KR20180013718A - Cyclic olefin-based polymer and method of preparing the same - Google Patents

Abstract

The present invention relates to a cyclic olefin-based copolymer and a method for preparing the same. More specifically, the present invention relates to a cyclic olefin-based copolymer containing three repeating units having a specific functional group in a predetermined ratio. The copolymer exhibits low dielectric properties and can be applied to a semiconductor substrate, a printed circuit board, or the like.

Description

CYCLIC OLEFIN-BASED POLYMER AND METHOD OF PREPARING THE SAME Technical Field [1] The present invention relates to a cyclic olefin-

The present invention relates to a cyclic olefin-based copolymer having low dielectric properties and a method for producing the same.

As electronic devices have become more sophisticated, there has been a demand for higher frequencies in the fields where semiconductor substrates and printed circuit boards are used. Since the transmission loss of the electric signal in the high frequency region is proportional to the dielectric loss and the frequency, the transmission loss increases as it goes to the high frequency region, and adversely affects the performance, durability and production yield of the electronic device. It is required to develop a material having dielectric loss characteristics.

In the conventional communication and network fields, polyphenylene ether has been applied as a low dielectric material, but the handling property has been problematic due to the impregnation of the prepreg, and heat resistance has not yet been sufficient.

Accordingly, it is still necessary to develop a material having sufficient mechanical properties and low dielectric constant and low dielectric loss characteristics.

The present invention is to provide a cyclic olefin-based copolymer having low dielectric constant, low dielectric loss and low dielectric constant.

The present invention also provides a process for producing the cyclic olefin-based copolymer.

The present invention relates to a resin composition comprising a repeating unit represented by the following general formula (1), a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3) Of the repeating unit is 15 to 60 mol%.

Further, the present invention relates to a process for producing a catalyst, which comprises reacting a monomer represented by the following general formula (4) and a monomer represented by the general formula (5) with a procatalyst of a Group 10 transition metal, an anionic promoter coordinating to the metal of the procatalyst and a ligand Lt; / RTI > And

 And subjecting the polymer to epoxidation by reacting with a peroxide. The present invention also provides a process for producing the cyclic olefin-based copolymer.

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin-based copolymer according to a specific embodiment of the present invention and a method for producing the same will now be described in detail.

According to one embodiment of the present invention, there is provided a polymer comprising repeating units represented by the following general formula (1), repeating units represented by the general formula (2) and repeating units represented by the general formula (3) A cyclic olefin-based copolymer containing from 15 mol% to 60 mol% of the repeating unit represented by the formula (1) may be provided:

[Chemical Formula 1]

In Formula 1,

p is an integer of 0 to 4,

R ₁ to R ₄ each independently represent hydrogen, an epoxy group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₁ and R ₂ , R ₃ and R ₄ , To form an epoxy group, provided that when R ₁ to R ₄ are all hydrogen,

(2)

In Formula 2,

q is an integer of 0 to 4,

R ₅ to R ₈ are each independently a hydrogen or a vinyl group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₅ and R ₆ , R ₇ and R ₈ , To form an alkylidene group, with the proviso that when R ₅ to R ₈ are both hydrogen,

(3)

In Formula 3,

r and m are each independently an integer of 0 to 4,

Each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S;

As used herein, the term "substituted or unsubstituted" A hydroxy group; And a C _3-60 cycloalkyl group, or a substituted or unsubstituted C _3-60 cycloalkyl group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, a dioxolene group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, A pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, a pyrimidinyl group, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a phenanthroline group, an imidazolyl group, , A thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group and a dibenzofuranyl group, but is not limited thereto.

The inventors of the present invention have conducted studies on a material having a low dielectric constant and low dielectric loss property and have found that a resin composition containing a repeating unit having an epoxy group, a repeating unit having a vinyl group or an ethylidene group, It was confirmed through experiments that the copolymer exhibits a low dielectric constant at a dielectric constant of 2.6 or less at 10 GHz and completed the invention.

More specifically, the repeating unit represented by the formula (1) of the cyclic olefin-based copolymer includes an epoxy group. If the proportion of the repeating unit represented by the formula (1) is high, the effect of improving the degree of curing and adhesion may be improved. The characteristics can be degraded. When the proportion of the repeating unit represented by the above formula (2) including the vinyl group is increased, low dielectric constant and low dielectric loss characteristics can be improved. When the proportion of the repeating unit represented by the general formula (3) including the aliphatic functional group is increased, the dielectric constant of the copolymer produced improves, but the degree of curing and the solubility of the resin can be reduced.

