Polymers and Varnishes

Abstract

To provide a polymer that is excellent in heat resistance and transparency and also excellent in adhesion to members, film formability, and solubility in organic solvent, and a varnish containing the polymer.SOLUTION: A polymer comprises constitutional units represented by the general formulae (1) and (2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to polymers and varnishes. [Background technology]

[0002] Conventionally, adhesive compositions for bonding to protective glass or the like to protect device parts from foreign matter such as moisture and dust, and resin compositions for protecting, sealing, bonding, etc., semiconductor lasers, photodiodes, phototransistors, and solar cells have been used for electronic components. Polymers contained in such resin compositions are required to have excellent adhesion to various components, heat resistance, transparency, film-forming properties, etc. Furthermore, from the viewpoint of handling, it is also preferable that the polymers have excellent solubility in organic solvents.

[0003] Patent Document 1 discloses a method for polymerizing cyclic olefins in the presence of a specific catalyst. The document states that the cyclic olefin may have a group containing an alkenyl group or an alkylcarbonyloxy group. However, the document does not disclose any specific examples of synthesis using cyclic olefins having such groups. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 6,455,650 Summary of the Invention [Problem to be solved by the invention]

[0005] The polymer synthesized in Patent Document 1 has room for improvement in heat resistance, adhesion, solubility in solvents, and curability, and there is particularly room for improvement in achieving both adhesion and permeability while structurally retaining curability. [Means for solving the problem]

[0006] The present inventors have found that the above problems can be solved by using a polymer having a specific structure, and have completed the present invention. That is, the present invention can be shown as follows.

[0007] According to the present invention, It is possible to provide a polymer containing constitutional units represented by the following general formulas (1) and (2). [ka] (In general formula (1), Q 1 represents an alkylene group having 1 to 5 carbon atoms, a is 0, 1 or 2, and m is an average number of 1 or more and 500 or less. 2 represents a single bond or an alkylene group having 1 to 5 carbon atoms, b is 0, 1 or 2, and n is an average number of 1 or more and 500 or less.

[0008] According to the present invention, A varnish is provided that includes the polymer and an organic solvent. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polymer that has excellent heat resistance and transparency, as well as excellent adhesion to components, film-forming properties, and solubility in organic solvents, and a varnish containing the polymer. In other words, the polymer of the present invention has an excellent balance of these properties. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a 1H-NMR chart of the polymer obtained in Example 1. [Figure 2] 1 is a graph showing the light transmittance at each wavelength of the resin film obtained in Example 4 measured with an ultraviolet-visible spectrophotometer. DETAILED DESCRIPTION OF THE INVENTION

[0011] The polymer of the present invention and a varnish containing the polymer will be described below based on embodiments. For example, "1 to 10" means "1 or more" to "10 or less" unless otherwise specified.

[0012] [polymer] The polymer of this embodiment contains constitutional units represented by the following general formulas (1) and (2).

[0013] [ka]

[0014] In general formula (1), Q 1 represents an alkylene group having 1 to 5 carbon atoms, and specific examples thereof include methylene, ethylene, propylene, butylene, and pentylene. Q 1 is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms.

[0015] In the general formula (1), a is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0016] The average value of the number m of repeating units is a number of 1 or more and 500 or less.

[0017] In general formula (2), Q 2 represents a single bond or an alkylene group having 1 to 5 carbon atoms. Specific examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene, and pentylene.

[0018] Q 2 is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably a single bond or an alkylene group having 1 to 2 carbon atoms, and even more preferably a single bond or an alkylene group having 1 carbon atom.

[0019] b is 0, 1 or 2, preferably 0 or 1, and more preferably 0. The average value of the number of repeating units n is a number of 1 to 500. In terms of the effects of the present invention, the ratio of the number of repeating units m to the number of repeating units n (m:n) of the polymer of this embodiment can be preferably 5:95 to 95:5, more preferably 15:85 to 85:15, and even more preferably 20:80 to 80:20.

[0020] Since the polymer of this embodiment contains the structural unit, it has excellent heat resistance and transparency, and also has excellent adhesion to members such as silicon wafers. Furthermore, the polymer of this embodiment has excellent film-forming properties, allowing the formation of cured films with a film thickness of 5 μm or more, and also has excellent solubility in organic solvents and excellent handleability.

