclic olefin (co) polymer The (A) cyclic olefin (co) polymer used in the present invention comprises a repeating unit (a-1) represented by the above general formula (1). ),
Further, if necessary, a repeating unit represented by the above general formula (2)
It is a cyclic olefin-based (co) polymer containing (a-2).

Here, the repeating unit (a-1) includes the 2,3 additional structural unit represented by the above general formula (1), and the repeating unit (a-1) includes the following general formula (a). The 2,7 additional structural unit shown in 3) may be contained in a small amount.

[0013]

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[In the general formula (3), A ^{1 to} A ⁴ and l are the same as those in the general formula (1). ]

Hereinafter, (A) the cyclic olefin (co) polymer used in the present invention will be described more specifically. The repeating unit (a-1) used in the (A) cyclic olefin (co) polymer of the present invention has the following general formula (4)
(Hereinafter, referred to as "specific cyclic olefin (1)").

[0016]

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[In the general formula (4), A ^{1 to} A ⁴ and l are
Each is the same as that shown in the general formula (1). ]

Specific examples of such a specific cyclic olefin (1) include 2-norbornene and 5-methyl-2-
Norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-butyl-2-norbornene, 5-pentyl-2-norbornene, 5-hexyl-2-norbornene, 5-heptyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2
-Norbornene, 5-dodecyl-2-norbornene,
5,6-dimethyl-2-norbornene, 5-methyl, 5
-Ethyl-2-norbornene, 5-phenyl-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-ethylidene-2-norbornene, 5- Cyclohexyl-2-norbornene, 5-fluoro-2-norbornene, 5-chloro-2-norbornene, methyl 5-norbornene-2-carboxylate, 5-norbornene-
Ethyl 2-carboxylate, butyl 5-norbornene-2-carboxylate, methyl 2-methyl, 5-norbornene-2-carboxylate, ethyl 2-methyl, 5-norbornene-2-carboxylate, 2-methyl, 5- Norbornene-2-
Propyl carboxylate, 2-methyl, 5-norbornene
Butyl 2-carboxylate, 2-methyl, 5-norbornene-2-trifluoroethyl carboxylate, 2-methyl, 5-
Ethyl norbornen-2-ylacetate, 5-norbornene-2-spiro-N-phenylsuccinimide 5-norbornene-2-spiro-N-cyclohexylsuccinimide 5-norbornene-2-spiro-N-methylsuccinimide 5-norbornene-2, 3-N-phenyldicarboximide 5-norbornene-2,3-N-cyclohexyldicarboximide 2-methyl-5-acrylate
Norbornene, 2-methyl-5-norbornene methacrylate, dimethyl 5-norbornene-2,3-dicarboxylate, diethyl 5-norbornene-2,3-dicarboxylate, 3-tricyclo [4.3.0.1 ^2,5 Desen,
3,7-Tricyclo [4.3.0.1 ^2,5 ] decadiene (dicyclopentadiene) 3-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecene, 8-methyl, 3-tetracyclo [4.4.0.1
^2,5 1 ^7,10 ] dodecene, 8-methyl, 8-methoxycarbonyl, 3-tetracyclo [4.4.0.1
^2,5 1 ^7,10 ] dodecene, 8-methyl, 8-ethoxycarbonyl, 3-tetracyclo [4.4.0.1
^2,5 1 ^7,10 ] dodecene.

The compound represented by the above general formula (4) forming the above repeating unit (a-1) can be used alone or in combination of two or more.

The proportion of the repeating unit (a-1) in all the repeating units is preferably 50 to 99.9 mol%, more preferably 80 to 99.5 mol%, and particularly preferably 90 to 98 mol%. . When the amount is less than 50 mol%, the polymer is easily hydrolyzed, and it is difficult to form a film or a sheet. On the other hand, if it exceeds 99.9 mol%, the film strength is reduced, the adhesion to metal substrates such as Si, Al, Au, and Cu is reduced, and at the same time, it becomes difficult to form a crosslinked product.

