CN101454384A - Norbornene compound addition polymer film, process for production thereof, and use thereof - Google Patents

Abstract

To provide a norbornene compound addition polymer film that is excellent in heat resistance, chemical resistance, dimensional stability and the like and favorable for use for optical parts and electric insulating parts. [MEANS FOR SOLVING PROBLEMS] The norbornene compound addition polymer film satisfies at least either one of the following: when it is heated from 25 DEG C up to 200 DEG C and then again cooled to 25 DEG C, the dimensional change rate thereof between before heating and after cooling is at most 100 ppm, or the dimensional change rate thereof between before and after dipping in propylene glycol monomethyl ether acetate at 25 DEG C for 1 hour is at most 100 ppm. The method for producing the norbornene compound addition polymer film comprises a step of maintaining the film having a residual solvent content of at most 5,000 ppm of the norbornene compound addition polymer having a glass transition temperature of T DEG C, at a temperature falling within a range of from the higher temperature of either (T-150) DEG C or 180 DEG C to T DEG C.

Description

The purposes of norbornene compound addition polymer film, its preparation method and this addition polymer film

Technical field

The present invention relates to be applicable to the good norbornene compound addition polymer film of dimensional stability of optics, electric insulation part.In more detail, the present invention relates to the purposes of norbornene compound addition polymer film, its making method and this addition polymer film, even this norbornene compound addition polymer film changes in environment for use temperature or humidity, under medicine etc. such as handles at situation, size does not change substantially yet.

Background technology

The film that is formed by the norbornene compound addition polymer is because thermotolerance, the transparency, resistance to chemical reagents and low water absorbable are all fine, therefore as optics, electric insulation part and, electrical and electronic parts, electronic part encapsulation material, medical equipment or wrapping material are of great use.For example, non-patent literature 1 discloses the electric insulation part that has used norbornene compound addition polymer film, and patent documentation 1 discloses the liquid crystal display substrate material that has used norbornene compound addition polymer film.

Usually, when resin molding is used for optics, electric insulation part,, therefore require resin molding to have thermotolerance and resistance to chemical reagents owing to will contact at film surface formation wired circuit or with medicaments such as liquid crystal or resists.And the norbornene compound addition polymer has these good characteristics, therefore is applicable to very much above-mentioned parts.

But recently because the multifunction of e-machine, the height of the densification that is used for the wiring route that electrical signal transmits at a high speed, display unit device become more meticulous to have high requirements.Therefore, it is particularly important that the dimensional stability of film becomes, even require film carried out pyroprocessing, coating medicine or in medicine behind the dipping, the size of film does not change yet.

So, as the method for keeping the film dimensional stability, patent documentation 2 discloses the cyclic olefin addition polymer with dissolving at the solvent (1) of 25 ℃ of these cyclic olefin addition polymers of dissolving, and carry out solution casting, then by contacting with following solvents (2), can do not produced thermal degradation when, low and the optical characteristics of residual solvent amount, strength at break, thermotolerance and dimensional stability good optical material film, described solvent (2) can not dissolve described cyclic olefin addition polymer, but can with solvent (1) uniform mixing, and boiling point under atmospheric pressure is below 150 ℃.

But in this method, carry out its vacuum-drying under heating condition the film immersion that must will form back or with after the saturation steam of solvent (1) contact in solvent (1) again, and operation is complexity very.This method is not as carrying out the operation that in solvent (1) impregnated membranes or this film do not contact with the saturated vapo(u)r of solvent (1), then shown in same document comparative example, even carry out the vacuum drying treatment under the high temperature, the residual solvent amount of gained film with handle before compare and only reduce 2～5%, at most just reduce half, and breaking tenacity is low, dimensional change does not improve, still very big, total light transmittance significantly reduces in addition, can not play a role fully as optical material.

Patent documentation 1: the spy opens flat 5-61026 communique

Patent documentation 2: the spy opens the 2004-59639 communique

Non-patent literature 1:Journal of Polymer Science:Part B:Polymer Physics, 1999, the 37th volume, pp3003-3010.

Summary of the invention

The problem that invention will solve

So, the object of the present invention is to provide norbornene compound addition polymer film applicable to optics, electric insulation part preparation technology and preparation method thereof, and the optics, electric insulation part, electrical and electronic parts, electronic part encapsulation material, medical equipment and the wrapping material that comprise this norbornene compound addition polymer film, the thermotolerance of above-mentioned norbornene compound addition polymer film, resistance to chemical reagents, dimensional stability etc. are good.

The method of dealing with problems

In order to address the above problem, present inventors are through concentrating on studies, even not found that norbornene compound addition polymer film carried out numerous and diverse processing such as solvent impregnated, and only this norbornene compound addition polymer is carried out the such simple operation of heat treated at its second-order transition temperature or the temperature range lower slightly than second-order transition temperature, the film that obtains like this, even its be exposed to the pyritous step or with step that medicine contacts in, neither warpage is also indeformable, and do not change substantially with respect to original dimensions, finished the present invention based on this discovery.

Like this, the invention provides a kind of norbornene compound addition polymer film, it satisfies in following two kinds of situations any one at least: after (1) is heated to 200 ℃ by 25 ℃, when being cooled to 25 ℃ again, before the heating and the size changing rate between the cooling back be below the 100ppm; (2) flooded 1 hour in propylene glycol methyl ether acetate under 25 ℃, dipping size changing rate preceding and that flood between the back is below the 100ppm.

Preferably, norbornene compound addition polymer film of the present invention flooded 1 hour in 25 ℃ of water, and dipping size changing rate preceding and that flood between the back is below the 100ppm.

In addition, preferably, the solvent of norbornene compound addition polymer film of the present invention is 1, below the 000ppm.

In addition, preferably, it is the following antioxidant of 0.01～10 weight % that norbornene compound addition polymer film of the present invention contains with respect to the norbornene compound addition polymer, and described antioxidant is to be selected from least a in phenol antioxidant, lactone antioxidant and the Phosphorus antioxidant.

By the present invention, a kind of preparation method of norbornene compound addition polymer film can be provided, this method comprises the steps, described step is: in the preparation process of norbornene compound addition polymer film, with the residual solvent amount is 5, and the following film of 000ppm maintains comparatively high temps from (T-150) ℃ or 180 ℃ to the scope of T ℃ (T is the second-order transition temperature of norbornene compound addition polymer).

Among the preparation method of norbornene compound addition polymer film of the present invention, be 5 with the residual solvent amount preferably, the following norbornene compound addition polymer casting films of 000ppm is carried out heat treated at comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃ temperature range.

In addition, in the preparation method of norbornene compound addition polymer film of the present invention, in following process, can use the method that film is imposed from (T-150) ℃ or the 180 ℃ comparatively high temps thermal history to T ℃ the temperature range, described process is without the step that forms casting films, and directly prepares norbornene compound addition polymer film by the norbornene compound addition polymer.

In addition, in the preparation method of norbornene compound addition polymer film of the present invention, preparing above-mentioned residual solvent amount is 5, and during the following film of 000ppm, preferably combination is used softening agent.

Norbornene compound addition polymer film of the present invention can also be further and the nesa coating lamination.

Further, by the present invention, can provide the optics, electric insulation part, electrical and electronic parts, electronic part encapsulation material, medical equipment and the wrapping material that comprise norbornene compound addition polymer film of the present invention.

And, by the present invention, can provide a kind of optics, comprise that norbornene compound addition polymer film of the present invention and light penetration are more than 80%, linear expansivity is the laminating material of the transparent substrate below 50ppm/ ℃.

The invention effect

By the present invention, must not carry out solvent treatment etc. to film, only can obtain just that solvent is few, optical characteristics is good, painted few norbornene compound addition polymer film with easy operation, even and this norbornene compound addition polymer film through heating, solvent impregnated and water retting after, size does not change yet.So norbornene compound addition polymer film of the present invention can be used for optics, electric insulation part, electrical and electronic parts, electronic part encapsulation material, medical equipment and wrapping material.

Embodiment

[norbornene compound addition polymer]

The norbornene compound addition polymer that is used for norbornene compound addition polymer film of the present invention is made of the repeated structural unit shown in the general formula (1).

[changing 1]

In the formula, R ¹～R ⁴Be hydrogen atom independently of one another; The functional group of containing periodictable the 15th～16 family's heteroatoms or Siliciumatom; The alkyl that perhaps can have the carbonatoms 1～20 of above-mentioned functional group.In addition, R ¹～R ⁴Can mutually combine and form ring.M is the integer more than 0 or 1.

