JPH10168289A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in adhesion to metallic materials, etc., without detriment to features, such as heat resistance, high transparency and low birefringency, inherent in the constituent. cyclic polyolefin resin by mixing the polyolefin resin with a polycarbodiimide resin. SOLUTION: The cyclic polyolefin resin (A) is a ring opening polymer of a monomer represente by the formula (wherein R<1> to R<4> are each H, a halogen or a 1-10 C hydrocarbon or the like; R<1> and R<2> may be combined with each other; m and p are each an integer of 0 or greater), a product of hydrogenation thereof or the like. Desirably, in the formula, R<1> and R<3> are each H or a 1-10 hydrocarbon group, either R<2> or R<4> is H or a polar group except a hydrocarbon group, m and p are each 0-3; especially m+p=1. The polycarbodiimide (B) is prepared by using an organic polyisocyanate and modifying the product with e.g. trimellitic anhydride. When used in combination with an epoxy compound, the properties can be further improved. The weight ratio of component A to component B is desirably 90/10 to 99.8/0.2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent adhesion and heat resistance.

[0002]

2. Description of the Related Art In recent years, a cyclic olefin polymer has attracted attention as a heat-resistant transparent thermoplastic resin.
No. 625, JP-A-1-132626, JP-A-63-218726, JP-A-2-133413, JP-A-61-120816, JP-A-61-115912 and the like. ing. The cyclic polyolefin-based resin has a high glass transition temperature due to the rigidity of the main chain structure, and has high transparency due to having a bulky group in the main chain structure, and has small anisotropy of polarizability. This has characteristics such as low birefringence. Utilizing these characteristics of the cyclic polyolefin-based resin, applications in applications such as optical lenses, optical fibers, optical disks, and optical semiconductor encapsulation have been promoted. Among applications in these fields, high adhesion to metal materials and other polymer materials may be required, and further improvement in such adhesion of cyclic polyolefin-based resins has been required.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having excellent adhesion without impairing the inherent heat resistance and mechanical properties of a cyclic polyolefin resin.

[0004]

That is, the present invention provides:
An object of the present invention is to provide a resin composition comprising (A) a cyclic polyolefin-based resin and (B) polycarbodiimide.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
As the component (A), a cyclic polyolefin resin is used. Examples of the cyclic polyolefin resin used in the present invention include the following polymers. A ring-opening polymer of a specific monomer represented by Chemical Formula 1; a ring-opening copolymer of a specific monomer and a copolymerizable monomer; a hydrogenated polymer of the ring-opening (co) polymer; Hydrogenated (co) polymer after cyclization of cyclic (co) polymer by Friedel-Crafts reaction Saturated copolymer of specific monomer and unsaturated double bond-containing compound

[0006]

Embedded image

In the formula, R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group. Good. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or It may form a polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. ]

<Specific monomer> Among the specific monomers represented by the above formula ( ¹⁾ , R ¹ and R ³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. , R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group; An integer,
p is an integer of 0 to 3, more preferably m + p = 0 to 0
4, more preferably 0 to 2, particularly preferably 1. Among the specific monomers, the polar groups are particularly those of the formula-(CH2) nC
The specific monomer which is a specific polar group represented by OOR is preferable in that a hydrogenated product of the obtained cyclic polyolefin polymer has a high glass transition temperature and a low hygroscopicity. In the above formula for the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained cyclic polyolefin-based polymer becomes higher.
Is preferred in that the synthesis is easy and the obtained cyclic polyolefin-based polymer has a high glass transition temperature. Further, in the general formula 1, R ¹ or R ³ is preferably an alkyl group, and is preferably an alkyl group having 1 to 4 carbon atoms, more preferably 1 alkyl group.
To 2, particularly preferably a methyl group, and particularly preferably this alkyl group is bonded to the same carbon atom to which the specific polar group represented by the above formula-(CH2) nCOOR is bonded. Moreover, the specific monomer in which m is 1 in the general formula 1 is preferable in that a cyclic polyolefin-based polymer having a high glass transition temperature can be obtained.

