JPH0674299B2 - Modified cyclic olefin copolymer - Google Patents

Description

The present invention relates to a cyclic olefin copolymer having improved adhesion.

[Conventional technology]

The applicant has previously proposed a new polymer having a cyclic olefin structure as shown in formula (ii) in the polymer. Such polymers have excellent transparency, heat resistance, chemical resistance, solvent resistance, electrical properties, mechanical strength, moldability and dimensional stability, and are amorphous due to their structure and properties. It is a polymer that can be called polyolefin. Unfortunately, however, this polymer has a problem in that it has poor adhesion or compatibility with other materials, particularly metals and resins other than polyolefin.

[Problems to be solved by the invention]

The problem to be solved by the present invention is to provide a cyclic olefin polymer which has good adhesiveness to metals and synthetic resins and is easily compatible when mixed with other resins.

[Means for solving problems]

That is, the present invention provides a cyclic olefin copolymer with α, β-
Unsaturated carboxylic acid and / or derivative thereof (a), styrene hydrocarbon (b), olefinic unsaturated bond and organosilicon compound (c) having hydrolyzable group, unsaturated epoxy monomer (d) A modified cyclic olefin copolymer obtained by graft-copolymerizing a monomer component selected from the group consisting of: [A] the cyclic olefin copolymer of (A-1) a cyclic olefin of the formula (i) and ethylene; It is a random copolymer, the units derived from cyclic olefins are in the amount of 60 to 10 mol%, and the units derived from ethylene are 40
Present in an amount of ~ 90 mol%, (Here, R ^{1 to} R ¹² are hydrogen, an alkyl group or halogen, which may be the same or different, and R ⁹ or R ¹⁰ and R
^{11 and} R ¹² may form a ring with each other. n is 0,
R ^{5 to} R ^{8 which} are 1 or 2 and are repeated a plurality of times may be the same or different. ) (A-2) The cyclic olefin is substantially represented by the formula (i
i) has the structure [B] The modified cyclic olefin copolymer has the ratio (B-1) of the graft monomer in the range of 0.5 to 35 parts by weight relative to 100 parts by weight of the cyclic olefin copolymer, ) The intrinsic viscosity [η] measured in decalin at 135 ℃ is
It is a modified cyclic olefin copolymer defined by being in the range of 0.03 to 20 dl / g.

[Action and effect]

Cyclic olefin copolymer In the present invention, the cyclic olefin copolymer in which any of the monomer components (a) to (c) is graft-copolymerized is:
The cyclic olefin represented by the formula (i) mainly has the structure represented by the formula (ii) in the copolymer.
A preferred embodiment uses a cyclic olefin in which any of R ^{1 to} R ^{12 in} formula (i) is hydrogen. Furthermore n
It is preferable to use a cyclic olefin having 1 or 2 because it has excellent heat resistance.

The cyclic olefin copolymer contains ethylene as a copolymerization component in addition to the cyclic olefin represented by the formula (i), and other α-olefin or other third monomer component is copolymerized if necessary. Good. The cyclic olefin represented by the formula (i) has the same formula (i)
It is considered as one monomer component as long as it is contained in. Usually, the molar ratio of ethylene / cyclic olefin of formula (i) in the copolymer can be in the range of 5/95 to 95/5. However, in many cases, there are more ethylene units between the cyclic olefin and the next cyclic olefin structural unit than in the case where the cyclic olefins are continuously bonded to each other. It is preferable to adopt the range of 60 to 90/10. When a multi-component monomer after the third monomer component is included, the total amount of these multi-component monomers / the molar ratio of the cyclic olefin of the formula (i) is 5/95 to 95/5, particularly
Within the range of 30/70 to 90/10.

The cyclic olefin has the structure of the formula (ii) in the copolymer, and by adopting this structure, it is excellent in heat resistance and heat aging resistance. That such a structure, the polymer iodine value of usually 5 or less, many of 1 or less, it is also often 5 or less after it has been polymerized connexion graft copolymer and is 1 or less, more ¹³ C-NMR It is also backed up.