R ¹～R ⁴Shown in periodictable the 15th～16 family's heteroatoms of containing in the functional group have no particular limits, can enumerate Sauerstoffatom, nitrogen-atoms and sulphur atom.

As the concrete example of functional group, can enumerate, hydroxyl, alkoxyl group, aryloxy, carbonyl, hydroxycarbonyl group, alkoxy carbonyl, aryloxycarbonyl, anhydride group etc. contain the functional group of Sauerstoffatom; Amino, alkylamino, arylamino, cyano group etc. contain the functional group of nitrogen-atoms; Aminocarboxyl, alkyl amino-carbonyl, aromatic yl aminocarbonyl etc. contain the functional group of Sauerstoffatom and nitrogen-atoms; Sulfydryl, alkyl sulfenyl, artyl sulfo, thiocarbonyl group etc. contain the functional group of sulphur atom; Silyl, alkyl silyl, aryl silyl etc. contain the functional group of Siliciumatom; Alkoxysilyl, aryloxymethyl silylation etc. contain the functional group of Sauerstoffatom and Siliciumatom etc.

R ¹～R ⁴As long as shown alkyl has 1～20 carbon atom, have no particular limits.Can be aliphatic alkyl, aromatic hydrocarbyl, also can be saturated hydrocarbyl or unsaturated alkyl.And aliphatic alkyl can be straight chain, side chain or ring-type.

In addition, alkyl can have above-mentioned functional group, and the part of carbon atom can be replaced by the heteroatoms of periodictable the 15th～16 family, Siliciumatom.

In general formula (1), R ¹～R ⁴The ring that forms that mutually combines can be saturated, undersaturated, also can be monocycle, condensed ring.

The used norbornene compound addition polymer of the present invention can be carried out addition polymerization and obtained by norbornene compound shown in the general formula (2).

[changing 2]

In the formula, R ¹～R ⁴And it is identical in m and the general formula (1).

As norbornene compound, m is that 0 o'clock dicyclo [2.2.1] hept-2-ene" class and m are 1 Fourth Ring [6.2.1.1 in the preferred formula (2) ^3,6.0 ^2,7] 12 carbon-4-alkene class.

Dicyclo [2.2.1] the hept-2-ene" class of the synthetic usefulness of the norbornene compound addition polymer that the present invention uses has no particular limits, and as its concrete example, can be listed below.

Dicyclo [2.2.1] hept-2-ene"; 5-methyl bicycle [2.2.1] hept-2-ene"; 5-ethyl dicyclo [2.2.1] hept-2-ene"; 5-butyl dicyclo [2.2.1] hept-2-ene"; 5-hexyl dicyclo [2.2.1] hept-2-ene"; 5-decyl dicyclo [2.2.1] hept-2-ene"; 5-cyclohexyl dicyclo [2.2.1] hept-2-ene"; 5-cyclopentyl dicyclo [2.2.1] hept-2-ene"; 5-ethylidene dicyclo [2.2.1] hept-2-ene"; 5-vinyl dicyclo [2.2.1] hept-2-ene"; 5-propenyl dicyclo [2.2.1] hept-2-ene"; 5-cyclohexenyl dicyclo [2.2.1] hept-2-ene"; 5-cyclopentenyl dicyclo [2.2.1] hept-2-ene"; 5-phenyl dicyclo [2.2.1] hept-2-ene"; 5; 6-dimethyl dicyclo [2.2.1] hept-2-ene"; dicyclo [2.2.1] heptan-2, the 5-diene; the benzoyl norbornadiene; Fourth Ring [9.2.1.0 ^2,10.0 ^3,8] 14 carbon-3,5,7,12-tetraene (being also referred to as " 1,4-endo-methylene group-1,4,4a, 9a-tetrahydrochysene-9H-fluorenes "), Fourth Ring [10.2.1.0 ^2,11.0 ^4,9] 15 carbon-4,6,8,13-tetraene (being also referred to as " 1,4-endo-methylene group-1,4,4a, 9,9a, 10-six hydrogen anthracenes "), Dicyclopentadiene (DCPD), methyl bicyclic pentadiene, dihydro Dicyclopentadiene (DCPD) (are also referred to as " three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-8-alkene ") etc. do not replace or have dicyclo [2.2.1] the hept-2-ene" class of hydrocarbon substituent;

5-norbornylene-2-carboxylate methyl ester, 5-norbornylene-2-carboxylic acid, ethyl ester, 2-methyl-5-norbornylene-2-carboxylate methyl ester, 2-methyl-5-norbornylene-2-carboxylic acid, ethyl ester etc. have dicyclo [2.2.1] the hept-2-ene" class of alkoxy carbonyl;

5-norbornylene-2-carboxylic acid, 5-norbornylene-2,3-dicarboxylic acid, 5-norbornylene-2,3-dicarboxylic anhydride etc. has dicyclo [2.2.1] the hept-2-ene" class of hydroxycarbonyl group or anhydride group;

5-hydroxyl-2-norbornylene, 5-hydroxymethyl-2-norbornylene, 5,6-two (hydroxymethyl)-2-norbornylene, 5,5-two (hydroxymethyl)-2-norbornylene, 5-(2-hydroxyl-oxethyl carbonyl)-2-norbornylene, 5-methyl-5-(2-hydroxyl-oxethyl carbonyl)-2-norbornylene etc. have dicyclo [2.2.1] the hept-2-ene" class of hydroxyl;

5-norbornylene-2-formaldehyde (カ Le バ Le デ ヒ De) etc. has dicyclo [2.2.1] the hept-2-ene" class of alkyl;

3-methoxycarbonyl-5-norbornylene-2-carboxylic acid etc. has dicyclo [2.2.1] the hept-2-ene" class of alkoxy carbonyl and hydroxycarbonyl group;

Acetate 5-norbornylene-2-base ester, acetate 2-methyl 5-norbornylene-2-base ester, vinylformic acid 5-norbornylene-2-base ester and methacrylic acid 5-norbornylene-2-base ester etc. have dicyclo [2.2.1] the hept-2-ene" class of ketonic oxygen base;

5-norbornylene-2-formonitrile HCN, 5-norbornylene-2-methane amide, 5-norbornylene-2,3-dicarboximide etc. has dicyclo [2.2.1] the hept-2-ene" class that contains nitrogen-atoms functional group;

5-trimethoxysilyl-2-norbornylene, 5-triethoxysilyl-2-norbornylene etc. have dicyclo [2.2.1] the hept-2-ene" class that contains Siliciumatom functional group.

Fourth Ring [the 6.2.1.1 that uses during norbornene compound addition polymer of the present invention is synthetic ^3,6.0 ^2,7] 12 carbon-4-alkene class has no particular limits, as its concrete example, can be listed below.

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-ethyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-cyclohexyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-cyclopentyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-methylene radical Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-ethylidene Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-vinyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-propenyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-cyclohexenyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-cyclopentenyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkene, 9-phenyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-nothings such as 4-alkene replace or have the Fourth Ring [6.2.1.1 of hydrocarbon substituent ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylate methyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylate methyl ester etc. has the Fourth Ring [6.2.1.1 of alkoxy carbonyl ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4,5-dicarboxylic acid, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4,5-dicarboxylic anhydride etc. has the Fourth Ring [6.2.1.1 of hydroxycarbonyl group or anhydride group ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-methyl alcohol and Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-alcohol etc. has the Fourth Ring [6.2.1.1 of hydroxyl ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-formaldehyde etc. has the Fourth Ring [6.2.1.1 of hydrogen carbonyl ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Acetate 9-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkenyl esters, acetate 9-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkenyl esters, vinylformic acid 9-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkenyl esters and methacrylic acid 9-Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-4-alkenyl esters etc. has the Fourth Ring [6.2.1.1 of carbonyl oxygen base ^3,6.0 ^2,7] 12 carbon-4-alkene class;

Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-formonitrile HCN, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-methane amide, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4,5-dicarboximide etc. has the Fourth Ring [6.2.1.1 that contains nitrogen-atoms functional group ^3,6.0 ^2,7] 12 carbon-4-alkene class;

4-trimethoxysilyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene, 4-triethoxysilyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene etc. has the Fourth Ring [6.2.1.1 that contains Siliciumatom functional group ^3,6.0 ^2,7] 12 carbon-4-alkene class.

These norbornene compound addition polymer can be homopolymer, also can be monomeric multipolymers more than two kinds.

In addition, also can be and cycloolefin except that norbornene compound and other monomeric multipolymer.