Specific examples of the specific monomer represented by the above formula 1 include the following compounds. Bicyclo [2.2.1] hept-2-ene, tricyclo [5.
2.1.02,6] -8-decene, tetracyclo [4.
4.0.12,5. 17,10] -3-dodecene, pentacyclo [6.5.1.13,6. 02,7. 09,13] -4-pentadecene, pentacyclo [7.4.0.12,5. 19,1
2.08,13] -3-pentadecene, tricyclo [4.
4.0.12,5] -3-undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxy Carbonylbicyclo [2.2.1] hept-2-ene, 5-
Methyl-5-methoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-cyanobicyclo [2.2.
1] Hept-2-ene, 8-methoxycarbonyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.
0.12,5. 17,10] -3-dodecene, 8-n-propoxycarbonyltetracyclo [4.4.0.12,5. 1
7,10] -3-dodecene, 8-isopropoxycarbonyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8-n-butoxycarbonyltetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8-
Methyl-8-methoxycarbonyltetracyclo [4.
4.0.12,5. 17,10] -3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.
12,5. 17,10] -3-dodecene, 8-methyl-8-n
-Propoxycarbonyltetracyclo [4.4.0.1
2,5.17,10] -3-dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.12,
5.17,10] -3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.12,5.
[17,10] -3-dodecene, dimethanooctahydronaphthalene, ethyltetracyclododecene, 6-ethylidene-
2-tetracyclododecene, trimetanooctahydronaphthalene, pentacyclo [8.4.0.12,5. 19,1
2.08,13] -3-Hexadecene, heptacyclo [8.
7.0.13,6. 110,17. 112,15. 02,7. 011,1
6] -4-eicosene, heptacyclo [8.8.0.1
4,7. 111,18. 113,16. 03,8. 012,17] -5
Hene eicosene, 5-ethylidene bicyclo [2.2.
1] Hept-2-ene, 8-ethylidenetetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 5-phenylbicyclo [2.2.1] hept-2-ene, 8
-Phenyltetracyclo [4.4.0.12,5. 17,1
0] -3-dodecene, 5-fluorobicyclo [2.2.
1] Hept-2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-pentafluoroethyl Bicyclo [2.2.1] hept-2
-Ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene, 5,6-difluorobicyclo [2.
2.1] Hept-2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,5,6-tris (fluoromethyl)
Bicyclo [2.2.1] hept-2-ene, 5,5
6,6-tetrafluorobicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6
-Difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-
Trifluoro-5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl)
Bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5-heptafluoro-iso-propyl-6
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2. 2.1] Hept-2-ene, 5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.
1] Hept-2-ene, 5,5,6-trifluoro-6
-Heptafluoropropoxybicyclo [2.2.1] hept-2-ene, 8-fluorotetracyclo [4.4.
0.12,5. 17,10] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.12,5. 17,10] -3
-Dodecene, 8-difluoromethyltetracyclo [4.
4.0.12,5. 17,10] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.12,5. 17
10] -3-dodecene, 8-pentafluoroethyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8,8-difluorotetracyclo [4.4.0.1
2,5. 17,10] -3-dodecene, 8,9-difluorotetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8-
Methyl-8-trifluoromethyltetracyclo [4.
4.0.12,5. [17,10] -3-dodecene, 8,8,9
-Trifluorotetracyclo [4.4.0.12,5. 1
7,10] -3-dodecene, 8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.12,5.17,1
0] -3-dodecene, 8,8,9,9-tetrafluorotetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17,10] −
3-dodecene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5
. [17,10] -3-dodecene, 8,9-difluoro-
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8,
8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.12,5. 17,10] -3
-Dodecene, 8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.12,5.
17,10] -3-dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8,9-difluoro-8-heptafluoroiso
-Propyl-9-trifluoromethyltetracyclo [4.4.0.12,5. 17, 10] -3-dodecene, 8-
Chloro-8,9,9-trifluorotetracyclo [4.
4.0.12,5. 17,10] -3-dodecene, 8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.12,5. 17,10] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl)
Tetracyclo [4.4.0.12,5. 17,10] -3-dodecene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.12,
Five . [17,10] -3-dodecene. Among these, from the viewpoint of heat resistance of the obtained polymer,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0} ] -3-dodecene, 8-
Ethylidenetetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [7.4.0.1 ^2,5 . ^19,12 . 0 ^8,13 ] -3
-Pentadecene is preferred, and from the viewpoint of compatibility with the component (A), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . And most preferably 1 ^{7,1 0]} -3- dodecene.

<Copolymerizable Monomer> In the ring-opening polymerization step, the above-mentioned specific monomer may be independently subjected to ring-opening polymerization. Ring-opening copolymerization may be performed. Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, and tricyclo [5.2.1.
0 ^{2, 6]} -3-decene, 5-ethylidene-2-norbornene, it can be mentioned cycloolefins such as dicyclopentadiene. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12.
It is. Specified in the presence of unsaturated hydrocarbon-based polymers containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene The monomer may be subjected to ring-opening polymerization. The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Unsaturated Double Bond-Containing Compound> Further, in order to obtain a cyclic olefin-based polymer comprising a saturated copolymer, examples of the unsaturated double bond-containing compound used together with the specific monomer include: Examples thereof include olefin compounds having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene, and butene.