Specific examples of the monomer component represented by the formula (i) include the followings, but the examples shown here are extremely limited and may be those represented by the formula (i). Anything can be the monomer component of the present invention.

Examples of the third and subsequent monomer components copolymerizable with the cyclic olefin and ethylene include propylene and 1
-Butene, 3-methyl-1-butene, 1-pentene, 4
-Methyl-1-pentene, 1-hexene, 1-decene and other α-olefins having 3 or more carbon atoms, cyclopentene, cyclohexene, cycloolefin such as 3-methylcyclohexene, styrene, styrenes such as α-methylstyrene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene or 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,
Mention may be made of polyenes such as 5-vinyl-2-norbornene.

In order to produce a cyclic olefin copolymer having the structure represented by the formula (ii) using the above-mentioned monomer components, polymerization may be carried out using a well-known Ziegler-based catalyst. The Ziegler catalyst is a catalyst composed of a titanium compound supported on a magnesium compound, which is known as a highly active catalyst, or a vanadium compound and a reducing agent such as an alkylaluminum compound, and a vanadium catalyst is particularly preferable. For more details on the polymerization catalyst and the polymerization method, see
Since it is disclosed in No. 60-110545, No. 113074, etc., it is omitted here. The copolymer thus obtained has low crystallinity, and most of it is amorphous.

Modified Monomer The modified monomer used in the graft copolymerization is (a) to (a) above.
Selected from (d).

An unsaturated carboxylic acid of (a) or a derivative component unit thereof;
For example, acrylic acid, methacrylic acid, α-ethyl
Luacrylic acid, maleic acid, fumaric acid, itaconic acid,
Citraconic acid, tetrahydrophthalic acid, methyltetrahi
Drophthalic acid, endocis-bicyclo [2.2.1] hept
-5-ene-2,3-dicarboxylic acid (naphthic acid ),
Cyl-endocis-bicyclo [2.2.1] hept-5-e
-2,3-dicarboxylic acid (methyl nadic acid ) Such as
Unsaturated dicarboxylic acid acid halides, amides, imides, acids
Derivatives of unsaturated dicarboxylic acids such as anhydrides and esters
Specific examples include maleenyl chloride, maleimide, and
Water maleic acid, citraconic anhydride, maleic acid monomethyi
And dimethyl maleate. Among these
Therefore, unsaturated dicarboxylic acid or its acid anhydride is preferable.
Especially maleic acid, nadic acid or these acids
Water is preferred.

The styrene-based hydrocarbon component unit of (b) has the formula [In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a lower alkyl group. ] It is a compound represented by these. Specifically, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-
Examples thereof include ethyl styrene, p-ethyl styrene, o-isopropyl styrene, m-isopropyl styrene and p-isopropyl styrene. Of these styrene-based hydrocarbon components, styrene, m-methylstyrene or p-methylstyrene component is preferable.

The organosilicon compound having a hydrolyzable group together with the olefinic unsaturated bond of (c) has a general formula of R ¹ R ² SiY ¹ Y ² , R ¹ XSiY.
Examples include those represented by ¹ Y ² or R ¹ SiY ¹ Y ² Y ³ . In the formula, R ¹ and R ² are monovalent groups having an olefinic unsaturated bond and consisting of carbon, hydrogen and optionally oxygen, and they may be the same or different.

Examples of such groups are vinyl, allyl, butenyl, cyclohexenyl, cyclopentadienyl,
A terminal olefinic unsaturated group is particularly preferable. Other preferred examples are CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ −, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) _2- O— (CH having an ester bond of a terminal unsaturated acid. _{2) 3 -, CH 2 =} C (CH 3) COOCH 2 OCH 2 CH 2 (OH) CH 2 O (CH 2) 3 - can be exemplified groups such as. Of these, the vinyl group is most suitable. X is an organic group having no olefinic unsaturated bond, for example, a monovalent hydrocarbon group such as methyl,
There are groups such as ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, and these groups may be halogen-substituted hydrocarbon groups. Groups Y ¹ , Y ² , Y ³
Are the same or different hydrolyzable groups, for example, an alkoxy group such as methoxy, ethoxy, butoxy and methoxyethoxy, an alkoxyalkoxy group, an acyloxy group such as formyloxy, acetoxy and propionoxy, an oxime such as -ON = _{C (CH 3) 2, -ON} = CHCH 2 C 2 H 5 and _{-ON = C (C 6 H 5} ) 2 or a substituted amino group, and an arylamino group, e.g. -NHCH _3, -NHC ₂ H ₃ and -NH (C ₆ H ₅ )
And other arbitrary hydrolyzable organic groups.