As can with the cycloolefin of norbornene compound copolymerization, can enumerate cyclobutene, cyclopentenes, tetrahydrobenzene, cyclooctene, 1, monocycle (two) alkene such as 5-cyclooctadiene.

As can with other monomer of norbornene compound copolymerization, can enumerate alpha-olefins such as ethene, propylene, 1-butylene, 1-hexene, 1-octene; Vinylbenzene, alpha-methyl styrene, p-methylstyrene, to aromatic ethenyl compounds such as methoxy styrenes; Divinyl, isoprene equiconjugate diene; (methyl) acrylic compound such as methyl acrylate, ethyl propenoate, tert-butyl acrylate, vinylformic acid 2-hydroxy methacrylate, methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic tert-butyl acrylate, 2-hydroxyethyl methacrylate etc.

In addition, " (methyl) acrylate " is meant acrylate and/or methacrylic ester among the present invention.

Consider that from dimensional stability and deliquescent angle the norbornene compound addition polymer that norbornene compound addition polymer film of the present invention uses is preferably from the dicyclo that does not replace or have hydrocarbon substituent [2.2.1] hept-2-ene" class or do not replace or have the Fourth Ring [6.2.1.1 of hydrocarbon substituent ^3,6.0 ^2,7] structural unit of 12 carbon-4-alkene class accounts for more than 70% of whole repeated structural units, more preferably more than 80%, further preferably accounts for more than 85%, especially preferably account for more than 95%.In addition, the preferred carbonatoms of above-mentioned hydrocarbon substituent is 1～3.

The norbornene compound addition polymer that norbornene compound addition polymer film of the present invention uses is preferred especially only to be made of structural unit shown in the general formula (1).

Only the norbornene compound addition polymer thermotolerance height that is made of structural unit shown in the general formula (1) preferably has the second-order transition temperature (Tg) more than 200 ℃, and is more preferably more than 220 ℃, preferred especially more than 240 ℃.

Second-order transition temperature is lower than 200 ℃, when then being used for a part of optics, electric insulation part, the insufficient problem of thermotolerance might occur.On the other hand, second-order transition temperature does not have the upper limit, but if be higher than 400 ℃, then probably can cause polymer unwinds, is difficult to measure Tg sometimes.

The molecular weight of the norbornene compound addition polymer that uses about norbornene compound addition polymer film of the present invention is preferably 10,000～500,000 with the number-average molecular weight (Mn) of polystyrene conversion, more preferably 20,000～450,000, be preferably 50,000～400,000 especially.Number-average molecular weight is too small, and then mechanical properties is difficult to film forming sometimes, and number-average molecular weight is excessive, and then soltion viscosity is too high, preparation difficulty sometimes.

The preparation method of the norbornene compound addition polymer that the present invention uses has no particular limits.

Polymerizing catalyst so long as norbornene compound addition polymerization catalyzer get final product, be not particularly limited, can enumerate, the flat 11-505880 communique of special table, WO00/20472 brochure, spy open the polymerizing catalyst that promotors such as the described nickel of 2001-98035 communique, the 10 families excessive metalcatalyzing agent of palladium grade in an imperial examination and aluminum compound, boron compound combine.

Wherein, preferably with having that palladium bond catalyzer carries out polymerization and the norbornene compound addition polymer that obtains, because of its mechanical characteristics good.

With regard to the norbornene compound addition polymer that the present invention uses, when having the alkene unsaturated link(age) with the norbornene compound addition polymer of aforesaid method gained, this alkene unsaturated link(age) can be hydrogenated.

Hydrogenation can carry out according to common known method, promptly in the presence of hydrogenation catalyst, and the method that the norbornene compound addition polymer is contacted with hydrogen.As hydrogenation catalyst, can use nickel, palladium, platinum, cobalt, ruthenium, rhodium grade in an imperial examination 8～10 group 4 transition metals maybe this compound to be supported the solid catalyst that forms on porous carriers such as carbon, aluminum oxide, silicon oxide, pure aluminium silicate, diatomite; Perhaps organic carboxylate, beta-diketone compound and the organoaluminum of the 4th～10 family's element of cobalt, nickel, palladium etc. or the combination of organolithium; And the homogeneous catalysts such as complex compound of ruthenium, rhodium, iridium etc.

Polymkeric substance after the polymerization or behind the hydrogenation contain as polymerizing catalyst, hydrogenation catalyst with and the transition metal and the halogen atom of the residue of promotor, according to the difference of catalyst type, also contain phosphorus atom, aluminium atom, sulphur atom etc.

The residue that these catalyzer can remainingly be arranged in the norbornene compound addition polymer that uses in norbornene compound addition polymer film of the present invention, but in order to keep high transparent, the total amount of the transition metal atoms that contains in the polymkeric substance, phosphorus atom, aluminium atom, sulphur atom and halogen atom and the weight ratio of polymkeric substance are preferably below the 50ppm, more preferably below the 40ppm, be preferably below the 30ppm especially.

The available atomic absorption analysis of amount (ICP-AES) of the transition metal atoms that contains in the polymkeric substance, phosphorus atom and aluminium atom is tried to achieve.About the amount of sulphur atom and halogen atom, can be with after the polymer combustion, make sulfate ion or the halide-ions aqueous solution is measured with column chromatography analysis.

Remove the catalyst residue in the polymkeric substance, available known method, the method that polymkeric substance is contacted with at least a mineral compound that is selected from clay, clay mineral and ion exchangeable layered inorganic compound.Clay is that principal constituent constitutes usually with the clay mineral.Most of clay mineral is the ion exchangeable layered inorganic compound.In addition, the ion exchangeable layered inorganic compound is meant the compound with following crystalline structure, and the ion that contains can exchange, and described crystalline structure is parallel stacked with weak bonding force mutually between the face that forms by ionic linkage etc.In addition, these clays, clay mineral and ion exchangeable layered inorganic compound are not limited to natural product, also can use the synthetic material.Specifically can enumerate clay; Clay mineral; Have the closeest arrange type of six sides, antimony type, CdCl ₂Type, CdI ₂The ionic linkage compound of layered crystal structures such as type etc.

[norbornene compound addition polymer film]

Norbornene compound addition polymer film of the present invention satisfies any one in following two kinds of situations at least: (1) is heated to 200 ℃ with film by 25 ℃, and when being cooled to 25 ℃ again, the size changing rate with cooled film before the heating is below the 100ppm; (2) under 25 ℃, film was flooded in propylene glycol methyl ether acetate 1 hour, before the dipping and the size changing rate of film behind the dipping be below the 100ppm.

These size changing rates are preferably below the 80ppm, more preferably below the 70ppm.

Herein, so-called size changing rate is being meant under the situation of above-mentioned (1): film is heated to before 200 ℃, the distance of any point-to-point transmission is designated as Y on 25 ℃ the film ⁰, film is heated to 200 ℃ after, the distance when being cooled to 25 ℃ again between above-mentioned 2 is designated as Y ¹, size changing rate is Y ⁰With Y ¹Between intensity of variation, with | Y ⁰-Y ¹|/Y ⁰Ask and calculate its value, specifically, use the value of asking calculation with aftermentioned embodiment same procedure exactly.

In addition, under the situation of above-mentioned (2), with film under 25 ℃ in propylene glycol monomethyl ether before the dipping, in the time of 25 ℃ on the film arbitrarily the distance of point-to-point transmission be designated as Y ⁰, be Y with the distance between above-mentioned 2 of the film of dipping after 1 hour ², size changing rate is Y ⁰With Y ²Between intensity of variation, with | Y ⁰-Y ²|/Y ⁰Ask and calculate its value, specifically, use the value of asking calculation with aftermentioned embodiment same procedure exactly.

Norbornene compound addition polymer film of the present invention is because thermotolerance is good, even heat in the scope of 200 ℃～second-order transition temperature, size changing rate still is below the 100ppm.No matter under air atmosphere, or at non-active gas for example under the nitrogen atmosphere, or under reduced pressure carry out the heating of film, all show above-mentioned good low gauge variations rate.

In addition, the norbornene compound addition polymer film of preferred the invention described above in 25 ℃ of water, flood before 1 hour and afterwards size changing rate be below the 100ppm.

This size changing rate more preferably below the 80ppm, is preferably below the 70ppm especially.

Herein, this size changing rate is asked calculation according to the described method of embodiment.

The solvent of norbornene compound addition polymer film of the present invention is preferably 1, below the 000ppm, more preferably below the 500ppm.

The thickness of norbornene compound addition polymer film of the present invention is generally 1～1, and 000 μ m is preferably 2～500 μ m.When thickness less than 1 μ m, then a little less than the film toughness, easily produce defective, the film that preparation 1,000 μ m is above, then to remove the curtain coating solvent very time-consuming in evaporation.