[0021] The polymer of this embodiment may contain other structural units as long as the effects of the present invention are achieved. Examples of other structural units include structural units derived from norbornene.

[0022] The weight average molecular weight Mw of the polymer of this embodiment is 30,000 or more and 800,000 or less, preferably 50,000 or more and 500,000 or less, and more preferably 100,000 or more and 300,000 or less.

[0023] When the weight average molecular weight is within this range, the effects of the present invention are excellent, in particular, the solubility in organic solvents is excellent, handling is excellent, and film formation is excellent, allowing the formation of a thick film of 5 μm or more.

[0024] The dispersity of the polymer (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 6.0, more preferably 1.5 to 5.0, and even more preferably 2.0 to 4.0. By appropriately adjusting the dispersity, the physical properties of the polymer can be made uniform, which is preferable.

[0025] The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are determined, for example, from a polystyrene-equivalent value obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions for GPC measurement are, for example, as follows: Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0026] The glass transition temperature of the polymer is preferably 150 to 350°C, more preferably 200 to 300°C. The polymer has a relatively high glass transition temperature due to the inclusion of structural units represented by general formulas (1) and (2). This is preferable in that a cured film formed between components or on the surface of a component can be stable in the manufacturing and use environment of electronic components. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0027] The polymer of this embodiment has excellent transparency and high light transmittance, which contributes to the performance stability of electronic components that require high transmittance. Specifically, the light transmittance of a resin film obtained under the following conditions in the wavelength range of 300 nm to 600 nm is preferably 95% or more, more preferably 96% or more, and even more preferably 98% or more. The upper limit is not particularly limited, but is about 100% or less. (conditions) A propylene glycol monomethyl ether solution with a polymer concentration of 20% by weight is applied and heated at 100°C for 1 minute in the atmosphere to obtain a resin film with a thickness of 3µm.

[0028] The polymer of the present embodiment has excellent solubility in various organic solvents, and therefore has excellent handleability. In addition, the types and amounts of additives in varnishes and the like can be adjusted as desired, providing excellent flexibility in formulation design.

[0029] Examples of organic solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, and cyclohexanone; esters such as propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, and butyl acetate; alcohols such as propylene glycol monomethyl ether (PGME), n-propyl alcohol, ethylene glycol, and diethylene glycol; ethers such as tetrahydrofuran, dioxane, and ethyl isobutyl ether; and other dissolving solvents such as toluene and chloroform.

[0030] <Polymer manufacturing method> The polymer of this embodiment can be synthesized by coordination polymerization of a cyclic olefin compound (1a) represented by the following general formula (1a) and a cyclic olefin compound (2a) represented by the following general formula (2a).

[0031] [ka]

[0032] In general formula (1a), Q 1 and a has the same meaning as in general formula (1). In general formula (2a), Q 2 and b have the same meaning as in general formula (2).

[0033] The above reaction can be carried out in an organic solvent in the presence of a polymerization catalyst and a cocatalyst. Examples of organic solvents include ketones such as methyl ethyl ketone (MEK); ethers such as propylene glycol monomethyl ether, diethyl ether, and tetrahydrofuran (THF); toluene; esters such as ethyl acetate and butyl acetate; and alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; and one or more of these may be used. The polymerization catalyst includes a nickel catalyst, a palladium catalyst, and the like.

[0034] The polymerization catalyst may be, for example, a cationic complex in which a phosphine- or diimine-based ligand is coordinated to a palladium complex or a nickel complex, and a counter anion. One type of organometallic catalyst may be used alone, or two or more types may be used in combination.

[0035] Examples of the palladium complex include allylpalladium complexes such as (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I) tetrakis(2,3,4,5,6-pentafluorophenyl)borate and π-allylpalladium chloride dimer; organic carboxylic acid salts of palladium such as acetate, propionate, maleate, and naphthoate of palladium; organic carboxylic acid complexes of palladium such as triphenylphosphine complex of palladium acetate, tri(m-tolyl)phosphine complex of palladium acetate, and tricyclohexylphosphine complex of palladium acetate; palladium organic sulfonates such as palladium dibutyl phosphite and p-toluenesulfonate; palladium β-diketone compounds such as palladium bis(acetylacetonato)palladium, bis(hexafluoroacetylacetonato)palladium, bis(ethylacetoacetate)palladium, and bis(phenylacetoacetate)palladium; palladium halide complexes such as dichlorobis(triphenylphosphine)palladium, bis[tri(m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, and acetonyltriphenylphosphonium complex; and the like.