The organosilicon compound preferably used in the present invention is a compound represented by the general formula R ¹ SiY ¹ Y ² Y ³ , and an organosilicon compound having the same groups Y ¹ , Y ² and Y ³ is particularly suitable. Of these, vinyltrisalkoxysilane is preferable, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (methoxyethoxy) silane. However, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane and the like can be used as well.

The unsaturated epoxy monomer (d) is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in each molecule. As such an unsaturated epoxy monomer, for example, a general formula, (Wherein, R is a hydrocarbon group having a polymerizable ethylenically unsaturated bond) and an unsaturated glycidyl ester represented by the general formula, (Where R is the same as in the previous formula, X is —CH ₂ —O— or Is a divalent group represented by) and an unsaturated glycidyl ether represented by (Wherein R is the same as in the above formula, R ¹ is hydrogen or a methyl group) and the like.

Specifically, glycidyl acrylate, glycidyl meta
Crylate, itaconic acid mono and diglycidyl ester
, Butene tricarboxylic acid mono, di and triglycidyl
Luster, citraconic acid mono- and diglycidyl es
Ten, endo-cis-bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboxylic acid (Nadic acid ) Things and
Diglycidyl ester, endo-cis-bicyclo [2.2
1] Hept-5-ene-2-methyl-2,3-dicarboxylic acid
(Methylnaphthic acid ) Mono and Diglycidyl Esthe
Mono- and diglycidyl esters of allylsuccinic acid,
Glycidyl ester of p-styrenecarboxylic acid, allyl
Glycidyl ether, 2-methylallyl glycidyl ether
Ter, styrene-p-glycidyl ether, 3,4-epo
Xy-1-butene, 3,4-epoxy-3-methyl-1-
Butene, 3,4-epoxy-1-pentene, 3,4-epoxy
-3-Methyl-1-pentene, 5,6-epoxy-1-f
Examples include xene and vinylcyclohexene monoxide.
can do. Among these, glycidyl acryl
And glycidyl methacrylate are preferred.

Grafting reaction Various known methods can be adopted to produce a graft copolymer, for example, a method of melting a cyclic olefin copolymer and adding a modifying monomer to graft copolymerizing it, or dissolving it in a solvent to prepare a modified monomer. There is a method of adding a body to carry out copolymerization. In either case, it is preferable to carry out the reaction in the presence of a radical initiator for efficient graft copolymerization. Examples of radical initiators include organic peroxides, organic peresters, and azo compounds, but ionizing radiation, ultraviolet rays, and the like can also be used for radical generation.

Modified cyclic olefin copolymer The graft amount of the modified monomer in the modified cyclic olefin copolymer obtained by the grafting reaction is usually 0.1 to 50 parts by weight, preferably 100 parts by weight of the cyclic olefin copolymer, Is in the range of 0.5 to 35 parts by weight. If the graft amount is less than 0.1 parts by weight, the adhesion performance with a metal will deteriorate, the compatibility with synthetic resins other than polyolefin will deteriorate, and the adhesion will also decrease. On the other hand, if it exceeds 50 parts by weight, the compatibility with the polyolefin becomes poor, the adhesive strength with the polyolefin decreases, and it is also economically disadvantageous.

The modified monomer is introduced by a graft reaction into the cyclic olefin structure unit or ethylene structure unit in the cyclic olefin copolymer and further into the multi-component monomer component units after the third monomer component.