In addition, strict general " film " and " sheet " can be made a distinction by its thickness, but in the present invention, " film " is to comprise " film " and " sheet " both notions.

Norbornene compound addition polymer film of the present invention can obtain by following operation: in the preparation process of norbornene compound addition polymer film, with the residual solvent amount is 5, and the following film of 000ppm remains on from (T-150) ℃ or 180 ℃ comparatively high temps to the temperature range of T ℃ (T is the second-order transition temperature of norbornene compound addition polymer).

Following 2 kinds of methods specifically can be shown.

That is, the 1st kind of method: with the residual solvent amount is 5, and the casting films of the norbornene compound addition polymer that 000ppm is following is carried out heat treated at the comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃ temperature range.

The 2nd kind of method: without forming casting films, and directly prepare norbornene compound addition polymer film, in this process, film is imposed the thermal history of comparatively high temps to the T ℃ of scope from (T-150) ℃ or 180 ℃ by the norbornene compound addition polymer.

In the 1st kind of method, at first obtain casting films by the curtain coating moulding method.

(curtain coating moulding method)

The curtain coating moulding method is following method: the norbornene compound addition polymer is dissolved or dispersed in forms solution (curtain coating solution) in the organic solvent, use then die head, spreader with this solution coat on metal drum, steel band, polyethylene terephthalate (PET) or supports such as PEN polyester films such as (PEN), tetrafluoroethylene system band, remove then and desolvate, dry polymer, stripping film from the support again.

In addition, on support, dry then removing desolvated with solution coat for also available atomizer, hairbrush, the coating machine that rolls spin, impregnating, and stripping film from the support prepares film thus.In addition, can be by being coated with control thickness, surface smoothing etc. repeatedly.

The solvent that curtain coating be shaped to be used can be any solvent as long as can dissolve or disperse the norbornene compound addition polymer.

As its concrete example, can enumerate aliphatic hydrocarbon solvents such as pentane, hexane, heptane; Clicyclic hydrocarbon solvents such as pentamethylene, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, ethylcyclohexane, naphthane, norbornane, tristane, hexahydro-indenes, cyclooctane; Aromatic hydrocarbon solvents such as benzene,toluene,xylene; Methylene dichloride, chloroform, 1,2-ethylene dichloride etc. contains the aliphatic hydrocarbon solvent of halogen; Chlorobenzene, benzene dichloride etc. contain the aromatic hydrocarbon solvents of halogen; Nitromethane 99Min., oil of mirbane, acetonitrile etc. contain the solvent of nitrogen; Aliphatics such as ether, tetrahydrofuran (THF) or alicyclic ethers kind solvent; Aromatic ether such as methyl-phenoxide, phenyl ethyl ether kind solvent etc.

In these solvents, optimization aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, clicyclic hydrocarbon solvent, ether solvent and contain the halogen hydrocarbon solvent.

In order to reduce soltion viscosity, except that using these solvents, the preferred solvent that does not dissolve the norbornene compound addition polymer on a small quantity that adds.As this kind solvent, can enumerate methylcyclohexane, ethyl cellosolve 1-methoxyl group-cellosolve kind solvents such as 2-propyl alcohol; Ketones solvents such as diacetone alcohol, acetone, pimelinketone, methyl ethyl ketone, 4-methyl-2 pentanone; Esters solvent such as methyl lactate, ethyl lactate; Alcoholic solvents such as 1-amylalcohol, 1-butanols.

When the norbornene compound addition polymer was dissolved or dispersed in the solvent, the concentration of polymkeric substance was preferably 0.1～50 weight %, more preferably 0.2～45 weight %, preferred especially 0.5～40 weight %.If polymer concentration is less than above-mentioned lower limit, then there is the problem of the thickness that is difficult to guarantee film, in addition, because the foaming that solvent evaporation is followed etc. are difficult to obtain good film surface smoothing etc.On the other hand, if concentration surpasses the above-mentioned upper limit, then soltion viscosity is too high, and the thickness of gained film, surface are difficult for evenly.

In addition, the viscosity of above-mentioned solution is generally 1～1 during room temperature, and 000,000mPas, preferred 10～100,000mPas, more preferably 100～50,000mPas, preferred especially 1,000～40,000mPas.

In the curtain coating moulding method, the formation of film is at room temperature carried out usually, but in order to reduce the solvability of soltion viscosity, raising polymkeric substance, polymers soln can be heated in advance.According to the solvent for use boiling point, Heating temperature can be different, can be 30 ℃～250 ℃, preferred 40 ℃～200 ℃.

In the making method of norbornene compound addition polymer film of the present invention, when adopting the curtain coating moulding method, can be 5 with the residual solvent amount, the casting films of the norbornene compound addition polymer that 000ppm is following is carried out heat treated under following temperature, described temperature is the temperature of comparatively high temps to T ℃ the temperature range from (T-150) ℃ or 180 ℃, but in the preparation process of film, when existing with the state of film, the residual solvent amount is greater than 5, during 000ppm, preferably do not carry out the thermal history in the said temperature scope.

About the drying step in the above-mentioned curtain coating moulding method, be not particularly limited, can utilize normally used method to implement, for example, the method that film is passed through by a plurality of rollers in drying oven, but since in drying step if follow solvent evaporation to produce bubble, then the characteristic of film significantly reduces, therefore for fear of this problem, preferably drying step is undertaken by 2 a plurality of steps more than the stage, suitably control the temperature or the air quantity of each step.

Residual solvent amount in the casting films by above-mentioned curtain coating moulding method gained (below, be called for short " casting films " sometimes) is 5, and is preferred 4 below the 000ppm, below the 000ppm, and more preferably 3, preferred especially 2 below the 000ppm, below the 000ppm.If the residual solvent amount in the casting films surpasses the above-mentioned upper limit, then with it after the certain temperature range internal heating is handled, the size changing rate of the norbornene compound addition polymer film of the present invention of gained increases.In addition, residual solvent causes the second-order transition temperature of norbornene compound addition polymer to reduce, and poor heat resistance is in the easy deterioration of heat treatment step, painted.

Residual solvent amount in the casting films is controlled to be 5, and the method that 000ppm is following is not particularly limited, and, can enumerate vacuum-drying, drying etc. under air-flows such as air, nitrogen as concrete method.

Then, gained norbornene compound addition polymer film (casting films) is carried out heat treated under the temperature of the comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃ the temperature range.

This treatment temp is preferably comparatively high temps from (T-120) ℃ or 180 ℃ to T ℃ temperature range, and more preferably the comparatively high temps from (T-100) ℃ or 180 ℃ is to T ℃ temperature range.

According to preparation condition, the thickness of film, the heat treated time set is more than 1 second, and the scope below 100 hours is preferred more than 1 minute, the scope below 10 hours.

Heating atmosphere can be under air atmosphere, under non-active gas (for example nitrogen) atmosphere, also can be under reduced pressure, preferably under non-active gas atmosphere or under reduced pressure.

In the 2nd kind of preparation method of norbornene compound addition polymer film, without the casting films form, directly prepare norbornene compound addition polymer film by the norbornene compound addition polymer, in this process, film is imposed comparatively high temps from (T-150) ℃ or 180 ℃ to the thermal history of T ℃ of scope.In addition, it is identical with the situation of above-mentioned casting films to impose time of this thermal history.

The direct formation method of film can be passed through for example realization such as extrusion molding method, press forming method.

In addition, preparing above-mentioned residual solvent amount is 5, and during the following film of 000ppm, preferably combination is used softening agent.Contain softening agent in the film by making, can easily remove residual solvent, even also can easily the residual solvent in the film be controlled at 5, below the 000ppm with short period of time and lower temperature.

Herein, said softening agent is meant boiling point greater than 200 ℃, and preferred normal temperature is that the organic compound of liquid, said solvent are meant that boiling point is below 200 ℃ down, and preferred normal temperature is the organic compound of liquid down.

In addition, consider that aforesaid combination uses the method for softening agent can preferably adopt above-mentioned " curtain coating moulding method " from the angle that softening agent is dispersed in the film.

When utilizing " curtain coating moulding method ", the norbornene compound addition polymer is dissolved or dispersed in forms solution (curtain coating solution) in the organic solvent, in this solution, add softening agent and make its dissolving, with above-mentioned similarly use die head, spreader to coat metal drum etc. to go up after, remove and desolvate dry polymer, stripping film from the support, the casting films of softening agent that can obtain homodisperse is compared with not containing softening agent, and the residual solvent in this casting films can more easily be removed.