[0036] Examples of the phosphine-based ligand include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

[0037] Examples of the counter anion include triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diphenylanilinium tetrakis(pentafluorophenyl)borate, and lithium tetrakis(pentafluorophenyl)borate. It is believed that the reaction product of the polymerization catalyst and the cyclic olefin compound is activated by the counter anion, thereby causing the polymerization of the cyclic olefin compound to proceed. The heating temperature is about 80° C. to 200° C., and the reaction time is about 0.5 to 72 hours. It is more preferable to carry out solution polymerization after removing dissolved oxygen in the solvent by nitrogen bubbling.

[0038] In this embodiment, the molecular weight of the polymer can be adjusted by the amount of catalyst, the reaction temperature, etc., or by adding a molecular weight adjuster or a chain transfer agent separately in the synthesis reaction.

[0039] In the polymerization step, a molecular weight modifier, a chain transfer agent, etc. can be used as needed. Examples of the chain transfer agent include alkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane; and organic aluminum compounds such as triethylaluminum, tributylaluminum, and MAO (methylalumoxane). The chain transfer agent may be used alone or in combination of two or more.

[0040] After the polymerization reaction, it is preferable to further carry out the following steps as appropriate in order to remove unnecessary components other than the desired polymer. For example, the reaction solution can be passed through a column of ion exchange resin or the like to remove metal impurities.

[0041] Furthermore, the reaction solution can be poured into a poor solvent to reprecipitate the polymer, remove unreacted monomers, and dry the resulting solid, which can then be dissolved in an organic solvent again and used as a purified product. In particular, in applications where impurities and foreign matter are a problem, it is preferable to dissolve the solid in an organic solvent again and filter it to produce a purified varnish. The polymer concentration in the varnish (polymer solution) (100% by weight) is not particularly limited, but is about 10 to 30% by weight.

[0042] [varnish] The varnish of this embodiment contains the above-mentioned polymer and an organic solvent. The polymer of the present embodiment has excellent solubility in various organic solvents, and therefore is easy to handle, and can be dissolved in an amount of, for example, 10 to 50 parts by mass, preferably 15 to 40 parts by mass, per 100 parts by mass of organic solvent. By adjusting the polymer viscosity by the concentration, excellent workability and the like can be achieved.

[0043] Examples of organic solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, and cyclohexanone; esters such as propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, and butyl acetate; alcohols such as propylene glycol monomethyl ether (PGME), n-propyl alcohol, ethylene glycol, and diethylene glycol; ethers such as tetrahydrofuran, dioxane, and ethyl isobutyl ether; and other dissolving solvents such as toluene and chloroform.

[0044] The varnish of this embodiment preferably further contains an antioxidant, which provides a cured film obtained from the varnish of this embodiment with better heat resistance and transparency. Examples of the antioxidant include hindered phenol-based antioxidants, thioether-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, thiol-based antioxidants, benzotriazole-based antioxidants, benzophenone-based antioxidants, hydroxylamine-based antioxidants, salicylic acid ester-based antioxidants, and triazine-based antioxidants, and the antioxidant may contain at least one selected from these.

[0045] Examples of hindered phenol antioxidants include 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene.

[0046] Examples of thioether antioxidants include 4,4'-thiobis[2-t-butyl-5-methylphenol]bis[3-(dodecylthio)propionate], thiobis[2-(1,1-dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(tetradecylthio)propionate], pentaerythritol tetrakis(3-n-dodecylthiopropionate), bis(tridecyl)thiodipropionate, and 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate].

[0047] Examples of phosphorus-based antioxidants include monophosphite such as triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, and 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Phosphite compounds: diphosphite compounds such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0048] Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, and 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl Examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine polycondensate, N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, and bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate.

[0049] Examples of thiol-based antioxidants include pentaerythritol tetrakis(3-mercaptobutyrate) and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0050] Examples of the benzotriazole antioxidant include 1,2,3-benzotriazole (1H-benzotriazole), 1H-benzotriazole sodium salt, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole potassium salt, 5-methyl-1H-benzotriazole potassium salt, 4-methyl-1H-benzotriazole amine salt, 5-methyl-1H-benzotriazole amine salt, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole.