The intrinsic viscosity [η] of the modified cyclic olefin copolymer by decalin at 135 ° C. is preferably in the range of 0.03 to 20 dl / g, particularly 0.05 to 5 dl / g. When it is less than 0.03 dl / g, the melt viscosity becomes too low, and when it is used as a pigment dispersant for resins other than polyolefin, for example, a sufficient dispersing effect cannot be obtained, resulting in uneven coloring. If it is more than 20 dl / g, the melt viscosity becomes too high and the moldability becomes poor.
Laminate formability becomes poor when used as an adhesive layer.

In addition, the modified copolymer of the present invention has excellent heat resistance. That is, the glass transition temperature, which is an index of heat resistance, is high. Glass transition temperature is usually 20-250 by dynamic elasticity meter (DMA)
℃, mostly 30 ~ 220 ℃, TMA (Thermo-mechanical Analys
er: Loaded by Deupon) 49g, quartz needle (diameter 0.63)
5 mm) and the temperature at which the needle penetrates 0.1 mm at a heating rate of 5 ° C / min is the softening temperature, usually 20-230 ° C, most of which is 30-200 ° C.
Is within the range of.

Density of the modified copolymer, ASTM D 1505 typically in a manner specified in 0.95~1.20g / cm ^3, a number in the range of 0.96~1.10g / cm ^3.

The modified copolymer of the present invention is molded by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical-two-screw extruder, cokneader, platey eater, mixer, twin-screw conical screw extruder, planetary screw extruder, gear type extrusion Extrusion molding, injection molding, blow molding, rotational molding, etc. using a machine, a screwless extruder, etc. In the molding process, known additives such as heat stabilizers, light stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, synthetic oils and natural oils are used as necessary. Inorganic and organic fillers, dyes and pigments may be added.

Examples of such additives include phenol-based or sulfur-based antioxidants. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-
Cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β-
(4-Hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-
Butyl-4-hydroxybenzylphosphonate, 2,4,6
-Tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate , 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1 -Methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-t)
ert-Butylphenyl) butyric acid] glycol ester, 4,4'-butylidene bis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4)
-Hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5 -Tris (2,6-dimethyl-
3-Hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3 , 5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl))
Propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert
-Butyl) phenoxy-1,3,5-triazine, phenols such as 4,4'-thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (2-tert-butyl-5- Examples include carbonic acid oligoesters of methylphenol (for example, polymerization degrees of 2,3,4,5,6,7,8,9,10, etc.) and polyvalent phenolic carbonic acid oligoesters.

Examples of sulfur antioxidants include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl-, and butyl-, octyl-, lauryl-,
Alkylthiopropionic acid polyhydric alcohols such as stearyl- (eg glycerin, trimethylolethane,
Trimethylolpropane, pentaerythritol, trishydroxyisocyanurate) ester (for example, pentaerythritol tetralauryl thiopropionate).

Alternatively, a phosphorus-containing compound may be added, for example, trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl)
Phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl-4,4 'isopropylidene diphenyl phosphite, tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert- Butyl-4-hydroxyphenyl) phosphite, tris (meno-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'- Butylidene bis (3-
Methyl-6-tert-butylphenol)] · 1,6-hexanedioldiphosphite, phenyl · 4,4′-isopropylidenediphenol · pentaerythritoldiphosphite, bis (2,4-di-tert-butylphenyl) )
Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidene bis (2-tert-butylphenol)] phosphite, phenyl Diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4'-isopropylidene bis (2-tert-
Butylphenol) -di (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-ter)
t-butylphenyl) -4,4'-biphenylenediphosphonite and the like.