The repeating unit (a) represented by the above general formula (2)
-2) is (a) a cyclic olefin represented by the following general formula (5)
It is referred to as “specific cyclic olefin (2)”. ) With the specific cyclic olefin (1) of the general formula (4). (B) As other methods, 5-trichlorosilyl-2-norbornene, 5-dichloromethylsilyl-2-norbornene, 5-dichloroethylsilyl-2-norbornene, 5-norbornene-
A specific cyclic olefin (3) having a trichlorosilyl group or a dichloroalkylsilyl group, such as trichlorosilylpropyl 2-carboxylate, trimethylsilylpropyl 2-methyl, 5-norbornene-2-carboxylate, and a specific cyclic olefin (1 )), And (b-1) reacting a trichlorosilyl group or a dichloroalkylsilyl group in the obtained copolymer with an alkali metal alkoxide or an alkali metal allyloxide to obtain another method. (B-2) in the presence of an amine compound to react with an alcohol or a phenol.

[0022]

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[In the general formula (5), B ^{1 to} B ⁴ and r are
It is the same as that shown in the general formula (2). ]

Specific examples of such a specific cyclic olefin (2) include 5-trimethoxysilyl-2-norbornene, 5-dimethoxy, chlorosilyl-2-norbornene, 5-methoxy, chloro, methylsilyl-2-norbornene, 5-dimethoxy, chlorosilyl-2-norbornene, 5-methoxy, hydride, methylsilyl-2-norbornene, 5-dimethoxy, hydridosilyl-2-norbornene, 5-methoxydimethylsilyl-2-norbornene, 5-triethoxysilyl-2 -Norbornene,
5-diethoxy, chlorosilyl-2-norbornene, 5
-Ethoxy, chloro, methylsilyl-2-norbornene, 5-diethoxy, hydridosilyl-2-norbornene, 5-ethoxydimethylsilyl-2-norbornene,
5-ethoxydiethylsilyl-2-norbornene, 5-
Propoxydimethylsilyl-2-norbornene, 5-triphenoxysilyl-2-norbornene, 5-diphenoxymethylsilyl-2-norbornene, 5-trimethoxysilylmethyl-2-norbornene, 5- (2-trimethoxysilyl) ethyl -2-norbornene, 5- (2-
Dimethoxy, chlorosilyl) ethyl-2-norbornene, 5- (1-trimethoxysilyl) ethyl-2-norbornene, 5- (2-trimethoxysilyl) propyl-
2-norbornene, 5- (1-trimethoxysilyl) propyl-2-norbornene, 5-triethoxysilylethyl-2-norbornene, 5-dimethoxymethylsilylmethyl-2-norbornene, 5-trimethoxypropylsilyl-2- Norbornene, trimethoxysilylpropyl 5-norbornene-2-carboxylate, triethoxysilylpropyl 5-norbornene-2-carboxylate, 5-
Dimethoxy, methylsilylpropyl norbornene-2-carboxylate, 2-methyl, 5-methoxysilylpropyl 5-norbornene-2-carboxylate, 2-methyl, 5-
And dimethoxy, methylpropyl norbornene-2-carboxylate, triethoxysilylpropyl 2-methyl, 5-norbornene-2-carboxylate, and the like.

In addition, when the cyclic unit (a-2) is contained in the cyclic olefin (co) polymer of the present invention at an appropriate ratio, adhesion and adhesion to metal are improved, and at the same time, A material having excellent solvent resistance can be obtained by hydrolysis and crosslinking reaction. The proportion of the repeating unit (a-2) in all the repeating units is preferably 0.1 to 50 mol%, more preferably 0.5 to 20 mol%, and particularly preferably 2 to 10 mol%. Its content is 0.1 mol%
If it is less than the above, the above-mentioned effects become insufficient. On the other hand, if it exceeds 50 mol%, the (co) silyl group or allyloxysilyl group present in excess in the cyclic olefin (co) polymer or the hydrolysis / condensation residue thereof may cause
The polymer is easily hydrolyzed, storage stability is poor, and the surface of the sheet film is not smooth.