Accordingly, the cyclic olefin-based copolymer needs to adjust the repeating units represented by the above formulas (1) to (3) at an appropriate ratio, and the repeating units represented by the above formulas When the unit is contained in an amount of 15 mol% to 60 mol%, preferably 20 mol% to 50 mol%, and more preferably 25 mol% to 40 mol%, low dielectric constant and low dielectric loss characteristics can be exhibited . If the proportion of the repeating unit represented by the formula (1) is out of the above range, poor dielectric properties, physical properties such as adhesion and durability may be insufficient for application in the field of communication and network.

으로 표시되는 작용기이거나, R₁와 R₂, R₃과 R₄로 이루어진 군에서 선택된 하나 이상의 조합이 서로 연결되어 에폭시기를 형성할 수 있다. 상기 화학식에서 n은 0 내지 4의 정수이고, R은 수소 또는 탄소수 1 내지 4의 알킬기이며, R₁ 내지 R₄가 모두 수소인 경우는 제외한다.In the repeating unit represented by the above formula (1), R ₁ to R ₄ are each independently hydrogen or

, Or a combination of at least one selected from the group consisting of R ₁ and R ₂ , R ₃ and R ₄ may be connected to each other to form an epoxy group. In the above formula, n is an integer of 0 to 4, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₁ to R ₄ are not all hydrogen.

으로 표시되는 작용기이거나, R₅와 R₆, R₇과 R₈로 이루어진 군에서 선택된 하나 이상의 조합이 서로 연결되어 알킬리덴기를 형성할 수 있다. 상기 화학식에서 n은 0 내지 4의 정수이고, R은 수소 또는 탄소수 1 내지 4의 알킬기이며, R₅ 내지 R₈가 모두 수소인 경우는 제외한다.In the repeating unit represented by the above formula (2), R ₅ to R ₈ are each independently hydrogen, or

, Or a combination of at least one member selected from the group consisting of R ₅ and R ₆ , R ₇ and R ₈ may be connected to each other to form an alkylidene group. In the above formula, n is an integer of 0 to 4, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₅ to R ₈ are not all hydrogen.

In the repeating unit represented by the above formula (3), each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S, preferably a substituted or unsubstituted C _1-20 ether or a substituted or unsubstituted O , C _2-60 heterocycle containing at least one of N, Si and S may be used.

Specifically, a substituted or unsubstituted C _1-20 ether used in the above general formula (3) by R may be a C _1-20 alkyl group substituted by C _1-20 alkoxy. Specific examples of the C _1-20 alkyl group substituted by a C _1-20 alkoxy group is a C _1-10 alkyl group, more specifically a C _1-3 alkyl group substituted by a C _1-3 alkoxy substituted with C _1-10 alkoxy . A preferable example of the C _1-20 alkyl group substituted by C _1-20 alkoxy is methoxymethyl group.

The C _2-60 heterocycle containing at least one of substituted or unsubstituted O, N, Si and S used as R in the above formula (3) may be a functional group represented by the following formula (7).

(7)

In Formula 7, at least one of A ₁ and A ₂ is O, N, Si, or S and the remainder is carbon, t is an integer of 1 or more, or an integer of 1 to 5, Bonds to atoms. In the above formula (7), "*" forms a bond to the same carbon atom, thereby forming a ring structure. That is, when the functional group of Formula 7 is introduced into R in Formula 3, the repeating unit of Formula 3 may have a spiro ring structure in which two different rings are adjacent to each other at one carbon atom.

Preferably, in Formula 7, A ₁ is O, A ₂ is carbon, t is 1, and "*" may be an ocetane functional group which forms a bond to the same carbon atom. In the above formula (7), A ₁ and A ₂ are O, t is 2, and "*" may be a 1,3-dioxane functional group forming a bond to the same carbon atom.

The cyclic olefin-based copolymer has a weight average molecular weight of about 1,000 g / mol to about 100,000 g / mol, preferably about 1,500 g / mol to about 50,000 g / mol, more preferably about 2,500 g / mol to about 10,000 g / g / mol. < / RTI >

As described above, in order to produce a copolymer having a low molecular weight of 2,500 g / mol to 10,000 g / mol, it is preferable to apply a phosphine having a bulky structure as an organic ligand in the catalyst constitution.