[0051] Examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0052] Examples of the hydroxylamine-based antioxidant include hydroxylamine, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine phosphate, hydroxylamine hydrochloride, hydroxylamine citrate, and hydroxylamine oxalate.

[0053] Examples of salicylate antioxidants include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine.

[0054] The varnish of this embodiment may contain an antioxidant in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polymer, which provides the cured film obtained from the varnish of this embodiment with even more excellent heat resistance and transparency.

[0055] The varnish of the present embodiment may contain, as needed, a polymerization initiator, a photoacid generator, a photobase generator, a thermal acid generator, a thermal base generator, an antioxidant, a surfactant, a dispersant, an ultraviolet absorber, an ultraviolet blocking agent, an infrared blocking agent, a reactive diluent, and the like.

[0056] A cured film obtained from the following varnish containing the polymer of this embodiment under the following conditions has a light transmittance of preferably 90% or more, more preferably 91% or more, and even more preferably 92% or more in the wavelength range of 350 nm or more and 600 nm or less. The upper limit is not particularly limited, but is about 98% or less. (conditions) A propylene glycol monomethyl ether solution (varnish) containing the polymer at a concentration of 20% by weight is applied and heated at 160° C. for 30 minutes in the atmosphere to obtain a cured film having a thickness of 3 μm. As described above, the cured film obtained from the varnish containing the polymer of this embodiment has excellent heat resistance and is inhibited from discoloring, and therefore has excellent transparency.

[0057] A cured film obtained from the varnish containing the polymer of this embodiment under the following conditions has a light transmittance at a wavelength of 350 nm of preferably 95% or more, more preferably 96% or more, and even more preferably 98% or more. Furthermore, the light transmittance at a wavelength of 400 nm is preferably 95% or more, more preferably 96% or more, and even more preferably 98% or more. There are no particular upper limits, but they are all about 100% or less. (conditions) A propylene glycol monomethyl ether solution (varnish) containing 20% ​​by weight of the polymer containing 3 phr of the antioxidant is applied and heated at 160° C. for 30 minutes in the atmosphere to obtain a cured film having a thickness of 3 μm.

[0058] Furthermore, a cured film obtained from the following varnish containing the polymer of this embodiment under the following conditions has a light transmittance at a wavelength of 350 nm of preferably 80% or more, more preferably 81% or more, and even more preferably 82% or more. Furthermore, the light transmittance at a wavelength of 400 nm is preferably 90% or more, more preferably 91% or more, and even more preferably 92% or more. There are no particular upper limits, but they are all about 100% or less. (conditions) A propylene glycol monomethyl ether solution (varnish) containing 20% ​​by weight of the polymer containing 3 phr of the antioxidant is applied and heated at 200° C. for 30 minutes in the atmosphere to obtain a cured film having a thickness of 3 μm.

[0059] As described above, the cured film obtained from the varnish containing the polymer of this embodiment and an antioxidant has even better heat resistance and is more inhibited from discoloring, resulting in even better transparency.

[0060] The polymers of this embodiment are bonded to each other via the vinyl group of the structural unit represented by general formula (2) of the polymer, and therefore the resulting cured film has excellent heat resistance and, in turn, excellent transparency.

[0061] A cured film made of a polymer obtained from the varnish of this embodiment can be used in various electronic components, such as semiconductor lasers, photodiodes, phototransistors, and solar cells.

[0062] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention. [Example]

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0064] (Preparation of catalyst solution 1) In a glass vessel that had been previously dehydrated and filled with a nitrogen atmosphere, 0.100 g (0.000083 mol) of (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I) tetrakis(2,3,4,5,6-pentafluorophenyl)borate and 20 g of dehydrated butyl acetate were added and stirred at room temperature for 1 hour to dissolve. Next, 0.265 g (0.00033 mol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was added and stirred for an additional 30 minutes. The solution was then filtered through a filter to obtain catalyst solution 1.

[0065] (Preparation of catalyst solution 2) Into a glass vessel that had been previously dehydrated and filled with a nitrogen atmosphere, 0.72 g (0.000015 mol) of (acetato-κ0)(acetonitrile)bis[tris(1-methylethyl)phosphine]palladium(I) tetrakis(2,3,4,5,6-pentafluorophenyl)borate and 20 g of dehydrated butyl acetate were added, and the mixture was stirred at room temperature for 1 hour to dissolve. Next, 2.90 g (0.00009 mol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was added, and the mixture was stirred for an additional 30 minutes. The solution was then filtered through a filter to obtain catalyst solution 2.