The weight of the specific cyclic olefin (1) of the present invention
Method, or cyclic olefin (1) and cyclic olefin
The copolymerization with the resin (2) is carried out by the following method.
It is. As the polymerization catalyst, usually, Ni of Group 8 of the periodic table,
Form a cation complex or cation complex such as Pd or Co
The resulting catalyst is used. As a typical example, [Pd
(CH_ThreeCN)_Four] [BF_Four]_Two, [Pd (PhCN)_Four]
[SbF₆], Di-μ-chloro-bis (6-methoxybi
Cyclo [2.2.1] hept-2-ene-endo-5
σ, 2π) Pd (hereinafter abbreviated as “I”), I and methyl
Alumoxane (hereinafter abbreviated as MAO), I and AgSbF
₆, I and AgBF_Four, [(Η3-aryl) PdC
l]_TwoAnd AgSbF₆, [(Η3-aryl) PdC
l]_TwoAnd AgBF_Four, [(Η3-crotyl) Pd (
Crooctadiene)] [PF₆], [(1,5-cyclo
Octadiene) Pd (CH_Three) (Cl)] and PPh_ThreeAnd N
aB [3,5- (CF_Three)_TwoC₆H_Three]_Four, [(Η3-
Rotyl) Ni (cyclooctadiene)] [B ((C
F_Three)_{2 (}C₆H_Four)_Four], [NiBr (NPMe_Three)]_Four
And MAO, Ni (Octoate)_TwoAnd MAO, Ni
(Octoate)_TwoAnd B (C₆ F_Five)_ThreeAnd AlEt_Three,
Ni (octoate)_TwoAnd HSbF₆Reactant and BF_Three・
Et_TwoO and AlEt_Three, Ni (octoate)_TwoAnd H
SbF₆Reactant and BF_Three・ Et_TwoO and AlEt_Threereaction
Material, Ni (octoate)_TwoAnd HSbF₆With the reactants
AlEt_TwoF, Ni (octoate)_TwoAnd HSbF₆of
Reactants and AlEtF_Two , Ni (Naphthoate)_TwoAnd H
SbF₆Reactant and BF_Three・ Et_Two O and AlBu_Three , N
i (Naphthoate)_TwoAnd HSbF₆Reactant and B (C
₆ F_Five)_ThreeAnd AlEt _ThreeReaction product, Ni (Octoate
G)_TwoAnd Ph_Three CB (C₆ F_Five)_ThreeAnd AlEt_Three, T
olune ・ Ni (C₆ F_Five)_Two, Xylene N
i (C₆ F_Five)_Two, Mesitylen Ni (C₆ 
F_Five)_Two, Co (Neodecanoate) and MAO, etc.
No.

Examples of the solvent include alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane; aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; and aromatic hydrocarbon solvents such as toluene, benzene and xylene. Solvent, halogenated hydrocarbon solvent such as dichloromethane, 1,2-dichloroethylene, chlorobenzene, etc., ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol, dimethyl ether, nitromethane, N-methylpyrrolidone, pyridine, N, N′-
Dimethylimidazolidinone, dimethylformamide,
A solvent selected from polar solvents such as acetamide is used.

As a method of polymerization, a solvent, a monomer comprising a cyclic olefin and a molecular weight modifier are charged into a reaction vessel under a nitrogen or argon atmosphere,
The polymerization system is set to a temperature in the range. Next, the above-mentioned catalyst component is added, and polymerization is carried out in the range of -20 ° C to 100 ° C. The solvent / monomer weight ratio is in the range of 1-20. The molecular weight is adjusted to the desired molecular weight by the amount of the polymerization catalyst, the amount of a molecular weight regulator such as α-olefin, hydrogen, diphenyldihydrosilane, the conversion into a (co) polymer, and the polymerization temperature. . Termination of the polymerization is carried out by water, alcohol, organic acid, carbon dioxide or the like. A water / alcohol mixture of an acid selected from maleic acid, fumaric acid and oxalic acid is added to the (co) polymer solution,
The catalyst residue is separated and removed from the (co) polymer solution.
The (co) polymer is obtained by placing the (co) polymer solution in an alcohol selected from methanol, ethanol, isopropanol and the like, coagulating and drying under reduced pressure. In this step, unreacted monomers remaining in the (co) polymer solution are also removed.