When the weight average molecular weight of the cyclic olefin-based copolymer is in the range of 2,500 g / mol to 10,000 g / mol, when the composition is prepared by mixing with other materials for film formation, it is possible to prevent an excessive increase in viscosity, . Specifically, the viscosity of the composition containing the cyclic olefin-based copolymer may be from 40 cps to 100 cps, or from 40 cps to 80 cps under the condition that the solid content ratio of the solvent exceeds 1 (solid content / solvent> 1).

When the weight average molecular weight of the cyclic olefin-based copolymer is out of the above-mentioned range, the viscosity and flowability of the film-forming composition do not satisfy an appropriate level, so that it is difficult to obtain a clean coated surface and formation of a film with a constant thickness is difficult Therefore, an error may occur in the measurement of the electrical properties.

In the present specification, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 DEG C, a tetrahydrofuran (THF) solvent, and a flow rate of 1 mL / min.

On the other hand, the cyclic olefin-based copolymer may have a glass transition temperature of 255 ° C or higher, or 255 ° C to 300 ° C, or 268 ° C or higher, or 268 ° C to 300 ° C, or 268 ° C to 280 ° C. The glass transition temperature can be confirmed by DSC measurement data. For example, the cyclic olefin-based copolymer is maintained at 300 ° C for 5 minutes, slowly cooled to room temperature, and then re-scanned at a rate of 10 ° C / , And the like. The glass transition temperature of the cyclic olefin-based copolymer is believed to be attributed to the chemical structural characteristics of the copolymer. The higher the glass transition temperature of the copolymer, the lower the CTE value as the modulus increases at high temperature, The thermal stability of CCL or PCB can be improved.

The cured product of the cyclic olefin-based copolymer may have a dielectric constant (Dk) of about 2.6 or less, preferably about 2.3 to 2.6 at 10 GHz. The permittivity was measured using a Vector network analyzer of Agilent tech at 10 GHz. When the dielectric constant exceeds 2.7, the isolation characteristic is not good and the transmission loss increases in the high frequency region. Therefore, the performance, durability, Can be adversely affected.

The cured product of the cyclic olefin-based copolymer may have a dielectric loss coefficient (Df) at 10 GHz of about 0.007 or less, preferably 0.002 to 0.007, and more preferably 0.003 to 0.007. The dielectric loss factor was measured by the same apparatus and method as those for measuring the dielectric constant.

The cured product of the cyclic olefin-based copolymer may have a copper foil adhesive strength of 0.6 kgf / cm or more, or 0.6 kgf / cm to 1.0 kgf / cm, or 0.8 kgf / cm to 1.0 kgf / cm. Examples of the method for measuring the adhesive strength of the copper foil are not particularly limited. For example, a laminate of a cured product of the cyclic olefin-based copolymer and a copper foil having a thickness of 35 mu m is cut into a rectangular shape having a width of 10 mm (Peel strength) when the copper foil is cut at a 90 ° angle and at a rate of 50 mm / min from the substrate layer by gripping the end portion of the cut copper foil using a tensile strength meter manufactured by ZWICK.

If the cured product of the cyclic olefin-based copolymer is excessively reduced to less than 0.6 kgf / cm, it may be difficult to produce the product because the prepreg and copper foil are easily peeled off when the CCL is produced. .

According to another embodiment of the present invention, the monomers represented by the following general formula (4) and the monomers represented by the general formula (5) are reacted with a procatalyst of a Group 10 transition metal, an anionic promoter coordinating to the metal of the procatalyst, In the presence of a ligand; And

And subjecting the polymer to epoxidation by reacting with a peroxyacid. The process for producing the cyclic olefin-based copolymer of claim 1 comprising:

[Chemical Formula 4]

In Formula 4,

q is an integer of 0 to 4,

R ₅ to R ₈ are each independently a hydrogen or a vinyl group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₅ and R ₆ , R ₇ and R ₈ , To form an alkylidene group, with the proviso that when R ₅ to R ₈ are both hydrogen,

[Chemical Formula 5]

In Formula 5,

r and m are each independently an integer of 0 to 4,

Each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S;

As described above, the cyclic olefin-based copolymer produced according to the above method contains a repeating unit having an epoxy group, a repeating unit having a vinyl group or an ethylidene group and a repeating unit having an aliphatic functional group in a predetermined ratio, Dielectric constant and low dielectric loss, as well as high peel strength.

In the monomer represented by Formula 5, each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S, preferably a substituted or unsubstituted C _1-20 ether or a substituted or unsubstituted O , C _2-60 heterocycle containing at least one of N, Si and S may be used.