[0066] (Preparation of catalyst solution 3) 0.0391 g (0.0001 mol) of allylpalladium(II) chloride (dimer), 0.072 g (0.00026 mol) of diphenylcyclohexylphosphine, and 20 g of dehydrated toluene were added to a glass vessel that had been previously dehydrated and filled with a nitrogen atmosphere, and the mixture was stirred at room temperature for 1 hour to dissolve. Next, 0.51 g (0.00064 mol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was added and stirred for an additional 30 minutes. The solution was then filtered through a filter to obtain catalyst solution 3.

[0067] Example 1: Synthesis of Copolymer 1 A cyclic olefin of the following chemical formula (a) (537 g, 3.23 mol) and a cyclic olefin of the following chemical formula (b) (209 g, 1.74 mol) were weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser and dissolved in 1,500 g of butyl acetate. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 100°C. The pre-prepared catalyst solution 1 was added and the reaction was carried out while maintaining the internal temperature at 100°C for 5 hours. This yielded a copolymer. The solution was then cooled to room temperature and reprecipitated using a large amount of methanol. The precipitate was then filtered and dried in a vacuum dryer, yielding 480 g of a white powder (copolymer 1). [ka] The resulting polymer had an Mw of 200,000, a molecular weight distribution (PDI) of 4.0, and a polymerization yield of 70%. The resulting polymer 1 The H-NMR chart is shown in Figure 1. The polymer had a molecular structure containing structural units represented by the following general formulas (a1) and (b1). The ratio of repeating units m to repeating units n (m:n) was 56.7:43.3. The average number of repeating units m was 13, and the average number of repeating units n was 10. [ka]

[0068] Example 2: Synthesis of Copolymer 2 In a reaction vessel of suitable size equipped with a stirrer and a condenser, the cyclic olefin of formula (a) (660 g, 3.98 mol) and the cyclic olefin of formula (b) (119 g, 0.99 mol) was weighed and dissolved in 1,500 g of butyl acetate. After removing dissolved oxygen from the system by nitrogen bubbling into the solution, the mixture was stirred and when the temperature reached 100°C, a pre-prepared catalyst solution 1 was added and the reaction was carried out while maintaining the internal temperature at 100°C for 5 hours. This yielded a copolymer. Next, the solution was cooled to room temperature and reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer to yield 440 g of a white powder (copolymer 2). The resulting polymer had an Mw of 160,000, a molecular weight distribution (PDI) of 3.2, and a polymerization yield of 68%. The polymer had a molecular structure containing structural units represented by the general formulas (a1) and (b1). The ratio of repeating units m to repeating units n (m:n) was 78.0:22.0. The average number of repeating units m was 35, and the average number of repeating units n was 10.

[0069] Example 3: Synthesis of Copolymer 3 In a reaction vessel of suitable size equipped with a stirrer and a condenser, the cyclic olefin of formula (a) (165 g, 0.99 mol) and the cyclic olefin of formula (b) (477 g, 3.98 mol) was weighed and dissolved in 1,500 g of butyl acetate. After removing dissolved oxygen from the system by nitrogen bubbling into the solution, the mixture was stirred and when the temperature reached 100°C, a pre-prepared catalyst solution 1 was added and the reaction was carried out while maintaining the internal temperature at 100°C for 5 hours. This yielded a copolymer. Next, the solution was cooled to room temperature and reprecipitated using a large amount of methanol, and the precipitate was collected by filtration and dried in a vacuum dryer to yield 520 g of a white powder (copolymer 3). The resulting polymer had an Mw of 300,000, a molecular weight distribution (PDI) of 4.2, and a polymerization yield of 77%. The polymer had a molecular structure containing structural units represented by the general formulas (a1) and (b1). The ratio of repeating units m to repeating units n (m:n) was 13.6:86.4. The average number of repeating units m was 10, and the average number of repeating units n was 64.