The molecular weight of the (A) cyclic olefin (co) polymer used in the present invention is preferably a number average in terms of polystyrene measured by gel permeation chromatography using o-dichlorobenzene as a solvent. Molecular weight 5,000-1,000,000, weight average molecular weight 1
000-1,500,000, more preferably,
The number average molecular weight is 10,000 to 700,000, and the weight average molecular weight is 20,000 to 1,000,000. If the number average molecular weight is less than 5,000 and the weight average molecular weight is less than 10,000, the breaking strength of a film, thin film or sheet is often insufficient. On the other hand, when the number average molecular weight exceeds 1,000,000 and the weight average molecular weight exceeds 1,500,000, the molding processability of the obtained sheet or film is reduced, and the solution viscosity during casting film formation is reduced. Problems such as an increase in the temperature and an increase in the insoluble matter in the casting solvent occur, so that handling becomes difficult.

The (A) cyclic olefin (co) polymer of the present invention has a glass transition temperature of 150 ° C. to 400 ° C.
° C, preferably 250-380 ° C, more preferably 2 ° C
70 to 370 ° C, particularly preferably 300 to 350 ° C. Here, the glass transition temperature of the (A) cyclic olefin (co) polymer of the present invention is measured by dynamic viscoelasticity.
It is determined by the peak temperature of the temperature dispersion of nδ. (Storage modulus E ′, Loss modulus E ″, (Tan δ = E ″ / E ′) When the glass transition temperature is less than 150 ° C., the heat resistance is insufficient, while when the glass transition temperature exceeds 400 ° C. ,
Problems such as easy breaking and difficulty in forming a film body occur.

(B) Antioxidant Next, the (B) antioxidant used in the heat-resistant composition of the present invention includes (b-1) a phenolic antioxidant, and (b-
2) at least one selected from the group consisting of a phosphorus antioxidant and (b-3) a thioether antioxidant;

(B-1) a phenolic antioxidant;
-1) The phenolic antioxidant has a linear or branched chain at the 2-position and / or 6-position of the phenol group (C
Is characterized _{in that 1} -C ₂₀₎ alkyl group is substituted. Specific examples of (b-1) include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- ( 3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] -1,1-dimethylethyl {2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2, 6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl)
Phosphonate, thiodiethylene glycol bis [(3,
5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m
-Cresol), 2-octylthio-4,6-di (3,
5-di-t-butyl-4-hydroxyphenoxy) -s
-Triazine, 2,2'-methylenebis (4-methyl-
6-t-butyl-6-butylphenol), 2, -2 '
-Methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-
Butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m
-Cresol), 2,2′-ethylidenebis (4,6-
Di-t-butylphenol), 2,2′-ethylidenebis (4-s-butyl-6-t-butylphenol),
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate,
1.3.5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,
3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,3,5-tris [(3,5-di-t-butyl-4-
[Hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2
-Acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4-8,10-tetraoxaspiro [5,5 ] Undecane-bis [β- (3-
t-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1′-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2
'-Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4-methylphenol), 4,4'-
Butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1
-Dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3
-Methyl-6-t-butylphenol), 4,4'-bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis (6-t-butyl-2-methylphenol), , 5-Di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6- (1-methylcyclohexyl, styrenated phenol, 2,4- Bis ((octylthio) methyl) -5-methylphenol,
And the like. Among these, hindered phenolic antioxidants are preferred.

(B-2) a phosphorus antioxidant; (b-2)
The phosphorus-based antioxidant is a phosphate, which is a trivalent phosphorus compound, or a phosphate. Specific examples include bis- (2,6-di-t-butyl-4-methylphenyl) pentapentaerythritol diphosphite, tris (2,4-di-t-butylphenyl phosphite), tetrakis (2 4-di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6-dicumyl) Phenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis (2,4-di -T-butylphenyl) pentapentaerythritol-di-phosphite, bis (2,6-di-t
-Butyl-4-methoxycarbonylethyl-phenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-t-butyl-4-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite; Of these, phosphites and phosphates are preferred.

(B-3) a thioether-based antioxidant;
(B-3) Specific examples of the thioether-based antioxidant include dilauryl 3,3'-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-. Butylphenyl) sulfide,
Distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate, and the like.