Specifically, a substituted or unsubstituted C _1-20 ether used in the above formula (5) to R may be a C _1-20 alkyl group substituted by C _1-20 alkoxy. Specific examples of the C _1-20 alkyl group substituted by a C _1-20 alkoxy group is a C _1-10 alkyl group, more specifically a C _1-3 alkyl group substituted by a C _1-3 alkoxy substituted with C _1-10 alkoxy . A preferable example of the C _1-20 alkyl group substituted by C _1-20 alkoxy is methoxymethyl group.

The C _2-60 heterocycle containing at least one of substituted or unsubstituted O, N, Si and S used as R in the above formula (5) may be a functional group represented by the following formula (7).

(7)

In Formula 7, at least one of A ₁ and A ₂ is O, N, Si, or S and the remainder is carbon, t is an integer of 1 or more, or an integer of 1 to 5, Bonds to atoms. In the above formula (7), "*" forms a bond to the same carbon atom, thereby forming a ring structure. That is, when the functional group of Formula 7 is introduced into R in Formula 3, the repeating unit of Formula 3 may have a spiro ring structure in which two different rings are adjacent to each other at one carbon atom.

Preferably, in Formula 7, A ₁ is O, A ₂ is carbon, t is 1, and "*" may be an ocetane functional group which forms a bond to the same carbon atom. In the above formula (7), A ₁ and A ₂ are O, t is 2, and "*" may be a 1,3-dioxane functional group forming a bond to the same carbon atom.

The step of polymerizing the monomers represented by Chemical Formulas 4 and 5 is carried out in the presence of a ligand comprising a Group 10 transition metal transition metal, an anion co-catalyst coordinating to the metal of the precatalyst, and a Group 15 element, As a precursor of the transition metal, PdCl ₂ (Palladium dichloride), PdBr ₂ (Palladium dibromide), [(Allyl ) Pd (Cl)] 2 (Allylpalladiumchloride dimer), (CH 3 CO 2) 2 Pd (Palladium acetate), [CH 3 COCH = C (O-) CH 3] 2 Pd (Palladium acetylacetonate), [PdCl (NB) O (CH 3)] 2, (dibenzylideneacetone) 2 Pd (Bis (dibenzylideneacetone) palladium), (dibenzylideneacetone) 3 Pd 2 (Tris (dibenzylideneacetone) dipalladium), Pd (NO 3) 2 ( Palladium nitrate), and NiBr (NP (CH ₃ ) ₃ ) ₄ .

The anionic co-catalyst capable of weakly coordinating to the metal of the procatalyst may be represented by the following formula (6)

[Chemical Formula 6]

[Cat] [Ani]

In Formula 6,

[Cat] is any one selected from the group consisting of a hydrogen cation, a cation of a Group 1 metal, a cation of a Group 2 metal, a cation of a transition metal, and an organic terminal containing the cation,

[Ani] refers to borate, aluminate, [SbF ₆ ] -, [PF ₆ ] -, [AsF ₆ ] -, perfluoroacetate (CF ₃ CO ₂ ) Perfluoropropionate ([C ₂ F ₅ CO ₂ ] -), perfluorobutyrate ([CF ₃ CF ₂ CF ₂ CO ₂ ] -), perchlorate ([ClO ₄ ] -) para-toluenesulfonate (p-toluenesulfonate; [p- CH 3 C 6 H 4 SO 3] -), [SO 3 CF 3] -, see other benzene, and substituted with halogen consisting of carborane unsubstituted Lt; / RTI >

In addition, the ligand including the Group 15 element has an electron stabilizing ability and can increase the solubility of the transition metal compound in the organic solvent, and can thermally and chemically activate the ligand. Specific examples of the ligand containing the Group 15 element include aliphatic, alicyclic or aromatic phosphine or phosphite, preferably (2-hydroxyphenyl) diphenylphosphine, tri (furan-2-yl ) Phosphine, bis (diphenylphosphino) methane, bis (diphenylphosphino) ethane, tris (2,4-di-tert-butylphenyl) phosphite, tri (ortho-tolyl) Tri-naphthylphosphine, tributylphosphine, tetrafluoroborate, triphenylphosphine, tricyclohexylphosphine, triphenylphosphite, 1,2-bis (diphenyl (Diphenylphosphino) ethane, tributylphosphine, triphenylphosphine oxide, and 1,2- (diphenylphosphino) butane.

(2-hydroxyphenyl) diphenylphosphine, tri (furan-2-yl) phosphine, bis (diphenylphosphino) methane, bis (Di-tert-butylphenyl) phosphite, tri (ortho-tolyl) phosphine, tri (para-tolyl) phosphine, tri-1-naphthylphosphine At least one selected from the group consisting of tin, tin butylphosphine, tetrafluoroborate and the like can be used.