[0070] (Comparative Example 1: Synthesis of Homopolymer 1) Bicyclo[2.2.1]hept-5-ene-2-methanol, 2-acetate (996 g, 6.0 mol) was weighed into an appropriately sized reaction vessel equipped with a stirrer and condenser and dissolved in 20,000 g of butyl acetate. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 80°C. When the temperature reached 80°C, a pre-prepared catalyst solution 2 was added and the reaction was continued for 24 hours, maintaining the internal temperature at 80°C. This resulted in the production of bicyclo[2.2.1]hept-5-ene-2-methanol, 2-acetate homopolymer. The solution was then cooled to room temperature and reprecipitated using a large amount of n-hexane. The precipitate was then filtered and dried in a vacuum dryer, yielding 550 g of a white powder (homopolymer 1). The homopolymer 1 thus obtained had a weight average molecular weight (Mw) of 150,000 and a dispersity (Mw / Mn) of 2.4.

[0071] (Comparative Example 2: Synthesis of Homopolymer 2) (Vinyl)norbornene (1000 g, 8.3 mol) was weighed into an appropriately sized reaction vessel equipped with a stirrer and a condenser and dissolved in 4000 g of toluene. After removing dissolved oxygen from the system by nitrogen bubbling, the solution was stirred until it reached 60°C. Preparative catalyst solution 3 was added and the reaction was carried out while maintaining the internal temperature at 60°C for 5 hours. This yielded a (decyl)norbornene homopolymer. The solution was then cooled to room temperature and reprecipitated using a large amount of methanol. The precipitate was then filtered and dried in a vacuum dryer, yielding 950 g of a white powder (homopolymer 2). The homopolymer 2 thus obtained had a weight average molecular weight (Mw) of 620,000 and a dispersity (Mw / Mn) of 3.9.

[0072] (Weight average molecular weight (Mw) · Number average molecular weight (Mn) · Molecular weight distribution (PDI)) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (PDI: Mw / Mn) are calculated using polystyrene equivalent values ​​obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions are as follows. The results are shown in Table 1. Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0073] (glass transition temperature (Tg)) Approximately 3 mg of the resulting copolymer and homopolymer were transferred to a standard aluminum TA-Instrument sample pan. The sample pan was closed with a lid, and measurements were performed under nitrogen using a TA-Instruments DSC 2920 Modulated DSC equipped with an RCS refrigerator under the following conditions, and DSC curves were recorded. The glass transition temperature (Tg) was calculated from the DSC curves. The unit is °C. The results are shown in Table 1. Modulation: Heat only 60 seconds Cycle: ±2℃ Incline: 5℃ / min Final temperature: 300℃

[0074] [Table 1]

[0075] The materials used to prepare the varnishes in the following examples are as follows: [Antioxidants] Antioxidant 1: Adekastab AO-50 (3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate; chemical formula below), manufactured by ADEKA Corporation [ka]

[0076] Antioxidant 2: Adekastab AO-60 (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; chemical formula below), manufactured by ADEKA Corporation [ka]

[0077] Antioxidant 3: Adekastab AO-412S (2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate]; chemical formula below), manufactured by ADEKA Corporation [ka]

[0078] Antioxidant 4: Adekastab PEP-36 (3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; chemical formula below), manufactured by ADEKA Corporation [ka]

[0079] [Example 4] (Preparation of Varnish) 20 parts by mass of the polymer obtained in Example 1 and 80 parts by mass of propylene glycol monomethyl ether acetate were mixed and stirred for 24 hours to completely dissolve the polymer. The obtained polymer solution was filtered, if necessary, through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matter.

[0080] [Transparency] The polymer solution obtained in Example 4 was applied to a Corning glass substrate measuring 100 mm long and 100 mm wide using a spin coater and dried at 100°C for 1 minute to obtain a resin film approximately 3.0 μm thick. The light transmittance of this resin film was evaluated using a UV-visible spectrophotometer at wavelengths from 250 nm to 600 nm in 10 nm intervals, and the obtained transmittance was defined as the transparency of the resin film at each wavelength. The measurement results are shown in Figure 2.

[0081] [Examples 5 to 7, Comparative Examples 3 to 4] (Preparation of Antioxidant-Containing Varnish) A photosensitive resin composition was prepared by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids concentration was 15% by mass. Solid content in polymer solution (each synthesized polymer): 100 parts by mass Antioxidant (ADK STAB AO-50): 3 parts by weight Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass Surfactant (DIC Corporation, F-556): 0.5 parts by mass The obtained photosensitive resin composition was filtered, if necessary, through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matter.