Also, 6-hydroxychroman derivatives such as α, β,
γ, δ various tocopherols and mixtures thereof, 2-
(4-Methyl-pent-3-enyl) -6-hydroxychroman substituted with 2,5-dimethyl, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2, 2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2,2,
5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-
Hydroxy chromans, 2,2-dimethyl -5-tert-butyl-6-hydroxy chromans such, also the general formula MxAly (OH) 2x + 3y- 2z (A) z · aH 2 O ( where M is a different Mg, Ca or Zn and A are anions other than hydroxyl group, x, y and z are positive numbers, and a is O or a positive number), for example, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg _{8 Al 2 (OH) 20 CO} 3 · 5H 2 O, Mg 5 Al 2 (OH) 14 CO 3 · 4H 2 O, Mg 10 Al 2 (OH) 22 (CO 3) 2 · 4H 2 O, Mg 6 Al ₂ (OH) ₁₆ HPO ₄ / 4H ₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ O, Zn ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ O, Zn ₆ Al ₂ (OH) _{16 SO 4 · 4H 2 O, Mg} 6 Al 2 (OH) 16 SO 4 · 4H 2 O, Mg 6 Al 2 (OH) 12 CO 3 · 3H 2 O, may be added and the like.

Further, 2-benzofuranone compounds disclosed in JP-A-55-501181, for example, 3-phenyl-2-benzofuranone, 3-phenyl-5,7-di-t-butyl-2-benzofuranone, etc. are blended. Good.

Examples of the light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydroxy-4-methoxybenzophenone and 2,4. -Hydroxybenzophenones such as dihydroxybenzophenone, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
Benzotriazoles such as (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, phenyl salicylates, p-tert-butylphenyl salicylates, 2,4-di-tert-butylphenyl-3 , 5-
Benzoates such as di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,2'-thiobis (4-tert-octylphenol) Ni salt, Nickel compounds such as 2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine Ni and (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt , Α-cyano-β-methyl-β-
Substituted acrylonitriles such as (p-methoxyphenyl) methyl acrylate and N'-2-methylphenyl-N
2-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide and other oxalic acid dianilides,
Bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{(6- (1,1,3,3-tetramethylbutyl) imino} -1,3,5-triazine-2 , 4-jiil {4
-(2,2,6,6-Tetramethylpiperidyl) imino} hexamethylene], 2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol condensation with dimethyl succinate And hindered amine compounds.

As the lubricant, for example, paraffin wax, polyethylene wax, polypropylene wax, and other aliphatic hydrocarbons, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and other higher grades Fatty acids or metal salts thereof, that is, lithium salts, calcium salts, sodium salts, magnesium salts, potassium salts, etc., fatty alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, caprin Aliphatic amides such as acid amides, lauric acid amides, myristic acid amides, palmitic acid amides, stearic acid amides, esters of fatty acids with alcohols, fluoroalkylcarboxylic acids or metal salts thereof, fluoroalkyls Fluorine compounds such as sulfonic acid metal salts.

As the filler, glass fiber, silver or aluminum coating
Glass fiber, stainless fiber, aluminum fiber, chi
Potassium tannate fiber, carbon fiber, Kevlar Fiber, super high
Inorganic or organic fibers such as elastic high strength polyethylene fibers
Fibrous filler, talc, calcium carbonate, magnesia hydroxide
Um, calcium oxide, magnesium sulfate, graph eye
G., nickel powder, silver powder, copper powder, carbon black, silver powder
Glass beads, aluminum coated glass beads,
Aluminum flakes, stainless flakes, nickel
Coat graphite powder, granular, flakes
Examples thereof include inorganic or organic fillers.