In the step of polymerizing the monomer, polymerization can be carried out at a temperature of 50 ° C to 200 ° C, or 70 ° C to 150 ° C, or 90 ° C to 140 ° C, or 100 ° C to 135 ° C.

Next, the step of epoxidizing the polymer produced by polymerizing the monomers represented by the above formulas (4) and (5) by reacting with the organic peroxy acid is carried out.

At this time, the peroxide may include at least one selected from the group consisting of peroxy benzoic acid, peracetic acid, peroxy formic acid, perphthalic acid, perpropionic acid, perbutyric acid, trifluoro peroxyacetic acid and hydrogen peroxide.

In the epoxidation step, the molar ratio of the polymer to the peroxide can be about 1: 0.1 to 1: 5, preferably about 1: 0.2 to 1: 3. The molar ratio of the polymer to the peroxide is related to the ratio of the respective repeating units of the cyclic olefin-based copolymer to be produced. When the polymer is reacted with the peroxide at the above-mentioned molar ratio, the repeating unit represented by the formula 15 to 60 mol% of the cyclic olefin-based copolymer.

In addition, the epoxidation may be carried out at a temperature of about 50 캜 or less, preferably about 0 캜 to 40 캜.

According to the present invention, it is possible to provide a cyclic olefin-based copolymer that exhibits low dielectric constant and low dielectric loss characteristics and can be applied to a semiconductor substrate, a printed circuit board, and the like.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Examples and Comparative Examples &

Example 1

(Step 1) A 250 ml Schlenk flask was charged with 22.8 g of 5-Ethylidene-2-norbornene and 1 g of 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- , 77.2 g of 8-dimethanonapthlalene, and 250 g of xylene. The temperature was heated to 130 while purging with N ₂ . 0.022 g of Palladium dichloride (PdCl ₂ ), 0.036 g of Trinaphthylphosphine (P (1-nap) ₃ ) and 0.025 g of Silver tetrafluoroborate (AgBF ₄ ) were added to 6 ml of dichloromethane and reacted for 16 hours at 130 ° C with stirring . After the reaction, the reaction product was poured into an excess amount of methanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel, and the recovered solid was dried in a vacuum oven at 30 for 24 hours to obtain a copolymer having a molar ratio of the repeating unit of formula (3): 3: 7 (Mw = 5010 g / mol , PDI = 1.95, yield: 48%).

(Step 2) 20 g of the copolymer obtained in the step 1 was dissolved in 60 g of methylenechloride. While stirring, the temperature was lowered to 0 占 폚 and 1.18 g of mCPBA (meta-Chloroperoxybenzoicacid) was slowly added dropwise. After stirring for 1 hour, the temperature was raised to room temperature and reacted for 5 hours. After the reaction, the reaction product was filtered, and the obtained reaction solution was poured into an excess amount of methanol to obtain a white solid precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 30 ° C for 24 hours to obtain an epoxy conversion of 90%, and the molar ratio of the repeating unit represented by formula (1): the repeating unit represented by formula (2): the repeating unit represented by formula 2.7: 0.3: 7 (Mw = 5300 g / mol, PDI = 1.95, 90% yield).

Example 2

(Step 1) In Step 1 of Example 1, 31.5 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- _{8-dimethanonapthlalene 68.5g, PdCl 2 0.022} g, P (1-nap) 3 0.037 g, AgBF 4 0.026 g except that the content of the change is repeated in the same manner of the general formula (2) unit: mole ratio of the repeating unit of formula (3) (Mw = 5015 g / mol, PDI = 1.95, yield: 48%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.63 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5305 g / mol, PDI = 1.96, yield: 89%).

Example 3

(Step 1) In Step 1 of Example 1, 27.15 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that the reaction was carried out at 125 ° C except that 72.9 g of 5-Etoxy-2-norbornene, 0.027 g of PdCl ₂ , 0.042 g of P (1-nap) ₃ and 0.029 g of AgBF ₄ were used instead of 8-dimethanonapthlalene (Mw = 5500 g / mol, PDI = 2.02, yield: 51%) was obtained in which the molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 3:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.40 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 5750 g / mol, PDI = 2.02, yield 86%).