In addition, when adopting above-mentioned the 2nd kind of method, for example: softening agent can be added by raw material (the norbornene compound addition polymer etc.) input port of extrusion shaper.

With respect to the norbornene compound addition polymer of 100 weight parts, plasticizer dosage is preferably 0.1～30 weight part, and more preferably 1～20 weight part is preferably 2～10 weight parts especially.The amount of softening agent is very few, and then residual solvent can not be easy to remove sometimes, and the amount of softening agent is too much, then oozes out sometimes.

Object lesson as softening agent, can enumerate butyl ethyl malonate, Diisopropyl malonate, dimethyl adipate, Polycizer W 260, Wickenol 116, diisobutyl adipate, hexanodioic acid two (2-ethylhexyl), diisononyl adipate, Octyl adipate, diisodecyl adipate, hexanodioic acid two (butanediol ester) (PVC ス (Block チ Le ジ グ リ コ-Le) ア ジ ペ-ト), nonane diacid two (2-ethylhexyl), dimethyl sebacate, Uniflex DBS, sebacic acid two (2-ethylhexyl), dioctyl sebacate, diethyl succinate, diisopropyl ester amber acid, fatty diacid ester plasticizers such as dibutyl succinate; Phthalic ester plasticizers such as dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dibutyl phthalate, phthalic acid two (2-ethylhexyl), dinoctyl phthalates, Di Iso Decyl Phthalate, butyl benzyl phthalate, 2-nonyl-phthalate ester, diisononyl phthalate, phthalic acid (ethyl ester) ethyl glycollate; Trihemellitic acid ester plasticizers such as trihemellitic acid three (2-ethylhexyl) ester, trioctyl trimellate; Ortho-phosphoric acid ester plasticizers such as trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2-ethylhexyl), tricresyl phosphate (butoxy ethyl ester), triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (diformazan phenyl ester), diphenyl tolyl phosphate, di(2-ethylhexyl)phosphate phenyl 2-ethylhexyl; Acetate esters softening agent such as vanay, acetate 2-ethylhexyl; Polyester/epoxidation ester plasticizers such as poly-(hexanodioic acid 1,3 butylene glycol ester), epoxidised soybean oil; Ricinoleic acid ester plasticizers such as methyl acetyl ricinoleate; Sulfonamide plasticizers such as N-butylbenzenesulfonamide etc.Wherein, from considering preferred aliphat diprotic acid ester plasticizer and phthalic ester plasticizer with the angle of the consistency of norbornene compound addition polymer.When the intermiscibility of softening agent and norbornene compound addition polymer hangs down, can cause that the film light penetration reduces, mist degree rises, optical characteristics reduces sometimes.

The norbornene compound addition polymer membrane solvent content of the present invention that obtains like this is preferably 1, below the 000ppm, especially preferably is low to moderate below the 500ppm, and its total light transmittance is good, and physical strength is good, and size changing rate is little.

Has the reason of little size changing rate for norbornene compound addition polymer film of the present invention, supposition may be when carrying out the preparation of film under approaching the above-mentioned high temperature of glass transition temperature of polymer, because solvent evaporates is few, can not cause stable on heating deterioration, due to residual stress is relaxed.

Norbornene compound addition polymer film of the present invention preferably contains antioxidant.By using antioxidant, can improve the stability of film under the high temperature.

Antioxidant is not particularly limited, and preferred use is selected from least a kind in phenol antioxidant, lactone antioxidant and the Phosphorus antioxidant, considers from the angle that improves antioxidant effect, more preferably these antioxidant combination more than 2 kinds is used.

As the object lesson of phenol antioxidant, can enumerate 2, the 6-di-tert-butyl-4-methy phenol, 4,4 '-sulphur connection two (the 6-tertiary butyl-3-methylphenol), 1,1 '-two (4-hydroxyl phenol) hexanaphthene, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 3,3 '; 3 ", 5,5 '; 5 "-six tertiary butyls-a, a ', a "-(mesitylene-2,4; 6-three bases) three p-cresol; 1; 3,5-three (3,5-two-tertiary butyl-4-hydroxy benzyl)-1; 3; 5-triazine-2,4,6 (1H, 3H, 5H)-triketone etc.

Concrete example as Phosphorus antioxidant, can enumerate tricresyl phosphite (4-methoxyl group-3, the 5-diphenyl ester), tricresyl phosphite (nonyl phenyl ester), tricresyl phosphite (2,4-di-t-butyl phenyl ester), three [2-[[2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] two oxa-phosphorus suberane (dioxaphosphephin)-6-yls] oxygen] ethyl] amine etc.

As the concrete example of lactone antioxidant, can enumerate 3-hydroxyl-5, the reaction product of 7-di-t-butyl furans-2-ketone and o-Xylol etc.

The addition of these antioxidants has no particular limits, and is preferably 0.01～10 weight % with respect to the norbornene compound addition polymer, more preferably 0.05～5 weight %.

Preferred heat-resisting processing stabilizers, UV light absorber, photostabilizer and other stablizer etc. of adding in the norbornene compound addition polymer film of the present invention.

As the example of heat-resisting processing stabilizers, can enumerate the heat-resisting processing stabilizers of azanol class; 3,3 '-sulphur di-propionic acid two (dodecane ester), 3, the heat-resisting processing stabilizers of 3 '-sulphur di-propionic acid two sulphur classes such as (octadecane esters) etc.

As the example of UV light absorber, can enumerate benzotriazole category UV light absorber, triazines UV light absorber, benzophenone UV light absorber etc.

As the example of photostabilizer, can enumerate benzoate light stabilizer, hindered amine light stabilizer etc.

Can cooperate various additives in the norbornene compound addition polymer film of the present invention in case of necessity.

As these additives, can enumerate tinting materials such as inorganic filling material, organic filler material, processing stabilizers, static inhibitor, near infrared ray absorption, dyestuff or pigment, fluor, lubricant, fire retardant, linking agent etc.

About adding the method for antioxidant and other additive in the norbornene compound addition polymer film,, can use any means as long as can make antioxidant and other additive uniform dissolution or dispersion in film of the present invention.Antioxidant and other additive are dissolved in norbornene compound addition polymer film or disperse the back to prepare the method for casting films, this method is comparatively easy.

Because the total light transmittance of norbornene compound addition polymer film of the present invention is more than 70%, and is preferred more than 80%, more preferably more than 85%, therefore applicable to optics with material and display element parts.

In addition, norbornene compound addition polymer film can be the composite membrane with woven cloths or non-woven.This composite membrane obtains by following operation, norbornene compound addition polymer solution is infiltrated in woven cloths such as woven fiber glass or the non-woven, drying is carried out heat treated then under the temperature of the comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃ the temperature range.

Further, norbornene compound addition polymer film can also be the film that mixes with other thermoplastic resin.The method that obtains this blend films is: other thermoplastic resin can be mixed in the curtain coating solution, the extrusion by melting that melt extrudes machine etc. by curtain coating moulding method or use obtains then.Under the temperature of the comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃ the temperature range, carry out heat treated subsequently.

[nesa coating laminated film]

Norbornene compound addition polymer film of the present invention can lamination has nesa coating lamination (below be sometimes referred to as " nesa coating laminated film ").

As the material that forms transparent conductive film layer (transparent and electrically conductive film), usually can use oxide compound of metals such as Sn, In, Ti, Pb, Au, Pt, Ag or these metals etc., for example: tin indium oxide (ITO), aluminum oxide, silicon oxide, titanium oxide, zinc oxide, Tungsten oxide 99.999, aluminium nitride, silicon nitride, titanium nitride, Cadmium Sulfide, zinc sulphide, zinc selenide etc.On substrate, form these pure metal overlay films, this pure metal overlay film oxidation can be formed transparent conductive film layer thus in case of necessity.In addition, the method that forms of the form by the adhesion metal oxide skin just when also having from initial formation overlay film, but also can when forming overlay film at first, the form with pure metal or lower oxyde form, carry out oxide treatment such as heated oxide, anodic oxidation or liquid-phase oxidation then, make it transparence.

These transparent conductive film layers can be by will having other transparent conductive film layer sheet material, film etc. be bonded in and form on the norbornene compound addition polymer film, also can pass through Plasma Polymerization, sputtering method, vacuum vapour deposition, plating method, ion plating method, spray method, electrolysis liberation method etc. and on above-mentioned norbornene compound addition polymer film, directly form.The thickness of these transparent conductive film layers can suitably determine according to desirable characteristic, has no particular limits, and is generally 10～10,000 dust, preferred 50～5,000 dust.