Blend with other polymer Further, the modified polymer of the present invention can be used by blending with various known high molecular weight or low molecular weight polymers, and also as an adhesive layer of various polymers. Can also be used. Examples of such a polymer include (a) a polymer derived from a hydrocarbon having one or two unsaturated bonds, specifically, a polyolefin such as polyethylene or polypropylene which may have a crosslinked structure, Polyisobutylene, polymethylbutene-1, poly-4-methylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, or a copolymer of monomers constituting the above polymer, such as an ethylene / propylene copolymer, propylene·
Butene-1 copolymer, propylene / isobutylene copolymer, styrene / isobutylene copolymer, styrene / butadiene copolymer, terpolymer of ethylene and propylene and a diene such as hexadiene, cyclopentadiene, ethylidene norbornene, etc., Alternatively, blends of these polymers, graft polymers, block copolymers, etc. (b) Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. (C) Polymers derived from α, β-unsaturated acids and their derivatives, specifically, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or monomers and other copolymers constituting the above polymers. Copolymer with polymerizable monomer Eg to acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-
(D) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, and polymalein. Vinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, or a copolymer of the above-mentioned polymer-constituting monomer and another copolymerizable monomer such as ethylene-vinyl acetate copolymer, (e) From epoxide Derived polymers, such as polymers derived from polyethylene oxide or bis-gidyl ether, (f) polyacetals, specifically polyoxymethylene, polyoxyethylene,
Such as polyoxymethylene containing ethylene oxide as a comonomer, (to) polyphenylene oxide, (h) polycarbonate, (ri) polysulfone, (nu) polyurethane and urea resin, (l) diamine and dicarboxylic acid and / or aminocarboxylic Polyamides and copolyamides derived from acids or the corresponding lactams, specifically nylon 6, nylon 66, nylon 11, nylon 12, etc. (wo) from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones Derived polyester, specifically polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, etc. (wa) From aldohydr and phenol, urea or melamine Polymers with an induced crosslinked structure, specifically phenol-formaldehyde resins, urea
Formaldehyde resin, melamine / formaldehyde resin, etc. (f) Argide resin, specifically glycerin / phthalic acid resin, etc. (yo) Derived from copolyester of saturated and unsaturated dicarboxylic acid and polyhydric alcohol, Unsaturated polyester resins and halogen-containing modified resins obtained by using vinyl compounds, (ta) Natural polymers, specifically cellulose, rubber, proteins or their derivatives such as cellulose acetate, cellulose propionate, cellulose ether Can be exemplified.

Furthermore, a modified copolymer having a low molecular weight, for example, a copolymer having a molecular weight of 0.5 dl / g or less, can be used in all fields usually used as wax, and in this case, various known waxes can be mixed and used. As an example, use can be made of the above-mentioned various polymers as a pigment dispersant, a polish, a carbon ink base, a toner for electrostatic copying, a coloring aid and the like.

Furthermore, the modified copolymer of the present invention is used in the state of a polymer solution dissolved in various organic solvents, or in the form of a dispersion liquid dispersed in water or an insoluble organic solvent (alcohol, ketone, ether, etc.). May be used in.

Other fields of application of the modified copolymer of the present invention include insulating coating agents, conductive coatings, capacitors, optical fiber claddings or cores, electrophotographic toners, laser printer toners, display element sealants, and ICs. A sealant, a metal / ceramics mirror surface protection coating material and the like can also be exemplified.

〔Example〕

The contents of the present invention will be described below with reference to preferred embodiments, but the present invention is not limited to these embodiments, and any embodiment is possible as long as the object is not impaired.

Reference Example The cyclic olefin copolymer used in this example was synthesized according to the following example.

Using a 2-glass polymerization vessel equipped with a stirring blade, ethylene and cyclic olefin (2-methyl-1,4,5,8) were continuously added.
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene: (3) in Table 1, hereinafter referred to as M-DMON) was subjected to a copolymerization reaction. That is, the polymerization vessel top, a toluene solution of M-DMON, hourly 0.9 so that M-DMON concentration in the polymerization vessel becomes 60 g /, a toluene solution of _{VO (OC 2 H 5) Cl} 2 as a catalyst, Vanadium concentration in the polymerization vessel is 0.5 mmol /
So that 0.7 hour / hour, and a toluene solution of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) are added so that the aluminum concentration in the polymerization vessel becomes 2 mmol / hour.
Each of them is continuously fed into the polymerization vessel at a rate of 0.4, while the polymerization solution in the polymerization vessel is continuously withdrawn from the lower portion of the polymerization vessel so as to be always 1. Further, ethylene is supplied at a rate of 35 / hour and nitrogen is supplied at a rate of 80 / hour from the upper portion of the polymerization vessel.
The copolymerization reaction was carried out at 10 ° C by circulating a refrigerant through a jacket attached outside the polymerization vessel. When the copolymerization reaction is performed under the above conditions, a polymerization reaction mixture containing an ethylene / M-DMON random copolymer is obtained. A small amount of notanol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the mixture was poured into a large amount of acetone / methanol to precipitate the produced copolymer. The copolymer was thoroughly washed with acetone and then dried under reduced pressure at 80 ° C for 24 hours. By the above operation, the cyclic olefin copolymer (ethylene / M-DMON
Random copolymer) was obtained at a rate of 30 g / h. The ethylene composition of the copolymer measured by ¹³ C-NMR analysis was 63 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.9.
It was 2.