Example 4

(Step 1) In Step 1 of Example 1, 36.7 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that 63.4 g of 5-Etoxy-2-norbornene, 0.027 g of PdCl ₂ , 0.043 g of P (1-nap) ₃ and 0.030 g of AgBF ₄ were used instead of 8-dimethanonapthlalene, (Mw = 5450 g / mol, PDI = 2.02, yield: 51%) was obtained in which the molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 4:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.90 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 5800 g / mol, PDI = 2.02, yield 86%).

Example 5

(Step 1) In Step 1 of Example 1, 23.7 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except for changing 76.4 g of 5-Butoxy-2-norbornene, 0.023 g of PdCl ₂ , 0.037 g of P (1-nap) ₃ and 0.026 g of AgBF _{4 in} place of 8-dimethanonapthlalene, and reacting at 125 ° C. (Mw = 5800 g / mol, PDI = 2.00, yield: 53%) was obtained in which the molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 3:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.22 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 5900 g / mol, PDI = 2.01, yield 85%).

Example 6

(Step 1) In Step 1 of Example 1, 32.6 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that 8-dimethanonaphtholene was replaced by 67.5 g of 5-butoxy-2-norbornene, 0.024 g of PdCl ₂ , 0.038 g of P (1-nap) ₃ and 0.026 g of AgBF ₄ and reacted at 125 ° C. (Mw = 5800 g / mol, PDI = 2.01, yield: 52%) was obtained in a molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) = 4: 6.

(Step 2) In the same manner as in Example 1 except that the content of mCPBA was changed to 1.68 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 5950 g / mol, PDI = 2.01, yield 85%).

Example 7

(Step 1) In Step 1 of Example 1, 27.15 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that instead of 8-dimethanonapthlalene, 72.9 g of 5- (Methoxymethyl) -2-norbornene, 0.027 g of PdCl ₂ , 0.042 g of P (1-nap) ₃ and 0.029 g of AgBF ₄ , (Mw = 5700 g / mol, PDI = 2.00, yield: 52%) in a molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 3:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.40 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 5850 g / mol, PDI = 2.01, yield 86%).

Example 8

(Step 1) In Step 1 of Example 1, 36.7 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that instead of 8-dimethanonapthlalene, 63.4 g of 5- (Methoxymethyl) -2-norbornene, 0.027 g of PdCl ₂ , 0.043 g of P (1-nap) ₃ and 0.030 g of AgBF ₄ , (Mw = 5750 g / mol, PDI = 2.00, yield: 52%) in a molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 4: 6.

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.90 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 5900 g / mol, PDI = 2.00, yield 86%).

Example 9

(Step 1) In Step 1 of Example 1, 27.4 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that 72.6 g of Spiro [bicycle [2,2,1] hept-5-ene-2,2'-oxetane], 0.027 g of PdCl ₂ , 0.040 g of P (1-nap) ₃ , 0.029 g of AgBF ₄ (Mw = 4500 g / mol, PDI = 2.10, Mw = 4500 g / mol) was obtained in the same manner as in Example 1, except that the reaction was conducted at 120 deg. Yield 40%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 2.83 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 4700 g / mol, PDI = 2.11, yield 85%).

Example 10

(Step 1) In Step 1 of Example 1, 37.0 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- 63.0 g of Spiro [bicycle [2,2,1] hept-5-ene-2,2'-oxetane], 0.026 g of PdCl ₂ , 0.040 g of P (1-nap) _{3 and} 0.028 g of AgBF _{4 in} place of 8-dimethanonapthlalene (Mw = 4,400 g / mol, PDI = 2.08, Mw = 4,400 g / mol) was obtained in the same manner as in Example 1, except that the reaction was carried out at 120 ° C. Yield: 41%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 3.93 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 4650 g / mol, PDI = 2.09, yield: 83%).

Example 11

(Step 1) In Step 1 of Example 1, 25.3 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-ocahydro-2-methyl- 8-dimethanonapthlalene instead Spiro [5,5- (1 ', 3' -dioxane) -2-norbornene] 74.7g, PdCl 2 0.025 g, P (1-nap) 3 0.039 g, AgBF 4 (Mw = 5000 g / mol, PDI = 1) was obtained in the same manner as in Example 1, except that the reaction was carried out at 120 deg. C and the molar ratio of the repeating unit of formula (3) 2.05, yield: 51%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.31 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 5300 g / mol, PDI = 2.07, yield: 88%).