The (B) antioxidant comprises (b-1) a phenolic antioxidant, (b-2) a phosphorus antioxidant and (b-3) a thioether antioxidant, each alone. Alternatively, they can be used in combination, but a combination system of two or more components (b-1) and (b-2) or (b-3) is preferable. The 5% weight loss temperature of these antioxidants by thermogravimetric analysis (TGA) was 250.
C. or higher is required, and more preferably 300 ° C. or higher.
When the temperature of 5% weight loss is less than 250 ° C., when the polymer is used at a high temperature of 150 ° C. or more, the polymer volatilizes and the effect of the antioxidant is lost.

In the heat-resistant resin composition of the present invention, (A) the cyclic olefin (co) polymer and (B) the antioxidant are used in an amount of (B) based on 100 parts by weight of the component (A).
The component is used in an amount of usually 0.05 to 5 parts by weight, preferably 0.3 to 5 parts by weight.
３3 parts by weight. (B) The use ratio of the component is 0.05
If the amount is less than 5 parts by weight, a sufficient effect of preventing oxidation deterioration cannot be obtained. On the other hand, if the amount exceeds 5 parts by weight, the quality of the obtained composition such as mechanical strength and glass transition temperature deteriorates, Undesirably, an increase in volatile components occurs.

(A) The cyclic olefin (co) polymer is
Examples of the method of adding the (B) antioxidant include a method of adding the specific cyclic olefin (1) or (2) at the time of synthesis or purification, a method of adding it to a cyclic olefin (co) polymer solution, A method of adding the (co) polymer at the time of purification is mentioned. In addition to the addition to the (co) polymer itself, it can be previously added to a solvent or the like, and is not particularly limited.

The (A) cyclic olefin-based (co) polymer of the present invention includes a norbornene-based polymer or an addition polymer which is a hydride of a conventionally known ring-opened polymer [for example, Japanese Patent Application Laid-Open No. -29260, JP-A-60-16870
JP, JP-A-60-26024, JP-A-2-5
JP-A-1511, JP-A-1-132625, JP-A-1-132626, JP-A-4-202404, JP-A-4-63807, JP-A-8-198
No. 919, Japanese Unexamined Patent Publication No. 9-508649, Japanese Unexamined Patent Publication No. 11-505880, Japanese Unexamined Patent Publication No. 61-292601.
And (co) polymers described in Japanese Patent Application Laid-Open Publication No. H10-15095), the resulting composition can be provided with excellent heat resistance, optical properties (transparency, low birefringence), and adhesion / adhesion.

In such a composition, the mixing ratio of the (A) cyclic olefin-based (co) polymer of the present invention and the other polymer depends on the type of the (co) polymer of the present invention and the other polymer. It is appropriately selected according to the compatibility between the two and the purpose of use of the composition, but in order to obtain a composition having excellent heat resistance, the (A) cyclic olefin-based (co) polymer of the present invention is required. The proportion is preferably from 5 to 95% by weight, more preferably from 10 to 90% by weight, particularly preferably from 20 to 80% by weight.

The heat-resistant resin composition of the present invention may further comprise one or more stabilizers having an effect of preventing deterioration of the resin due to light as long as the heat resistance is not impaired. Is also good. Among those used as stabilizers, examples of ultraviolet absorbers include benzophenone-based, salicylate-based, and benzotriazole-based agents.
Hereinafter, specific examples of the stabilizer are listed.

As the amine-based stabilizer, phenyl-α-
Naphthylamine, phenyl-β-naphthylamine, dioctylphenylamine, N, N′-diphenyl-p-phenylenediamine, N ′, N′-di-β-naphthyl-p
-Phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 2- (3,5-t-
Bis (1,2,2,6,6-pentamethyl-4-butyl-4-hydroxybenzyl) -2-n-butylmalonate
Piperidyl), poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6
6-tetramethyl-4-piperidyl) imino]}, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate.

Examples of the benzophenone-based stabilizer include 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone and the like.