The cyclic olefin copolymers used in the following examples were synthesized by the above method, but other cyclic olefins (the cyclic olefins used are listed in Table 1) were also synthesized along with the above polymerization examples.

Example 1 Ethylene / M-DMON random copolymer (135 in decalin
Intrinsic viscosity at ℃ [η] 0.92dl / g, ethylene content 63
Mol%) 50 g in a glass reactor in a nitrogen atmosphere at 125 ° C.
Was dissolved in 500 ml of toluene. After that, a toluene solution of maleic anhydride (abbreviated as MAH) (9.8 g / 30 ml) and a toluene solution of dicumyl peroxide (abbreviated as DCP) (0.27 g / 30 m)
l) was fed gradually from separate conduits over 4 hours.

Since MAH has low solubility in toluene, it was heated by an infrared lamp to dissolve it, and heating was continued until the supply was completed.

After the supply was completed, the reaction was continued for another 2 hours, and after the reaction was completed, it was cooled to room temperature. The reaction solution was poured into a large amount of acetone to precipitate a polymer. The graft ethylene M-DM
After passing the ON copolymer, wash it with acetone repeatedly,
After drying under reduced pressure at 80 ℃ for one day, MAH / graft / MD
A MON copolymer was obtained. Oxygen analysis of this modified copolymer was carried out to find the graft amount of MAH, and it was found that 1.6 wt% MAH was grafted. The intrinsic viscosity [η] of this modified copolymer measured in decalin at 135 ° C was 0.8.
It was 7 dl / g. The density according to ASTM D1505 is 1.021 g /
is cm ³ . Glass transition temperature Tg is
Loss modulus E ″ by MEchanical Analyser (DMA)
Was measured at a temperature rising rate of 5 ° C / min, and the peak temperature was 136 ° C.

Examples 2 to 9 Grafting conditions of Example 1 or ethylene of Example 1
A MAH graft copolymer was synthesized in the same manner except that the random copolymer of cyclic olefin and ethylene shown in Table 1 was used instead of the M-DMON random copolymer. The results are shown in Table 2.

Examples 10 to 18 Reactions were carried out in the same manner as in Examples 1 and 2 except that the monomers used in the grafting reaction were changed.
The results are shown in Table 3.

In addition, in Examples 10 to 12, methyl ethyl ketone was used as the solvent for recovering the polymer instead of acetone as the solvent.

Example 19 The modified cyclic olefin copolymer obtained in Example 1 was blended with an unmodified cyclic olefin copolymer in an amount of 10 wt% and pelletized using a 15 mmφ pelletizer. The pellet obtained above was placed on a 0.1-mm-thick 6-nylon film, and a 1.1 mm-thick nylon film and a modified cyclic olefin copolymer composition laminated sheet were prepared using a press molding machine. A test piece having a width of 10 mm and a length of 65 mm was taken from this sheet, and the interlayer adhesive strength between the nylon and the cyclic olefin composition was measured. As a result, the peel strength was 2.16 kg / inch.

Comparative Example 1 A laminated sheet was prepared in the same manner as in Example 19 except that only the unmodified cyclic olefin copolymer was used, but it did not adhere substantially and the test could not be conducted.

Example 20 The styrene-modified cyclic olefin copolymer obtained in Example 10 was melted with one extruder and fed to a two-layer composite T-die sheet molding die. Separately acrylonitrile copolymer [Vist
von Co., trade name Barex210] was melted by another extruder to prepare a 1 mm + 1 mm two-layer sheet.

A 10 mm test piece was cut out from this sheet, and the inter-layer adhesive strength between Barex 210 and the styrene-modified cyclic olefin copolymer was measured and found to be 550 g / cm.