<Polymerization catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo and Re, and (b) a periodic table IA of Deming.
Group II elements (eg, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Z
n, Cd, Hg, etc.), Group IIIA elements (eg, B,
Al, a group IVA element (eg, Si, Sn, Pb, etc.) or a group IVB element (eg, Ti, Zr, etc.) having at least one element-carbon bond or element-hydrogen bond A catalyst comprising a combination with at least one member selected from the group consisting of: In this case, in order to enhance the activity of the catalyst, an additive (c) described below is used.
May be added. Representative examples of compounds of W, Mo or Re suitable as the component (a) include:
Japanese Patent Application Laid-Open No. 1-2 such as WCl ₆ , MoCl ₅ , ReOCl ₃
Compounds described in Japanese Patent No. 40517 can be exemplified. (B) Specific examples of the _{component, n-C 4 H 9 Li} ,
(C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C _{2
H 5) 1.5 AlCl 1.5, (} C 2 H 5) AlCl 2, methylalumoxane, LiH, etc. JP 1-240517
Can be mentioned. As typical examples of the component (c), which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 are used. be able to.

The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the specific monomer is such that "component (a): specific monomer" is usually 1: 500 to 1: 50000. , Preferably in the range of 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that (a) :( b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. The molar ratio of the component (a) to the component (c) is such that (c) :( a) is 0.1.
005: 1 to 15: 1, preferably 0.05: 1 to 7:
1 range.

In the present invention, a catalyst comprising a vanadium compound and an organoaluminum compound is used as a catalyst for synthesizing a saturated copolymer of a monomer represented by the formula 1 and an unsaturated double bond-containing compound. Is used. As the vanadium compound, the general formula VO (OR) _{a Xb} or V
(OR) _c X _d (however, RHA hydrocarbon group, 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
≦ 4, 3 ≦ c + d ≦ 4) a vanadium compound represented by the following formula:
Alternatively, these electron donor adducts are used. Examples of electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles, Examples include nitrogen-containing electron donors such as isocyanates. As the organoaluminum compound catalyst component, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond
Seeds are used. The ratio of the catalyst component is 2 or more, preferably 2 to 50, particularly preferably 3 to 20 in terms of the ratio of aluminum atoms to vanadium atoms (Al / V).

<Solvent for Ring-Opening Polymerization Reaction> Solvent used in ring-opening polymerization reaction (solvent constituting molecular weight modifier solution, solvent for specific monomer and / or metathesis catalyst)
Examples thereof include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; and aromatics such as benzene, toluene, xylene, ethylbenzene, and cumene. Hydrocarbons, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibromide, chlorobenzene, chloroform, compounds such as halogenated alkanes such as tetrachloroethylene, aryl, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate And saturated carboxylic esters such as dimethoxyethane, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. There can be used as a mixture. Of these, aromatic hydrocarbons are preferred. As the amount of the solvent used, “solvent: specific monomer (weight ratio)”
The amount is usually 1: 1 to 10: 1, preferably 1:
The amount is 1 to 5: 1.

<Molecular Weight Controlling Agent> The molecular weight of the ring-opened polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight controlling agent must be present in the reaction system. Adjust with. Here, suitable molecular weight regulators include, for example, ethylene, propene,
Α- such as butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene
Olefins and styrene can be mentioned, of which 1-butene and 1-hexene are particularly preferred.
These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier to be used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.
5 moles.

The cyclic olefin polymer used in the present invention has an intrinsic viscosity (ηinh) of 0.2 to 5.0, and a number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC). Is 8,
000-100,000, weight average molecular weight (Mw) is 2
Those having a range of from 000 to 300,000 are preferable.

<Hydrogenation catalyst> The ring-opened polymer obtained as described above can be hydrogenated using a hydrogenation catalyst. The hydrogenation reaction is carried out in a conventional manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and a normal pressure to 300
Atmospheric pressure, preferably 3 to 200 atm.
The reaction is carried out at 0 ° C, preferably at 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the homogeneous catalyst include nickel / naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octanoate / n-butyllithium, titanocene dichloride /
Diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like can be mentioned. it can. The form of the catalyst may be powdery or granular. These hydrogenation catalysts, ring-opening polymer: hydrogenation catalyst (weight ratio),
It is used at a ratio of 1: 1 × 10 ⁻⁶ to 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating at the time of molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

The polycarbodiimide particularly preferably used as the component (B) of the present invention will be described below. As the polycarbodiimide, those having a repeating unit represented by the following formula can be used. -N = C = NR ^1- [wherein, R ¹ represents a divalent organic group]

The method for synthesizing the polycarbodiimide is not particularly limited. For example, an organic polyisocyanate may be prepared in the presence of a catalyst for promoting the carbodiimidation reaction of an isocyanate group (hereinafter also referred to as a “carbodiimidation catalyst”). By reacting, polycarbodiimide can be synthesized.

The organic polyisocyanate used for the synthesis of the polycarbodiimide is preferably an organic diisocyanate. Examples of such organic diisocyanates include phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-triene Range isocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4'-
Diisocyanate, 3,3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane -4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, Cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, 1-methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexane-1,3-bis (methylisocyanate), cyclohexane-1,4-
Bis (methyl isocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate Nate, hexamethylene-1,
Reaction of 6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, and the like, and a stoichiometric excess of these organic diisocyanates with a bifunctional active hydrogen-containing compound And an isocyanate prepolymer obtained at the same time. These organic diisocyanates can be used alone or as a mixture of two or more.