Examples of the salicylate-based stabilizer include phenyl salicylate, 2,4-di-t-butylphenyl-
3 ', 5'-di-t-butyl-4'-hydroxybenzoate, phenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-methyl-4-t-butylphenyl-3', 5 '-Di-t-butyl-4'-hydroxybenzoate and the like

As the benzotriazole-based stabilizer, 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- (Hydroxy-3'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-3 ', 5'-di-t-amylphenyl ) Benzotriazole and the like.

Examples of the hydrazine-based stabilizer include maleic hydrazide, N, N'-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyl] hydrazine, N-salicyloyl-N'-aldehyde hydrazine and the like.

Epoxy stabilizers include epoxidized linseed oil, epoxidized soybean oil, epoxy butyl stearate, epoxy octyl stearate, epoxy lauryl stearate, and low molecular weight epoxy resin. Each of the above stabilizers is used alone or in combination of two or more.

The heat-resistant resin composition of the present invention may further contain, if necessary, a lubricant such as a metal salt of a higher dicarboxylic acid or a higher carboxylic acid ester, a plasticizer, an antistatic agent, an inorganic or organic colorant, a foaming agent, Inorganic and organic fillers, flame retardants other than those described above, surface gloss improvers, matting agents, and the like can be added. These various additives can be added during the production process of the resin composition.

The heat-resistant resin composition of the present invention contains (A) a cyclic olefin-based (co) polymer, the above-mentioned (B) an antioxidant, and optionally additives used in a solvent during casting. Obtained by mixing. As the casting solvent, a solvent in which both (A) and (B) are soluble is preferable.

The heat-resistant resin composition of the present invention can be used alone. However, since it has good affinity with various polar materials, it can be used as a glass fiber, a metal fiber, a carbon fiber, or a powder thereof. , Calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, potassium titanate and the like.

The heat-resistant resin composition of the present invention comprising a cyclic olefin copolymer and an antioxidant is suitable for applications requiring high heat resistance, for example, as a substitute for plastics for glass of liquid crystal substrates. That is, the TFT on the liquid crystal display substrate
The heat resistance required for the substrate material can be satisfied in processes such as exposure, development, and etching in the formation of (thin film transistor). Further, the heat-resistant resin composition of the present invention,
Since it has excellent optical transparency, heat resistance, adhesion / adhesion, and moisture absorption resistance, it can be used for light guide plates, polarizing films, liquid crystal panels, retardation films, transparent conductive films, OHP films, optical disks, optical fibers, lenses, and other electronic devices. It is also used for parts, medical containers, containers and the like.

[0051]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Further, the weight average molecular weight / number average molecular weight, intrinsic viscosity, and hue in Examples are measured as follows. Weight-average molecular weight / number-average molecular weight 150C gel permeation chromatography apparatus manufactured by Waters, Tosoh Corporation
Was measured at 120 ° C. using o-dichlorobenzene as a solvent using an H-type column manufactured by Toshiba Corporation. The obtained molecular weight is a standard polystyrene conversion value. Hue various antioxidants are added to the polymer solution at the time of casting,
Using the uniform solution, a film was formed by a casting method. Each of the obtained samples was used as a 15% methylene chloride solution, and the yellowness (YI value) was measured according to JIS K7103.
Was measured with transmitted light.

Synthesis Example 1 5-n-hexyl-2-norbornene 9 as a monomer
3.75 mmol, 500 mmol 2-norbornene,
5-triethoxysilyl-2-norbornene 31.25
As a solvent, 500 g of toluene as a solvent was charged into a 1-liter reactor under nitrogen. The temperature of the reaction system was adjusted to 10 ° C., 0.5 mmol of triethylaluminum, boron trifluoride / diethyl ether (BF ₃ .Et ₂ O) 0.1.
4 mmol, and finally nickel octanoate and antimony hexafluoride (HSbF ₆ ) were previously added at −15 ° C.
The polymerization was initiated by adding 0.2 mmol of a nickel compound reacted at a molar ratio of 1: 1 with a nickel atom. 30 ° C
For 2 hours, and the polymerization was terminated with ethanol. The conversion to the copolymer was 89%. 60 mmol of lactic acid was added to this copolymer solution and reacted with the catalyst component. The copolymer solution was placed in 5 liters of isopropanol, and the copolymer was coagulated, and unreacted monomers, the above-mentioned reactants and catalyst residues were removed from the copolymer. The coagulated copolymer was dried to obtain a copolymer A. The content of the structural unit containing a triethoxysilyl group in A is 270 MHz, ¹ H-N
According to MR analysis (absorption of ethoxylyl group methylene of 4 ppm, solvent: toluene-toluene, TMS standard), it was 4.9 mol%. The content of the structural unit derived from 5-n-hexyl-2-norbornene was 14.0 mol% from a calibration curve based on characteristic absorption of 721 cm ^-1 of infrared analysis. GPC measurement revealed that the copolymer A had a polystyrene-equivalent number average molecular weight of 200,000 and a weight average molecular weight of 440,000.