[0082] [Transparency] The photosensitive resin composition was applied to a Corning glass substrate measuring 100 mm in length and 100 mm in width using a spin coater, dried at 100°C for 120 seconds, and then irradiated with g+h+i rays at an integrated light intensity of 100 mJ / cm using a g+h+i ray mask aligner (Canon Inc., PLA-501F (ultra-high pressure mercury lamp)). 2The entire surface was exposed to light so that the temperature reached 160°C, yielding a resin film approximately 3.0 μm thick. This resin film was heated in air at 160°C for 30 minutes to obtain a cured film, which was then evaluated for light transmittance at wavelengths of 350 nm and 400 nm using a UV-visible spectrophotometer. The transmittance values ​​obtained were used to determine the transparency of the cured film at each wavelength. Furthermore, a sample was prepared by separately preparing a sample after pre-baking, and measurements were also performed for a sample that had been post-baked at an even higher temperature of 200°C for 30 minutes.

[0083] [Film-forming properties and adhesion] The photosensitive resin composition was spin-coated onto a 3-inch silicon wafer and pre-baked using a hot plate at 100°C for 120 seconds to obtain a resin film. After pre-baking, the film was cured at 200°C for 30 minutes. Resin films were formed with different thicknesses (1 μm, 50 μm, 100 μm), and the surfaces after pre-baking and post-baking were observed with an optical microscope to check for the presence or absence of cracks. Since cracks occur in resin films that have poor adhesion to the substrate, the presence or absence of cracks also serves as an indicator of adhesion to the substrate.

[0084] [Table 2]

[0085] The polymers obtained in the examples of the present invention had excellent solubility in organic solvents, were capable of forming thick films, and suppressed cracking, which resulted in excellent film-forming properties and excellent adhesion to components. Furthermore, the cured films obtained from the polymers had excellent heat resistance and transparency.

Claims

1. A polymer containing structural units represented by the following general formulas (1) and (2): 【Chemistry 1】 (In general formula (1), Q １ represents an alkylene group having 1 to 5 carbon atoms, a is 0, 1 or 2, and m is a number of 1 or more and 500 or less on average. ２ represents a single bond or an alkylene group having 1 to 5 carbon atoms, b is 0, 1 or 2, and n is an average number of 1 to 500.

2. The polymer according to claim 1, having a weight average molecular weight of 30,000 or more and 800,000 or less.

3. 3. The polymer according to claim 1, wherein a resin film obtained under the following conditions has a light transmittance of 95% or more in the wavelength range of 300 nm or more and 600 nm or less. (conditions) A propylene glycol monomethyl ether solution containing 20% ​​by weight of the polymer is applied and heated at 100° C. for 1 minute in the atmosphere to obtain a resin film having a thickness of 3 μm.

4. A varnish comprising the polymer according to any one of claims 1 to 3 and an organic solvent.

5. 5. The varnish of claim 4, further comprising an antioxidant.

6. 6. The varnish according to claim 5, wherein the antioxidant is at least one selected from the group consisting of hindered phenol-based antioxidants, thioether-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, thiol-based antioxidants, benzotriazole-based antioxidants, benzophenone-based antioxidants, hydroxylamine-based antioxidants, salicylic acid ester-based antioxidants, and triazine-based antioxidants.

7. The polymer according to any one of claims 1 to 3, wherein a cured film obtained under the following conditions has a light transmittance of 95% or more at a wavelength of 350 nm and a light transmittance of 95% or more at a wavelength of 400 nm. (conditions) A propylene glycol monomethyl ether solution containing 3 phr of an antioxidant and having a concentration of 20% by weight of polymer is applied and heated at 160° C. for 30 minutes in the atmosphere to obtain a cured film having a thickness of 3 μm.

8. The polymer according to any one of claims 1 to 3, wherein a cured film obtained under the following conditions has a light transmittance of 80% or more at a wavelength of 350 nm and a light transmittance of 90% or more at a wavelength of 400 nm. (conditions) A propylene glycol monomethyl ether solution containing 3 phr of an antioxidant and having a concentration of 20% by weight of polymer is applied and heated at 200° C. for 30 minutes in the atmosphere to obtain a cured film having a thickness of 3 μm.

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