Other organic polyisocyanates optionally used together with organic diisocyanates include, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, Diphenylmethane-2,5,4'-triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4"-
Triisocyanate, diphenylmethane-2,4,
2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methylisocyanate Nate), 3,5-dimethylcyclohexane-1,3,5-
Tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2 '
Triisocyanate, dicyclohexylmethane-2,
A trifunctional or higher organic polyisocyanate such as 4,4'-triisocyanate or a stoichiometric excess of these trifunctional or higher polyisocyanate and a bifunctional or higher polyfunctional active hydrogen-containing compound; And a terminal isocyanate prepolymer obtained by the above reaction.

The above-mentioned other organic polyisocyanates can be used singly or as a mixture of two or more kinds. The amount of the organic polyisocyanate used is usually 100 parts by weight of the organic diisocyanate. 0 to 40 parts by weight, preferably 0 to 20 parts by weight.

Further, when synthesizing the polycarbodiimide, if necessary, an organic monoisocyanate is added so that when the organic polyisocyanate contains the above-mentioned other organic polyisocyanate, the molecular weight of the obtained polycarbodiimide is reduced. It can be appropriately regulated, and a polycarbodiimide having a relatively low molecular weight can be obtained by using an organic diisocyanate in combination with an organic monoisocyanate.

Examples of such organic monoisocyanates include alkyl monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, lauryl isocyanate and stearyl isocyanate, and cyclohexyl. Cycloalkyl monoisocyanates such as isocyanate, 4-methylcyclohexyl isocyanate and 2,5-dimethylcyclohexyl isocyanate, phenyl isocyanate, o-tolyl isocyanate, m
-Tolyl isocyanate, p-tolyl isocyanate,
2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-chlorophenyl isocyanate, 4-chlorophenyl isocyanate, 2-trifluoromethylphenyl isocyanate, 4-trifluoromethylphenyl isocyanate, naphthalene-1-isocyanate And aryl monoisocyanates.

These organic monoisocyanates can be used singly or as a mixture of two or more. The amount used depends on the desired molecular weight of the polycarbodiimide and the other organic polyisocyanates. Total organic polyisocyanate component 1 varies depending on the presence or absence of isocyanate
0 to 40 parts by weight, preferably 0 to 2 parts by weight, per 100 parts by weight
0 parts by weight.

Examples of the carbodiimidation catalyst include 1-phenyl-2-phospholene-1-oxide,
-Phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide,
1-phenyl-3-methyl-2-phospholene-1-sulfide, 1-ethyl-2-phospholene-1-oxide,
1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-sulfide, 1
-Ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-
Methyl-3-methyl-2-phospholene-1-oxide,
1-methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide and phosphorene compounds such as 3-phospholene isomers thereof, iron pentacarbonyl, diiron nonacarbonyl, Metal carbonyl complexes such as tetracarbonyl nickel, hexacarbonyl tungsten, hexacarbonyl chromium, beryllium, aluminum, zirconium, chromium, acetylacetone complexes of metals such as iron, trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tri-t-butyl phosphate, Phosphate esters such as triphenyl phosphate and the like can be mentioned.

The above carbodiimidization catalyst can be used alone or in combination of two or more. The amount of the catalyst to be used is generally 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of all organic isocyanate components.

The polycarbodiimide synthesis reaction can be carried out without a solvent or in a suitable solvent. The solvent may be any solvent that can dissolve the polycarbodiimide by heating during the synthesis reaction. For example, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
1,1,1,2-tetrachloroethane, 1,1,2,2
-Tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-
Halogenated hydrocarbon solvents such as trichlorobenzene and trichloromethylbenzene, dioxane, anisole,
Ether solvents such as tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl ether; Cyclohexanone, 2-acetylcyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,
Cycloheptanone, 1-decalone, 2-decalone, 2,
4-dimethyl-3-pentanone, 4,4-dimethyl-2
-Pentanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5
-Methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone,
Ketone solvents such as -decanone and 4-decanone; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and cumene; N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-benzyl- 2
-Pyrrolidone, N-methyl-3-pyrrolidone, N-acetyl-3-pyrrolidone, N-benzyl-3-pyrrolidone, formamide, N-methylformamide, N, N-
Dimethylformamide, N-ethylformamide, N,
N-diethylformamide, acetamide, N, N-methylacetamide, N, N-dimethylacetamide, N
Amide solvents such as -methylpropionamide, aprotic polar solvents such as dimethyl sulfoxide, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate; Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate,
Acetate solvents such as diethylene glycol monobutyl ether acetate can be exemplified. These solvents can be used alone or in combination of two or more.