Synthesis Example 2 Synthesis Example 1 was repeated except that 5-n-hexyl-2-norbornene 1
Copolymer B was obtained in the same manner as in Synthesis Example 1, except that 25 mmol and 500 mmol of 2-norbornene were used. The conversion to the copolymer was 92%. 5-n-hexyl-
The content of the structural unit derived from 2-norbornene was determined to be 19.0 from the calibration curve based on characteristic absorption of 721 cm ^-1 of infrared analysis.
Mole%. The copolymer B had a polystyrene-equivalent number average molecular weight of 117,000 and a weight average molecular weight of 270,
000.

Synthesis Example 3 5-n-hexyl-2-norbornene 9 as a monomer
3.75 mmol, 500 mmol 2-norbornene,
8-methyl, 8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^{2, 5} 1 ^7,10] dodecene 31.25 but using mmol, copolymer C is performed in the same manner as in Synthesis Example 1
I got The conversion to the copolymer was 75%. 8-methyl in C, 8-methoxycarbonyl-3-tetracyclo [4.4.0.1 ^{2, 5} 1 ^7,10] ratio of the structure derived from dodecene infrared analysis 1730 cm ^{- 1} characteristic absorption Was 4.9 mol% from the calibration curve obtained by the above. The content of the structure derived from 5-n-hexyl-2-norbornene was 1 from the calibration curve based on the characteristic absorption of 721 cm ^{-1 in} the infrared analysis.
It was 4.5 mol%. The polystyrene equivalent number average molecular weight of C is 158,000, and the weight average molecular weight is 3
00,000.

Synthesis Example 4 5-n-hexyl-2-norbornene 9 as a monomer
3.75 mmol, 500 mmol 2-norbornene,
Copolymer D was obtained in the same manner as in Synthesis Example 1 except that 31.25 mmol of 5-ethylidene-2-norbornene was used. The conversion to the copolymer D was 80%. 5 in D
The proportion of structural units derived from -ethylidene-2-norbornene was 4.9 mol% by iodination titration. The content of the structure derived from 5-n-hexyl-2-norbornene was 14.0 mol% from a calibration curve obtained by characteristic absorption at 721 cm ^{-1 in} infrared analysis. The copolymer D had a number average molecular weight of 138,000 and a weight average molecular weight of 29.
It was 0000.

Example of Film Formation by Casting Method The cyclic olefin-based copolymer obtained in each of the above Synthesis Examples was dissolved in toluene and prepared so that TSC = 10%. After the solution was filtered through a 1-micrometer mesh filter, seed antioxidants (b-1), (b-2), and (b-3) were added in the amounts shown in Table 1 below, and a homogeneous solution was added. did. After applying this on a stainless steel substrate, the solvent was evaporated at room temperature. The obtained film is heated under vacuum at 210 ° C.
By heating for 2 hours, the solvent remaining in the film was completely vaporized, and the desired transparent film was obtained.