When on norbornene compound addition polymer film of the present invention, directly forming transparent conductive film layer, can between this norbornene compound addition polymer film and transparent conductive film layer, form tack coat and key coat (ア Application カ-コ-ト in case of necessity

).Tack coat can use heat stable resins such as Resins, epoxy, pi, polyhutadiene, resol, polyether-ether-ketone to form.In addition, key coat can use the key coat agent of acrylic acid or the like prepolymers such as containing epoxy diacrylate, carbamate diacrylate, polyester diacrylate etc., and for example UV solidifies, being heating and curing forms by known curing.

In nesa coating laminated film of the present invention,, can be provided with tack coat in order to improve the binding property of smoothness, norbornene compound addition polymer film and nesa coating between norbornene compound addition polymer film and the nesa coating.Tack coat can pass through coating resin varnish, and drying obtains except that desolvating again.At this moment, consider, added preferably that to remove the resin that has film-forming properties after desolvating be the varnish of solid resin from the angle of even coating.As the resin of realizing this purpose, specifically can enumerate light-cured resins such as so-called acrylic acid or the like prepolymer such as Resins, epoxy diacrylate, urethane diacrylate, polyester diacrylate; The epoxies of ortho-cresol phenolic varnish type, bisphenol type, amino formate, acrylic acid or the like, urea class, melamine class, unsaturated polyester class heat-curing resin; Electronics line curable resin etc.Wherein, consider the preferred light curable resin from the angle of productivity and cost.

As the method that forms above-mentioned cured resin overlay film, intaglio plate coating method, contrary roller coating method are arranged, lick roller coating method etc., can use any means.

Nesa coating laminated film of the present invention can have gas barrier layer in a side opposite with nesa coating.Gas barrier layer can be formed also and can be formed by organic materials by inorganic materials.As spendable inorganic materials, can enumerate, silicon oxide, aluminum oxide, Indium sesquioxide etc. as organic materials, can be enumerated, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymeric amide etc.

About the thickness of gas barrier layer, be preferably 100～2,000 when using inorganic materials

, be preferably when using organic materials

These inorganic materials can be passed through known method system films such as sputtering method, ion plating method, electrical resistance heating, CVD method.In addition, when using organic materials, organic materials can be dissolved in the solvent, by above-mentioned coating method coating, drying is made film then.

In addition, between film and gas barrier layer, tack coat can be set.

Further, also can be used to protect the supercoat of this gas barrier layer at the gas barrier layer superimposed layer.Supercoat is preferably used the method system film same with above-mentioned tack coat.

[optics]

Except colour filter with the substrate, norbornene compound addition polymer film of the present invention also transmits with opticses such as waveguide, optical element sealing materials with substrate, liquid crystal display substrate, organic EL display base plate etc., light applicable to optical recording substrates such as light guiding plate, protective membrane, polarizing coating, phase retardation film, touch pad, transparent electrode substrate, CD, MD, DVD, TFT.

Film of the present invention is used in particular for the parts of display element specifically applicable to colour filter substrate, light guiding plate, protective membrane, polarizing coating, phase retardation film, touch pad, transparent electrode substrate, TFT substrate, liquid crystal display substrate, organic EL display base plate etc.

[colour filter]

Can be by pressing color-filter layer to obtain colour filter with the substrate upper strata at the colour filter that comprises norbornene compound addition polymer film of the present invention or nesa coating laminated film of the present invention.As laminating method, can use known colo(u)rant dispersion method, staining, electrodip process, print process, transfer printing etc.

For example, the colo(u)rant dispersion method be colour filter with substrate on, form black matrix (Block ラ with sputtering method or vacuum vapour deposition by metal photomasks such as chromium cpds such as chromium metal, chromic oxide, chromium nitride, nickel/tungstenalloys _StarNetwork マ ト リ _StarNetwork ス), the photosensitive polymer combination (chromatic photoresist (color resist)) that will be dispersed with red pigment with method of spin coating, metal bar coating method, flow coat method, mould coating method, roller coating method, spraying coating method etc. carries out full surface coated then, via mask exposure, develop after the exposure, form red pixel (picture element).After the same method, coating blueness and green pixel, exposure and development make it to form 3 color pixels.In addition, the order that 3 color pixels form not is specific, can select arbitrarily.When the black matrix between each pixel partly has pit, for making its smoothing, can with the surface with redix, transparent resin such as acrylic resin applies, and forms protective membrane.In addition, when matrix is deceived in formation, can adopt above-mentioned colo(u)rant dispersion method.Specifically, can will be dispersed with photoresist (black photoresistance (black resist)) coating, the exposure of black pigment and develop.

Aspect the method for the constituent of chromatic photoresist and black photoresistance composition and coating, exposure and development, for example can using, the spy opens the 2004-56151 communique, the spy opens described constituent and methods such as 2004-347831 communique.In addition, print process can be used known method, for example can use that the spy opens flat 6-347637 communique, the spy opens flat 11-326622 communique and the spy opens described printing ink of 2004-333971 communique and printing process.

Because norbornene compound addition polymer film of the present invention has very high patience to medicines such as photoresistance, ink, developing solutions, base plate deformation, fracture can not take place in colour filter lamination step.

In order to improve surface physical property such as cohesiveness, in case of necessity can be and formed and carry out processing that Corona discharge Treatment, ozonize, silane coupling agent, polyurethanes resin etc. form various resin films etc. on the substrate of black matrix to transparency carrier.When implementing to form the processing of various resin films, its thickness is generally 0.01～10 μ m, preferred 0.05～5 mu m range.

The colour filter that above-mentioned colour filter can be used as liquid crystal indicator uses, and further, also can be used as parts parts such as color monitor, liquid crystal indicator and uses.

Optics of the present invention can be to be more than 80% in norbornene compound addition polymer film upper strata press polish line transmitance of the present invention, and preferred more than 85%, linear expansivity is below 50ppm/ ℃, preferred below 40ppm/ ℃ transparent substrate and the parts that form.By the lamination of transparent base material, can suppress the deflection of colour filter, liquid crystal display substrate, the substrate that also can suppress due to the temperature variation expands, shrinks.

Used transparent substrate can use optical transmittance more than 80%, any base material below linear expansivity 50ppm/ ℃.Its concrete example can be enumerated, glass substrates such as optics white glass, soda-lime glass, film glass; Resin system substrates such as polyethylene terephthalate, PEN, polyimide etc.Wherein, glass substrates such as preferred especially optics white glass, film glass.

In order to improve the surface physical properties such as cohesiveness between norbornene compound addition polymer film and transparent substrate, can carry out Corona discharge Treatment, ozonize or plasma treatment to both surfaces in case of necessity, or can form various resin films such as silane coupling agent, urethane resin in surface both.When forming various resin film, film thickness is generally 0.01～10 μ m, the scope of preferred 0.05～5 μ m.

Further, in order to improve the adaptation between norbornene compound addition polymer film and transparent substrate, tack coat can be set between the two.Bonding can be passed through coating resin varnish, and drying realizes except that desolvating.At this moment, consider preferably be added with the varnish of solid resin, and this resin has film-forming properties except that after desolvating from the angle of even coating.

As the concrete example of this resinoid, can enumerate light-cured resins such as so-called acrylic polymer such as epoxy diacrylate, urethane diacrylate, polyester diacrylate; The epoxy resin of ortho-cresol phenolic varnish type, bisphenol type, amino formate, acrylic acid or the like, urea class, melamine class, unsaturated polyester class thermosetting resin; The electrocuring resin; Cyclic olefin resin or its modifier; Cyclisation polyisoprene resin or its modifier etc.

As the method that forms above-mentioned resin film, can enumerate intaglio plate coating method, contrary roller coating method, lick roller coating method etc., can use any means.

Except that optics, norbornene compound addition polymer film of the present invention also can be used for electric insulation part, electrical and electronic parts, electronic part encapsulation agent, medical equipment and wrapping material.

[electric insulation part]

Because the thermotolerance and the electrical characteristic of norbornene compound addition polymer film of the present invention are good, even carry out pyroprocessing, medicine processing, dimensional change is also very little, is suitable for use in electric insulation part most.

As electric insulation part, can enumerate, the insulating material of OA machines such as the coating material of electric wire/cable, computer, printer, duplicating machine, the insulating element of flexible circuit board etc. are particularly suitable for using as flexible circuit board.