Example 12

(Step 1) In Step 1 of Example 1, 34.5 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-ocahydro-2-methyl- 65.5 g of Spiro [5,5- (1 ', 3'-dioxane) -2-norbornene], 0.026 g of PdCl ₂ , 0.040 g of P (1-nap) ₃ and 0.028 g of AgBF ₄ were used instead of 8-dimethanonapthlalene (Mw = 5000 g / mol, PDI = 2.06, yield: 51%) was obtained in the same manner as in Example 1, except that the reaction was carried out at 120 deg. ).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA was changed to 1.78 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 5300 g / mol, PDI = 2.06, yield: 87%).

Example 13

(Step 1) In Step 1 of Example 1, 25.3 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- ( ₃ ) was repeated in the same manner except that 64.7 g of 2-Norbornene, 0.035 g of PdCl ₂ , 0.055 g of P (1-nap) _{3 and} 0.038 g of AgBF ₄ were used instead of 8-dimethanonapthlalene, (Mw = 6000 g / mol, PDI = 2.10, yield: 55%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.83 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 6100 g / mol, PDI = 2.10, yield 90%).

Example 14

(Step 1) In Step 1 of Example 1, 46.0 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- ( ₃ ) was repeated in the same manner except that 54.0 g of 2-Norbornene, 0.034 g of PdCl ₂ , 0.054 g of P (1-nap) _{3 and} 0.037 g of AgBF ₄ were used instead of 8-dimethanonapthlalene, (Mw = 6050 g / mol, PDI = 2.11, yield: 55%).

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 2.38 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 6100 g / mol, PDI = 2.11, 89% yield).

Example 15

(Step 1) In Step 1 of Example 1, 22.4 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- (2) was repeated in the same manner except that 77.6 g of 5- n- hexyl-2-Norbornene, 0.022 g of PdCl ₂ , 0.035 g of P (1-nap) _{3 and} 0.024 g of AgBF ₄ were used instead of 8-dimethanonapthlalene (Mw = 5950 g / mol, PDI = 2.10, yield: 54%) was obtained in a molar ratio of the repeating unit represented by the formula (3): 3: 7.

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.16 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 6050 g / mol, PDI = 2.11, yield 90%).

Example 16

(Step 1) In Step 1 of Example 1, 31.0 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- (2) was repeated in the same manner except that 69.0 g of 5- n- hexyl-2-Norbornene, 0.023 g of PdCl ₂ , 0.036 g of P (1-nap) _{3 and} 0.025 g of AgBF ₄ were used instead of 8-dimethanonapthlalene (Mw = 6000 g / mol, PDI = 2.10, yield: 54%) was obtained in a molar ratio of the repeating unit represented by the formula (3): 4: 6.

(Step 2) In the same manner, except that the content of mCPBA in Step 2 of Example 1 was changed to 1.60 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 6100 g / mol, PDI = 2.10, yield 90%).

Example 17

(Step 1) In Step 1 of Example 1, 25.6 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- Except that in place of 8-dimethanonaphtholene, 74.5 g of 5- n- Butyl-2-Norbornene, 0.025 g of PdCl ₂ , 0.040 g of P (1-nap) _{3 and} 0.028 g of AgBF ₄ (Mw = 5900 g / mol, PDI = 2.09, yield: 56%) was obtained in a molar ratio of repeating units represented by the following formula (3): 3: 7.

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.32 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 copolymer (Mw = 6000 g / mol, PDI = 2.09, yield 90%).

Example 18

(Step 1) In Step 1 of Example 1, 34.8 g of 5-Ethylidene-2-norbornene, 1,2,3,4,4a, 5,8,8a-octahydro-2-methyl- 8-dimethanonapthlalene instead 5- n -Butyl-2-Norbornene 65.2g , PdCl 2 0.026 g, P (1-nap) 3 0.041 g, AgBF 4 (Mw = 5900 g / mol, PDI = 2.10, yield: 56%) was obtained in the same manner as in Example 1, except that the amount of the repeating unit represented by Formula (3) was changed to 0.028 g. .

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.80 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 copolymer (Mw = 6000 g / mol, PDI = 2.10, yield 90%).

Example 19

(Step 1) In the same manner as in Step 1 of Example 1 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (Mw = 5000 g / mol, PDI = 1.95, yield: 48%).

(Step 2) In the same manner as in Step 2 of Example 1, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 2.7: 0.3: 7 was obtained (Mw = 5300 g / mol , PDI = 1.97, yield 90%).

Example 20

(Step 1) In the same manner as in Example 1 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in the step 1 of Example 2, the molar amount of the repeating unit represented by formula (Mw = 5005 g / mol, PDI = 1.95, yield: 47%).

(Step 2) According to the same manner as in Step 2 of Example 2, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5310 g / mol , PDI = 1.95, yield 90%).