In the synthesis of polycarbodiimide, the solvent is usually used when the concentration of all organic isocyanate components is 0.5%.
６０60% by weight, preferably 5-50% by weight. If the concentration of the total organic isocyanate component is too low, the reaction rate will be slow and the productivity will be reduced, while if the concentration is too high, the polycarbodiimide formed may gel during the synthesis reaction.

The temperature of the polycarbodiimide synthesis reaction is as follows:
It is appropriately selected according to the type of the organic isocyanate component and the carbodiimidization catalyst, but is usually from 20 to 200 ° C. In the synthesis reaction of polycarbodiimide, the organic isocyanate component may be added in its entirety before the reaction, or a part or all of it may be added continuously or stepwise during the reaction.

In addition, a compound capable of reacting with the isocyanate group is added at an appropriate reaction stage from the initial stage to the late stage of the polycarbodiimide synthesis reaction, and the terminal isocyanate group of the polycarbodiimide is sealed to obtain a polycarbodiimide. The molecular weight of the carbodiimide can be adjusted, and it can be added at a later stage of the polycarbodiimide synthesis reaction to regulate the molecular weight of the obtained polycarbodiimide to a predetermined value. Examples of the compound capable of reacting with such an isocyanate group include alcohols such as methanol, ethanol, isopropanol and cyclohexanol, and amines such as dimethylamine, diethylamine and benzylamine.

The polycarbodiimide synthesized as described above is separated from the solution if necessary. In this case, as a method for separating polycarbodiimide, for example, a polycarbodiimide solution is added to a non-solvent inert to the polycarbodiimide, and the resulting precipitate or oil is separated and collected by filtration or decantation. , A method of separating and collecting by spray drying, a method of separating and collecting by utilizing a change in solubility of the obtained polycarbodiimide with respect to the solvent used in the synthesis, that is, a polycarbodiimide dissolved in the solvent immediately after synthesis. When is precipitated by lowering the temperature of the system, a method of separating and collecting the suspension from the suspension by filtration and the like can be mentioned, and these separation and collecting methods can be appropriately combined.

In the present invention, the polycarbodiimide has a number average molecular weight (Mn) in terms of polystyrene, determined by gel permeation chromatography (GPC), of usually 400 to 500,000, preferably 1,000 to 500.
200,000, more preferably 2,000 to 10
It is 0000.

In the present invention, the polycarbodiimide used as the component (B) is, if necessary, one of compounds containing a graft-reactive group and a carboxylic anhydride group (hereinafter also referred to as “reactive compound”). Resin grafted with more than one kind (hereinafter also referred to as “modified polycarbodiimide”),
Alternatively, by using an epoxy compound in combination with the modified polycarbodiimide, the curing properties are improved, and the rigidity of the obtained resin composition of the present invention is improved,
Furthermore, the impact resistance when using an inorganic filler is further improved.

Here, the reactive compound used in the synthesis of the modified polycarbodiimide is a compound having a graft reactive group and a carboxylic anhydride group, and is an aromatic compound,
It can be an aliphatic compound or an alicyclic compound. Among these, the alicyclic compound may be a carbocyclic compound or a heterocyclic compound. The graft-reactive group in the reactive compound means a group that reacts with polycarbodiimide to give a modified polycarbodiimide in which a residue of the reactive compound having a carboxylic anhydride group is grafted. Such a graft reactive group may be any functional group having active hydrogen, such as a carboxyl group or a primary group.
Grade or secondary amino groups can be mentioned. In this reactive compound, one or more same or different graft-reactive groups can be present, and one or more carboxylic anhydride groups can be present.

Examples of such a reactive compound include trimellitic anhydride, benzene-1,2,3-tricarboxylic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, and naphthalene-1,4. , 5-tricarboxylic anhydride, naphthalene-2,3,6-tricarboxylic anhydride, naphthalene-1,2,8-tricarboxylic anhydride,
4- (4-carboxybenzoyl) phthalic anhydride, 4
-(4-carboxyphenyl) phthalic anhydride, 4-
(4-carboxyphenoxy) aromatic tricarboxylic anhydrides such as phthalic anhydride, pyromellitic monoanhydride monomethyl ester, 3,3 ', 4,4'-benzophenonetetracarboxylic monoanhydride monomethyl ester,
Aromatic tetracarboxylic monoanhydride monoalkyl esters such as 3,3 ', 4,4'-biphenyltetracarboxylic monoanhydride monomethyl ester, 3-carboxymethylglutaric anhydride, butane-1,2,4 Aliphatic tricarboxylic anhydrides such as tricarboxylic acid-1,2-anhydride and propene-1,2,3-tricarboxylic acid-1,2-anhydride; 3-amino-4-cyano-5-methylphthalic acid Anhydride, 3-amino-4-cyano-5,6-diphenylphthalic anhydride, 3-methylamino-4-cyano-5
Aminoaromatic dicarboxylic anhydrides such as -methylphthalic anhydride, 3-methylamino-4-cyano-5,6-diphenylphthalic anhydride; aminosuccinic anhydride;
-Amino-1,2-butanedicarboxylic anhydride, 4-aminohexahydrophthalic anhydride, N-methylaminosuccinic anhydride, 4-methylamino-1,2-butanedicarboxylic anhydride, 4-methyl Examples thereof include amino aliphatic dicarboxylic anhydrides such as aminohexahydrophthalic anhydride. Among these reactive compounds, trimellitic anhydride is particularly preferred. The above-mentioned reactive compounds can be used alone or in combination of two or more.