[electrical and electronic parts]

With regard to electrical and electronic parts, norbornene compound addition polymer film of the present invention can be used for container, pallet, conveying belt, separatory membrane, washing container, pipe, conduit etc., the sealing material of semiconductor element, the sealing material of unicircuit, top layer material etc.

[medical equipment]

With regard to medical equipment, norbornene compound addition polymer film of the present invention can be used for drug container, transfusion bag, sampling receptacle, sterilising vessel, conduit etc.

Embodiment

Below, enumerate embodiment and comparative example, the present invention is more specifically illustrated.But the present invention is not limited to these embodiment.In addition, part among the embodiment and % are if no special instructions by weight.

In addition, test in embodiment and the comparative example and evaluation are carried out as follows.

(1) weight-average molecular weight of polymkeric substance (Mw) and number-average molecular weight (Mn)

By being that the gel permeation chromatography (GPC) of solvent is measured with tetrahydrofuran (THF) or chloroform, and obtain the polystyrene conversion value.

(2) copolymerization ratio of polymkeric substance

By ¹H-NMR measures and asks calculation.

(3) second-order transition temperature (Tg)

By measuring by the inflection temperature of the storage modulus E ' of Measurement of Dynamic Viscoelasticity.In the mensuration of dynamic viscoelastic, use DMS6100 (Seiko Instruments Inc system), the mensuration frequency is 10Hz, heat-up rate is 5 ℃/minute, exciting (add and shake) pattern is single waveform, and excitation amplitudes is 5.0 μ m, measures the inflection temperature of storage modulus E '.

(4) the residual solvent amount in the heat treated cephacoria

Use before heat treated, prepare solvent the film solvent for use with the dissolving of non-heat treated film after, with the residual solvent amount in the quantitative heat treated cephacoria of gas-chromatography.

(5) solvent in the norbornene compound addition polymer film

Use is the solvent the solvent for use in the membrane prepare of norbornene compound addition polymer, and is after the dissolving of norbornene compound addition polymer film, quantitative with gas-chromatography.

The size changing rate of (6) 200 ℃ of heating front and back norbornene compound addition polymer films

On the film of thickness 100 μ m, length and each 100mm of width, do a plurality of marks, in atmosphere, heated 1 hour in 200 ℃.To before and after the heat treated 25 ℃ the time between each mark range difference average, obtain size changing rate.

(7) use propylene glycol methyl ether acetate (PGMEA) to flood the size changing rate of front and back norbornene compound addition polymer film

On the norbornene compound addition polymer film of thickness 100 μ m, length and each 100mm of width, do a plurality of marks, in in propylene glycol methyl ether acetate (PGMEA), flooding 1 hour under 25 ℃, then, 100 ℃ of vacuum-dryings 1 hour, remove the PGMEA that adheres on the striping.To with before and after the PGMEA dipping between each mark 25 ℃ the time range difference average, obtain size changing rate.

(8) size changing rate of norbornene compound addition polymer film before and after the usefulness water retting

At thickness 100 μ m, do a plurality of marks on the norbornene compound addition polymer film of each 100mm in length and breadth, under 25 ℃ in water dipping 1 hour, then,, remove the water that adheres on the striping 100 ℃ of vacuum-dryings 1 hour.To with before and after the water retting between each mark 25 ℃ the time range difference average, obtain size changing rate.

(9) total light transmittance of norbornene compound addition polymer film

To the norbornene compound addition polymer film of thickness 100 μ m,, in wavelength 400～700nm scope, measure with UV, visible light spectrometer (JASCO society system, trade(brand)name " V-550 ").

(reference example 1)

(synthesizing of norbornene compound addition polymer (a))

Close 1.14 parts of 0.77 part of palladium and four (pentafluorophenyl group) lithium tetraborates in the glass reactor of nitrogen replacement, adding chlorine (allyl group) (tricyclohexyl phosphine), add 2 parts of toluene then, preparation catalyzer liquid.

Subsequently, in the withstand voltage glass reactor that has stirrer of nitrogen replacement, adding dicyclo [2.2.1] hept-2-ene" (NB; Molecular weight=94) 1,650 part, 5-ethyl dicyclo [2.2.1] hept-2-ene" (EtNB; Molecular weight=122) 915 parts, adjust 1,300 part of the vinylbenzene of agent and as 7,200 parts of the toluene of polymer solvent, then to wherein adding above-mentioned catalyst solution, initiated polymerization as molecular weight.After 4.5 hours, polymerization liquid is injected a large amount of methyl alcohol 45 ℃ of reactions, polymkeric substance is separated out fully, behind the filtration washing,, obtain 2,462 parts in polymkeric substance (a) 50 ℃ of drying under reduced pressure 18 hours.

The number-average molecular weight of polymkeric substance (a) (below, sometimes abbreviate " Mn " as) be 140,000, weight-average molecular weight (below, sometimes abbreviate " Mw " as) be 502,000, the unitary ratio of components of NB unit/EtNB is 71/29 (moles/mole) in the polymkeric substance (a), and second-order transition temperature (Tg) is 281 ℃.

(reference example 2)

(synthesizing of norbornene compound addition polymer (b))

Except monomer being replaced by 2-norbornylene (NB; Molecular weight=94) 1,175 part and 5,6-dimethyl dicyclo [2.2.1] hept-2-ene" (DMNB; Molecular weight=122) 1,525 especially, and other is all identical with embodiment 1, obtains 2,027 parts in polymkeric substance (b).

The Mn of polymkeric substance (b) is 117,000, and Mw is 377,000, and the NB unit/DMNB unit ratio of components is 52/48 (moles/mole) in the polymkeric substance (b), and Tg is 301 ℃.

(reference example 3)

(synthesizing of norbornene compound addition polymer (c))

Except monomer being replaced by 2-norbornylene (NB; Molecular weight=94) 1,650 part and Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylate methyl ester (TCDMC; Molecular weight=218) 675 parts especially, other is all identical with embodiment 1, obtains 1,800 part in polymkeric substance (c).

The Mn of polymkeric substance (c) is 105,000, and Mw is 278,000, and the NB unit/TCDMC unit ratio of components is 85/15 (moles/mole) in the polymkeric substance (b), and Tg is 335 ℃.

(embodiment 1～3)

10% toluene solution of preparation polymkeric substance (a), interpolation is 0.5% 3-(3 with respect to polymkeric substance (a) in this solution, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid stearyl, be 1.0% tricresyl phosphite (2 with respect to polymkeric substance (a), 4-di-t-butyl phenyl ester), with respect to polymkeric substance (a) be 0.3% by 3-hydroxyl-5, the product that 7-di-t-butyl furans-2-ketone and o-Xylol react, as antioxidant, and make it dissolving.With this solution (a) curtain coating on smooth teflon plate, under room temperature, the air draught through 24 hours the evaporation remove toluene after, 80 ℃ of vacuum-dryings 24 hours, 150 ℃ of vacuum-dryings 24 hours, obtaining the residual solvent amount was the casting films (A) of 100 μ m less than 500ppm and thickness.

Equally, by polymkeric substance (b) with (c) obtain the casting films (B) of thickness 100 μ m respectively and (C).The residual solvent amount of gained casting films (A)～(C) is as shown in table 1.

Subsequently, with casting films (A) and (B) under nitrogen atmosphere in 250 ℃ of heat treated 1 hour, with casting films (C) under nitrogen atmosphere in 280 ℃ of heat treated 1 hour, obtain norbornene compound addition polymer film respectively.

Measure these norbornene compound addition polymer films before and after 200 ℃ of heating, with before and after the PGMEA dipping and with size changing rate, solvent and the total light transmittance of water retting front and back.The result is as shown in table 1.In addition, "＜50 " and "＜500 " refer to " less than 50ppm " and " less than 500ppm " respectively in the table 1.In addition, the Tg in the table 1 is the measurement result of film.

(embodiment 4)

In the solution (a) of the polymkeric substance (a) that obtains with embodiment 1 described method, further adding with respect to polymkeric substance (a) is 5.0% butyl ethyl malonate (softening agent), and makes it dissolving.

With this solution casting on smooth teflon plate, under room temperature, the air draught with 24 hours the evaporation remove toluene after, 80 ℃ of vacuum-dryings 1 hour, 150 ℃ of vacuum-dryings 1 hour, obtaining the residual solvent amount was the casting films (D) of 100 μ m less than 500ppm and thickness.

Subsequently, similarly to Example 1 casting films (D) is carried out heat treated, obtain norbornene compound addition polymer film.This film is carried out the mensuration identical with embodiment 1, and the result is as shown in table 1.