Example 21 In Example 20, instead of the styrene-modified cyclic olefin copolymer, the silane-modified cyclic olefin copolymer obtained in Example 13 was used, and instead of the acrylonitrile-based copolymer, polyvinylidene chloride (Dow Chemical Co Made, product name S
ARAN, XO5253-16] was used, and the interlayer adhesive strength was measured in the same manner. The adhesive strength was 570 g / cm.

Example 22 In Example 20, instead of the styrene-modified cyclic olefin copolymer, the glycidyl methacrylate-modified cyclic olefin copolymer obtained in Example 16, polyethylene terephthalate instead of the acrylonitrile copolymer [Mitsui Petres Co., Ltd. , J-135] was used, and the adhesive strength was measured in the same manner. As a result, the adhesive strength was 680 g / cm.

Example 23 Ethylene / M-DMON random copolymer (135 in decalin
Intrinsic viscosity at ℃ [η] 0.92dl / g, ethylene content 63
50% (mol%) was dissolved in 500 ml of toluene at 160 ° C. in a glass autoclave under a nitrogen atmosphere. Then in the system
Keep at 160 ℃, 300g of styrene (hereinafter referred to as "St") and dicumyl peroxide (hereinafter referred to as "DC" under stirring).
P)) in toluene (1.0 g / 30 ml) was fed gradually via separate conduits over 10 hours.

After the supply was completed, the reaction was continued for another 2 hours, and after the reaction was completed, it was cooled to room temperature. The reaction solution was poured into a large amount of methyl ethyl ketone to precipitate a polymer. After filtering the St-graft-ethylene-M-DMON copolymer, it was repeatedly washed with methyl ethyl ketone to remove the homopolystyrene produced as a by-product, and then dried under reduced pressure at 80 ° C for 1 day to obtain the desired St-graft-ethylene-M -DMON copolymer was obtained. The modified copolymer was analyzed by ¹ H-NMR to determine the graft amount of St. It was found that 17.3 wt% of St was grafted. The intrinsic viscosity [η] of this modified copolymer measured in decalin at 135 ° C. was 1.52 dl / g, and the density according to ASTM D1505 was 1.032 g / cm ³ . Also, the glass transition temperature Tg
Is a Dynamic Mechanical Analyser (DMA) manufactured by DuPont.
The loss elastic modulus E ″ was measured at a temperature rising rate of 5 ° C./min, and the peak temperature was 133 ° C.

Claims (2)

[Claims] 1. An organic compound having an α, β-unsaturated carboxylic acid and / or its derivative (a), a styrene hydrocarbon (b), an olefin unsaturated bond and a hydrolyzable group in a cyclic olefin copolymer. A modified cyclic olefin copolymer obtained by graft-copolymerizing a monomer component selected from the group consisting of a silicon compound (c) and an unsaturated epoxy monomer (d), wherein [A] the cyclic olefin copolymer is A-1) A random copolymer of a cyclic olefin represented by the formula (i) and ethylene, wherein the amount of the unit derived from the cyclic olefin is 60 to 10 mol% and the amount of the unit derived from ethylene is 40 to 90 mol. Exists in the amount of%, (Here, R ^{1 to} R ¹² are hydrogen, an alkyl group or halogen, and may be the same or different, and R ⁹ or
R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. n is 0, 1 or 2 and is repeated multiple times
R ^{5 to} R ⁸ may be the same or different. ) (A-2) The cyclic olefin is substantially represented by the formula (i
i) has the structure [B] The modified cyclic olefin copolymer has (B-1) the grafting amount of the graft monomer is within a range of 0.5 to 35 parts by weight relative to 100 parts by weight of the cyclic olefin copolymer, 2) The intrinsic viscosity [η] measured in decalin at 135 ℃ is
A modified cyclic olefin copolymer defined by the following: within the range of 0.03 to 20 dl / g. 2. The modified cyclic olefin copolymer according to claim 1, wherein n is 1 or 2 in the cyclic olefin of the formula (i).