The modified polycarbodiimide is obtained by adding at least one reactive compound to a polycarbodiimide having a repeating unit represented by the following formula (2) in the presence of a suitable catalyst.
Alternatively, it can be synthesized by grafting (hereinafter also referred to as “denaturation reaction”) at an appropriate temperature in the absence of the compound. In this case, the polycarbodiimides can be used alone or as a mixture of two or more.

The amount of the reactive compound used in the modification reaction is appropriately adjusted according to the kind of the polycarbodiimide, the compound and the use of the resin composition. For moles,
It is used so that the amount of the graft reactive group in the reactive compound is 0.01 to 1 mol, preferably 0.02 to 0.8 mol. In this case, if the proportion of the graft-reactive group is less than 0.01 mol, long-time heating is required to cure the polycarbodiimide, while if it exceeds 1 mol, the original properties of the polycarbodiimide may be impaired. . In the above modification reaction, the reaction between the graft reactive group of the reactive compound and the polycarbodiimide progresses quantitatively, and a graft reaction suitable for the amount of the compound used is achieved.

The denaturation reaction can be carried out without solvent, but is preferably carried out in a suitable solvent. Such a solvent is not particularly limited as long as it is inert to the polycarbodiimide and the reactive compound and can dissolve them. As this solvent,
Examples thereof include the above-mentioned ether solvents, amide solvents, ketone solvents, aromatic hydrocarbon solvents, aprotic polar solvents and the like used in the synthesis of polycarbodiimide. These solvents can be used alone or in combination of two or more. When the solvent used during the synthesis of the polycarbodiimide can be used for the modification reaction, the polycarbodiimide solution obtained by the synthesis can be used as it is.

The amount of the solvent used in the modification reaction is usually from 10 to 10,000 per 100 parts by weight of the total amount of the reaction raw materials.
0 parts by weight, preferably 50 to 5,000 parts by weight.
The temperature of the modification reaction is appropriately selected depending on the types of the polycarbodiimide and the reactive compound.
Hereinafter, it is preferably −10 to + 80 ° C. The number average molecular weight (Mn) in terms of polystyrene of the modified polycarbodiimide obtained as described above determined by gel permeation chromatography (GPC) is usually 500.
~ 1,000,000, preferably 1,000-40
000, more preferably 2,000 to 200,0
00.

The modified polycarbodiimide obtained as described above is usually used after being separated from a solution. As a method for separating the modified polycarbodiimide obtained as a solution at the time of the synthesis from the solvent, a method similar to the above-described method for separating polycarbodiimide can be exemplified.

The modified polycarbodiimide of the present invention is obtained by reacting a graft reactive group in a reactive compound with a repeating unit (-N = C = NR1-) of the polycarbodiimide to form a carboxylic anhydride group of the compound. Has a structure in which a residue having a structure is grafted, and has a structure substantially different from that of the polycarbodiimide before the modification reaction. Therefore, the modified polycarbodiimide is different in properties from the polycarbodiimide before the modification reaction,
By mixing and heating with an epoxy compound described below, even without using a curing catalyst due to the action of the carboxylic acid anhydride group in the modified polycarbodiimide, it is usually 100 to 100%.
It has the property of easily curing at a temperature of 350 ° C, preferably 150 to 300 ° C.

The epoxy compound used for the modified polycarbodiimide of the component (B) of the present invention is a compound having one or more epoxy groups in the molecule, and may have a functional group other than the epoxy group. The molecular weight is not particularly limited, but is, for example, 70 to 20,000. Such epoxy compounds include, for example, glycidol, glycidyl acrylate, glycidyl methacrylate,
3,4-epoxycyclohexyl acrylate, 3,4
-Epoxycyclohexyl methacrylate and various epoxy resins. Further, a part of the epoxy compound may be substituted with a halogen atom.

Preferred epoxy compounds are epoxy resins. Examples thereof include glycidyl ether type epoxy resins and glycidyl ester type epoxy resins represented by bisphenol type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin and the like. , Aromatic glycidylamine type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, liquid rubber-modified epoxy resins, and the like.