Examples 1 to 23 and Comparative Examples 1 to 3 The transparent films obtained by the above casting method were heated in air, and the oxidation resistance was evaluated by the change in hue (YI value). (B-1), (b-
Details of the various antioxidants 2) and (b-3) are as follows. (b-1) component; phenolic antioxidant a: pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate b: 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl
-4-hydroxybenzyl) benzene c: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate d: 2,6-di-t-butyl-4-methylphenol (b-2 ) Component: Phosphorus antioxidant e: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite f: tetrakis (2,4-di-t-butyl-5-) Methylphenyl)-
4,4'-biphenylenediphosphonite g: tris (2,4-di-t-butylphenyl) phosphite h: 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (b -3) Component: thioether-based antioxidant i: bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

According to the heat-resistant resin composition of the present invention, the coloring caused by the oxidative deterioration is greatly improved by combining a specific antioxidant with a cyclic olefin (co) polymer having a sufficiently high glass transition temperature. An object of the present invention is to solve the problem of yellow discoloration under severe conditions, which has been a problem in the past. With the development of this technology, it has become possible to make the glass substrate of the TFT liquid crystal plastic, a semiconductor encapsulant having high heat resistance and transparency, etc., which were not possible with conventional resins in terms of heat resistance.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C08F 232/00 C08F 232/00 (72) Inventor Noboru Oshima 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term in the company (reference) 4J002 BK001 EJ016 EV056 EV066 EW046 EW066 FD076 4J100 AR11P AR11Q AR28P AS15P AU21P BA77Q BB01P BB07P BC03P BC43P

Claims (5)

[Claims] 1. A cyclic olefin (co) polymer containing a repeating unit (a-1) represented by the following general formula (1) and (B) a thermogravimetric analysis (TGA) % Anti-oxidant having a weight loss temperature of 250 ° C. or higher,
Heat resistance containing at least one antioxidant selected from the group consisting of (b-1) a phenolic antioxidant, (b-2) a phosphorus antioxidant, and (b-3) a sulfur antioxidant. Resin composition. Embedded image [In the general formula (1), A ^{1 to} A ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkenyl group, a halogen atom, a halogenated hydrocarbon group, or - it indicates a (CH ₂₎ a polar group represented by _k X. Here, X is -C (O) OR ¹ , -OC
(O) R ² , wherein R ^{1 to} R ² are a hydrogen atom, and have ^{1 to 2} carbon atoms.
0 represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group and a halogen substituent thereof, and k represents an integer of 0 to 3. A ^{1 to} A ⁴ include A ¹ and A ² or A ³
And Binirideniru group formed by A ^4, A ¹ and A ^2, A ¹ and A
Also included are imide groups formed by ³ or A ³ and A ⁴ , and A ² and A ⁴ . l is an integer of 0 or 1. ] 2. The (A) cyclic olefin (co) polymer further comprises a repeating unit represented by the following general formula (2):
The heat-resistant resin composition according to claim 1, comprising (a-2). Embedded image [In the general formula (2), B ^{1 to} B ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and-(CR ⁴
R ⁵ ) _n Si (OR ³ ) _m R ⁶ _(3-m) ,-(CR ⁴ R ⁵ ) Si
^{(R 7 R 8) OSi (} OR 3) m R 6 (3-m), -C (O) O
(CH ₂ ) _n Si (OR ³ ) _m R ⁶ _(3-m) represents an alkoxysilyl group or an alloxysilyl group or a hydrolyzed / condensed residue thereof, and represents at least one of B ^{1 to} B ⁴ One includes an alkoxysilyl group or an allyloxysilyl group, or a hydrolyzed / condensed residue thereof. Where R ³
Represents a 1-10 alkyl or aryl group, R ⁴
To R ⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 0 to 3, n is an integer of 0 to 5, and r is 0 or 1. ] 3. The method according to claim 1 or 2,
(A) a cyclic olefin-based (co) polymer; and (B) a temperature at which 5% weight loss measured by thermogravimetric analysis (TGA) is 250 ° C.
(B-1) a hindered phenol-based antioxidant, (b-2) a phosphorus-based antioxidant comprising phosphite and / or phosphate, and (b-3) a thioether-based antioxidant. A heat-resistant resin composition containing at least one antioxidant selected from the group of antioxidants. 4. The (A) cyclic olefin (co) polymer comprises a repeating unit represented by the general formula (1):
1) is 50 to 99.9 mol%, and the repeating unit (a-2) represented by the general formula (2) is 50 to 0.1 mol% [(a
-1) + (a-2) = 100 mol%]. 5. The heat resistant resin composition according to claim 1, wherein the temperature at which the (B) antioxidant loses 5% by weight is 300 ° C. or higher.