(comparative example 1～3)

For casting films (A), (B) and (C), all do not carry out under nitrogen atmosphere in 250～280 ℃ heat treated size up velocity of variation, solvent and total light transmittance.The result is as shown in table 1.

(comparative example 4)

To casting films (C) under nitrogen atmosphere in 160 ℃ of heat treated of carrying out 1 hour.Measure size changing rate, solvent and the total light transmittance of this film.The result is as shown in table 1.

(comparative example 5)

10% toluene solution of preparation polymkeric substance (a), interpolation is 0.5% 3-(3 with respect to polymkeric substance (a) in this solution, the 5-di-tert-butyl-hydroxy phenyl) the propionic acid stearyl, be 1.0% tricresyl phosphite (2 with respect to polymkeric substance (a), 4-di-t-butyl phenyl ester), with respect to polymkeric substance (a) be 0.3% by 3-hydroxyl-5,7-di-t-butyl furans-2-ketone and o-Xylol react the product that obtains as antioxidant, and make it dissolving.With this solution casting on smooth teflon plate, under room temperature, the air draught after toluene is removed in evaporation in 24 hours, 200 ℃ of vacuum-dryings 1 hour, obtain the casting films (A ') of thickness 100 μ m.The residual solvent amount is 25 in the film, 000ppm.

With casting films (A ') under nitrogen atmosphere in 250 ℃ of heat treated of carrying out 1 hour.Measure this film before and after 200 ℃ of heating, with before and after the PGMEA dipping and with size changing rate, solvent and the total light transmittance of water retting front and back.The result is as shown in table 1.

[table 1]

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Polymkeric substance composition (mole %) ( ＊1)	(a)	(b)	(c)	(a)
NB	71	52	85	71
					EtNB	29	-	-	29
DMNB	-	48	-	-
					TCDMC	-	-	15	-
Film	(A)	(B)	(C)	(D)
					The T=second-order transition temperature (℃)	281	301	335	260
Residual solvent amount (ppm)	<500	<500	<500	<500
					Heat treated	Have	Have	Have	Have
The T=second-order transition temperature (℃)	281	301	335	260
					T1=heat treated temperature (℃)	250	250	280	250
T2:(T-150) comparatively high temps and in 180 ℃	180	180	185	180
					T2 ≦ T1 ≦ T whether?	Be	Be	Be	Be
Time	1 hour	1 hour	1 hour	1 hour
					Residual solvent amount (ppm)	<500	<500	<500	<500
Size changing rate (ppm)
					Before and after 200 ℃ of heating	<50	<50	<50	<50
Before and after PGMEA floods	<50	<50	<50	<50
					Before and after the water retting	<50	<50	<50	<50
Total light transmittance (%)	91	91	91	91

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
						Polymkeric substance is formed (mole %) (* 1)	(a)	(b)	(c)	(c)	(a)
NB	71	52	85	85	71
						EtNB	29	-	-	-	29
DMNB	-	48	-	-	-
						TCDMC	-	-	15	15	-
Film	(A)	(B)	(C)	(C)	(A′)
						The T=second-order transition temperature (℃)	281	301	335	335	281
Residual solvent amount (ppm)	<500	<500	<500	<500	25，000
						Heat treated	Do not have	Do not have	Do not have	Have	Have
The T=second-order transition temperature (℃)	281	301	335	335	281
						T1=heat treated temperature (℃)	-	-	-	160	250
T2:(T-150) comparatively high temps and in 180 ℃	180	180	185	185	180
						T2 ≦ T1 ≦ T whether?	Not	Not	Not	Not	Be
Time	-	-	-	1 hour	1 hour
						Residual solvent amount (ppm)	<500	<500	<500	<500	<500
Size changing rate (ppm)
						Before and after 200 ℃ of heating	6，500	5，500	4，500	2，500	1，800
Before and after PGMEA floods	500	400	2，000	500	1，500
						Before and after the water retting	<50	<50	250	150	<50
Total light transmittance (%)	91	91	91	91	85

(footnote of table 1)

^*1:NB: dicyclo [2.2.1] hept-2-ene"

EtNB:5-ethyl dicyclo [2.2.1] hept-2-ene"

DMNB:5,6-dimethyl dicyclo [2.2.1] hept-2-ene"

TCDMC: Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylate methyl ester

Result by table 1 can draw as drawing a conclusion.

After casting films forms, if without the heat treated under the temperature of the comparatively high temps from (T-150) ℃ or 180 ℃ to the temperature range of T ℃ (T is the second-order transition temperature of norbornene compound addition polymer), norbornene compound addition polymer film might be before and after 200 ℃ of heating and before and after the PGMEA dipping, its size changing rate all increases (comparative example 1～3), size changing rate variation (comparative example 3) before and after the water retting.In addition, even carry out heat treated, but the heat treated temperature finds that its size changing rate all increases (comparative example 4) before and after 200 ℃ of heating, before and after the PGMEA dipping and before and after water retting beyond the above-mentioned scope of the present invention regulation the time.Residual solvent amount before the heat treated in the casting films surpasses the scope of the present invention's regulation when a lot, in the said temperature scope of the present invention's regulation, carry out heat treated even find, before and after 200 ℃ of heating, before and after the PGMEA dipping, the size changing rate of film still all can increase, and the total light transmittance of these samples low (comparative example 5).

By contrast, find: will in preparation process, the residual solvent amount be 5, the following casting films of 000ppm remains under the temperature of comparatively high temps to the temperature range of T ℃ (T is the second-order transition temperature of norbornene compound addition polymer) from (T-150) ℃ or 180 ℃, through behind the said process, before and after 200 ℃ of heating, before and after the PGMEA dipping, before and after water retting, the size changing rate of film is all very little, total light transmittance also very high (embodiment 1～4).

In addition, when containing the casting films softening agent (embodiment 4), (embodiment 1～3) is compared during with plasticizer-containing not, can make the residual solvent amount reach 5 at short notice, below the 000ppm.

Claims (11)

1. norbornene compound addition polymer film, it satisfies at least a in following two kinds of situations:

(1) be heated to 200 ℃ by 25 ℃ after, when being cooled to 25 ℃ again, before the heating and the size changing rate between the cooling back be below the 100ppm;

(2) under 25 ℃, impregnated in the propylene glycol methyl ether acetate 1 hour, before the dipping and the size changing rate between the dipping back be below the 100ppm.

2. the described norbornene compound addition polymer of claim 1 film floods it 1 hour in 25 ℃ of water, and dipping size changing rate preceding and that flood between the back is below the 100ppm.

3. claim 1 or 2 described norbornene compound addition polymer films, its solvent is 1, below the 000ppm.

4. each described norbornene compound addition polymer film of claim 1～3, it contains with respect to the norbornene compound addition polymer is the following antioxidant of 0.01～10 weight %, and described antioxidant is to be selected from phenol antioxidant, lactone antioxidant and Phosphorus antioxidant at least a kind.

5. the method for preparing each described norbornene compound addition polymer film of claim 1～4, this method may further comprise the steps: in the preparation process of norbornene compound addition polymer film, with the residual solvent amount is 5, the following film of 000ppm keeps in the following temperature range, described temperature range be comparatively high temps from (T-150) ℃ or 180 ℃ to T ℃, T is the second-order transition temperature of norbornene compound addition polymer.

6. the described method for preparing norbornene compound addition polymer film of claim 5, wherein, with the residual solvent amount is 5, the following norbornene compound addition polymer casting films of 000ppm is carried out heat treated in following temperature range, described temperature range is that comparatively high temps from (T-150) ℃ or 180 ℃ is to T ℃.

7. the described method for preparing norbornene compound addition polymer film of claim 5, wherein, in following process, film is imposed the thermal history of comparatively high temps to the T ℃ of scope from (T-150) ℃ or 180 ℃, described process is: without the casting films form, and the direct process for preparing norbornene compound addition polymer film by the norbornene compound addition polymer.

8. each described method for preparing norbornene compound addition polymer film of claim 5～7 wherein, is 5 in the above-mentioned residual solvent amount of preparation, during the following film of 000ppm, is used in combination softening agent.

9. each described norbornene compound addition polymer film of claim 1～4, its further lamination has nesa coating.

10. optics, electric insulation part, electrical and electronic parts, electronic part encapsulation material, medical equipment or wrapping material, it comprises each described norbornene compound addition polymer film in claim 1～4 and the claim 9.

11. optics, it is more than 80% by each described norbornene compound addition polymer film and light penetration in claim 1～4 and the claim 9 and linear expansivity is that transparent substrate lamination below 50ppm/ ℃ forms.