The above-mentioned epoxy compounds can be used alone or in combination of two or more. The amount used is usually 5 to 500 parts by weight, preferably 10 to 100 parts by weight of the modified polycarbodiimide.
３００300 parts by weight. In this case, if the amount of the epoxy compound used is less than 5 parts by weight, the effect of improving the curing rate tends to decrease, while if it exceeds 500 parts by weight, the heat resistance of the resin composition tends to decrease.

The weight ratio (A) / (B) of the component (A) and the component (B) in the resin composition of the present invention is preferably 50/50 to 99.99 / 0.01, more preferably. Is 70/30 to 99.95 / 0.05, more preferably 80/20 to 99.9 / 0.1, and particularly preferably 90 /
10 to 99.8 / 0.2. When the amounts of the components (A) and (B) are within this range, the effect of improving workability, transparency and adhesion is large.

In order to improve mechanical properties, the resin composition of the present invention contains glass fiber, carbon fiber, metal fiber, metal flake, glass bead, wollastonite, rock filler, calcium carbonate, talc, mica, Fillers such as glass flakes, milled fibers, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, and potassium titanate whiskers can be used alone or in combination of two or more. Can also be used.

Next, the resin composition of the present invention contains known flame retardants, antibacterial agents, wood flour, coupling agents, antioxidants, plasticizers, coloring agents, lubricants, antistatic agents, silicone oil, foams Additives such as agents can be blended. Can be granted.

The resin composition of the present invention can be prepared by using various extruders,
It is obtained by kneading each component using a Banbury mixer, kneader, roll, feeder ruder, or the like. The kneading temperature is preferably 100 to 350C, more preferably 150 to 300C. When kneading each component, each component may be kneaded at once, or may be added and kneaded in several times. Kneading may be carried out in a multi-stage addition type using an extruder,
Alternatively, the mixture can be kneaded with a Banbury mixer, a kneader, or the like, and then pelletized with an extruder. From the composition produced by the production method of the present invention, a molded article can be produced by known molding means, for example, injection molding, compression molding, extrusion molding and the like.

The surface of the prepared composition is made of an inorganic compound, an organic silicon compound such as a silane coupling agent, an acrylic resin, a vinyl resin, a melamine resin, an epoxy resin, a fluorine resin, a silicone resin, or the like. A hard coat layer can be formed. Examples of the means for forming the hard coat layer include known methods such as a thermosetting method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method. Thereby, heat resistance, optical properties, chemical resistance, abrasion resistance, moisture permeability and the like of the molded product can be improved.

The use of the composition produced by the production method of the present invention is not particularly limited, and it can be used in a wide range. For example, eyeglass lenses, general camera lenses, pickup lenses, video cameras Lenses such as lenses, telescope lenses and laser beam lenses, optical video disks, audio disks, document file disks, optical disks such as memory disks, optical materials such as optical films such as OHP films,
It can be particularly suitably used as a sealing material for optical semiconductors such as photointerrupters, photocouplers and LED lamps, and a sealing material for IC memories such as IC cards.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

REFERENCE EXAMPLE 1 As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3 rd decene
250 parts and 41 parts of 1-hexene were charged into a nitrogen-purged reaction vessel with 750 parts of toluene and heated to 60 ° C. To this, triethylaluminum (1.5 mol /
l) Toluene solution 0.62 parts, tBuOH / Me
Denaturation with OH (tBuOH / MeOH / W = 0.35 /
0.3 / 1; molar ratio) WCl ₆ solution (concentration 0.05
(Mol / l), and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a ring-opened polymer solution (a). The polymerization conversion in this polymerization reaction was 97%, and the intrinsic viscosity (ηin
h) was 0.45.

[0055]

Embedded image

Reference Example 2 4000 parts of the polymer solution (a) obtained in Reference Example 1 was placed in an autoclave, and R was added thereto.
0.48 parts of uHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ were added, the hydrogen gas pressure was 100 kg / cm ² , and the reaction temperature was 165.
The mixture was heated and stirred for 3 hours under the condition of ° C. After cooling the obtained reaction solution, hydrogen gas was released to obtain a hydrogenated polymer solution (b). The hydrogenated polymer thus obtained was poured into a large amount of methanol to coagulate the polymer. The hydrogenation rate of the hydrogenated polymer A-1 thus obtained was substantially 100%.

REFERENCE EXAMPLE 3 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
A ring-opening polymerization reaction was performed in the same manner as in Reference Example 1 except that 200 parts of dodecene was used to obtain a polymer solution (c). [Reference Example 4] A hydrogenation reaction was carried out in the same manner as in Reference Example 2 except that the polymer solution (c) was used instead of the polymer solution (a) to obtain a hydrogenated polymer A-2.

REFERENCE EXAMPLE 5 A reaction vessel equipped with a stirring blade, a gas inlet tube, a thermometer and a dropping funnel was sufficiently replaced with nitrogen gas, and 2,000 parts of cyclohexane dehydrated and dried with a molecular sieve was placed in the reaction vessel. Under an atmosphere of nitrogen, 75 parts of tetracyclododecene, n-hexane solution of ethyl aluminum sesquichloride (1 mol /
l) 6.6 parts were added. Then, the internal temperature of the reaction vessel was set at 10
While maintaining the temperature at ° C., a mixed gas of ethylene and nitrogen (ethylene: 10 l / Hr, nitrogen: 40 l / Hr) was passed through the gas introduction tube for 10 minutes. VO in this solution
(OC ₂ H ₅₎ Cl ₂ in n- hexane (0.07Mo
1 / l) 23 parts was dropped from a dropping funnel to start a copolymerization reaction, and the reaction was carried out while passing the mixed gas. After a lapse of 30 minutes from the start of the reaction, a small amount of methanol was added to the reaction solution to stop the polymerization reaction, and then the polymerization solution was poured into a large amount of methanol to coagulate and collect the polymer A-3.

[0059]

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 unless it exceeds the gist thereof. In the examples, parts and% are by weight unless otherwise specified. Various evaluations in the examples are values measured as follows. Adhesion (A) The adhesion to the metal material was determined by sealing a part (approximately 5 mm long) of a metal piece of about 30 mm × 1 mm by a press molding method and impregnating the molded article with red ink for 24 hours. The percentage of the red ink impregnated along the metal piece in the molded article was evaluated. Adhesion (B) Each composition was laminated on a glass cloth base epoxy substrate to a thickness of about 0.5 mm by a press molding method, and the adhesion was evaluated by the degree of easy removal of the claw from the epoxy substrate. As the adhesion,
○: It is difficult to peel off, △: It peels off if a little force is applied,
X: Evaluated with an index of easy peeling. A flat plate having a thickness of about 0.1 mm was prepared from the transparent composition by a press molding method, and cloudiness of the flat plate was visually observed to evaluate the transparency.

Polycarbodiimide (B) -1 to (B)-
7 (B) -1; polycarbodiimide was obtained by the following method. 50 g of diphenylmethane-4,4'-diisocyanate (MDI) and 3.1 g of phenylisocyanate
And 1-phenyl- in 200 g of cyclohexanone
0.044 3-methyl-2-phospholene-1-oxide
The reaction was carried out at 80 ° C. for 4 hours in the presence of g to obtain a solution of polycarbodiimide (P-MDI) (Mn = 3,500). Then, it was separated and dried.

(B) -2: A modified polycarbodiimide was obtained by the following method. To the above polycarbodiimide solution, 3.8 g of trimellitic anhydride was added as a reactive compound and reacted at 20 ° C. for 3 hours to obtain a solution of a modified polycarbodiimide having Mn of 3,800. Thereafter, it was separated and dried. As a result of infrared spectroscopy, the modified polycarbodiimide was found to have an infrared absorption characteristic of a carbodiimide unit (wave number 2,150 to 2,100 cm ^-1 ) and an infrared absorption characteristic of a carboxylic anhydride (wave number 1,850 to 1,1). 780
cm ^-1 ).

(B) -3: A modified polycarbodiimide using an epoxy compound in combination was obtained as follows. In the modified polycarbodiimide solution, as an epoxy compound,
After adding 20 g of an epoxy resin comprising a diglycidyl ether derivative of bisphenol A [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.] to 20 g of the solid content of the modified polycarbodiimide in the above solution, the pore diameter was 1 μm.
The mixture was filtered under pressure using a filter of m, and cyclohexanone was added so that the total solid concentration in the solution was 20% to prepare a solution. Then, it was degassed under vacuum to obtain a paste-like resin. (B) -4; Carbodilite HMV-8CA [manufactured by Nisshinbo Co., Ltd.] (B) -5; Carbodilite IM-25P [manufactured by Nisshinbo Co., Ltd.] (B) -6; Carbodilite 9010 [Nisshinbo Co., Ltd.]
Made)

Examples 1 to 6 and Comparative Examples 1 to 3 Melting and kneading were carried out at a set temperature of 260 ° C. using a kneader according to the formulation shown in Tables 3 and 4, and then pelletized by a feeder ruder. Using the cyclic polyolefin resin composition thus produced, a molded product in which a metal piece was sealed and a laminate with an epoxy substrate were produced, and the adhesion was evaluated. Tables 1 and 2 show the evaluation results.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

The resin composition of the present invention can improve the adhesion to metal materials and organic materials while maintaining excellent properties such as high heat resistance and transparency of the cyclic olefin polymer. . This allows, for example, semiconductor encapsulation, optical semiconductor encapsulation,
It can contribute to the expansion of the application field of the cyclic olefin polymer in the fields of optical lenses, optical fibers, optical disks, and the like, and is extremely high in industrial value.

Claims (1)

[Claims] 1. A resin composition comprising (A) a cyclic polyolefin-based resin and (B) polycarbodiimide.