Example 21

(Step 1) In the same manner as in Example 1 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in the step 1 of Example 3, the molar amount of the repeating unit represented by formula (Mw = 5410 g / mol, PDI = 2.01, yield: 51%).

(Step 2) In the same manner as in Step 2 of Example 3, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 2.7: 0.3: 7 was obtained (Mw = 5650 g / mol , PDI = 2.01, yield 86%).

Example 22

(Step 1) In the same manner as in Example 1 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in Step 1 of Example 4, the molar amount of the repeating unit represented by Formula (Mw = 5450 g / mol, PDI = 2.00, yield: 51%).

(Step 2) In the same manner as in Step 2 of Example 4, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5610 g / mol , PDI = 2.01, yield: 87%).

Example 23

(Step 1) In the same manner as in the step 1 of Example 5 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (Mw = 5700 g / mol, PDI = 2.00, yield: 51%).

(Step 2) In the same manner as in Step 2 of Example 5, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 2.7: 0.3: 7 was obtained (Mw = 5800 g / mol , PDI = 2.00, yield: 87%).

Example 24

(Step 1) In the same manner as in Step 1 of Example 6 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by Formula (Mw = 5720 g / mol, PDI = 2.00, yield: 51%).

(Step 2) According to the same manner as in Step 2 of Example 6, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5810 g / mol , PDI = 2.00, yield 86%).

Example 25

(Step 1) In the same manner as in Step 1 of Example 7, except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, (Mw = 5740 g / mol, PDI = 1.98, yield 50%).

(Step 2) According to the same manner as in Step 2 of Example 7, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 2.7: 0.3: 7 was obtained (Mw = 5800 g / mol , PDI = 1.98, yield 85%).

Example 26

(Step 1) The same procedure was followed except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in Step 1 of Example 8 to obtain the repeating unit represented by Formula (Mw = 5700 g / mol, PDI = 1.98, yield: 51%).

(Step 2) In the same manner as in Step 2 of Example 8, a copolymer having a molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 3.6: 0.4: 6 was obtained (Mw = 5800 g / mol , PDI = 1.98, yield 86%).

Example 27

(Step 1) In the same manner as in Example 1 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in the step 1 of Example 9, the molar amount of the repeating unit represented by formula To obtain a copolymer having a ratio of 3: 7 (Mw = 4600 g / mol, PDI = 2.10, yield 40%).

(Step 2) In the same manner as in Step 2 of Example 9, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 2.7: 0.3: 7 was obtained (Mw = 4700 g / mol , PDI = 2.10, yield 82%).

Example 28

(Step 1) In the same manner as in Example 10 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (2) (Mw = 4400 g / mol, PDI = 2.08, yield: 41%).

(Step 2) In the same manner as in Step 2 of Example 10, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 4600 g / mol , PDI = 2.08, yield: 83%).

Example 29

(Step 1) The same procedure was followed except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene in the step 1 of Example 11 to obtain the repeating unit represented by formula (Mw = 5100 g / mol, PDI = 2.05, yield: 51%).

(Step 2) In the same manner as in Step 2 of Example 11, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 2.7: 0.3: 7 was obtained (Mw = 5250 g / mol , PDI = 2.06, yield 90%).

Example 30

(Step 1) In the same manner as in Example 12 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (2) (Mw = 5120 g / mol, PDI = 2.05, yield: 49%).

(Step 2) In the same manner as in Step 2 of Example 12, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5300 g / mol , PDI = 2.05, yield 90%).

Example 31

(Step 1) In the same manner as in Step 1 of Example 13 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by Formula (Mw = 5900 g / mol, PDI = 2.09, yield: 54%).

(Step 2) In the same manner as in Step 2 of Example 13, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): the repeating unit represented by Formula (2) was 2.7: 0.3: 7 was obtained (Mw = 5950 g / mol , PDI = 2.09, yield: 89%).

Example 32

(Step 1) In the same manner as in Example 14 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (2) (Mw = 5870 g / mol, PDI = 2.08, yield: 55%).

(Step 2) In the same manner as in Step 2 of Example 14, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5940 g / mol , PDI = 2.08, yield 90%).

Example 33

(Step 1) In the same manner as in Step 1 of Example 15 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by Formula (Mw = 6000 g / mol, PDI = 2.10, yield: 53%).

(Step 2) In the same manner as in Step 2 of Example 15, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2): 2.7: 0.3: 7 was obtained (Mw = 6040 g / mol , PDI = 2.10, yield 87%).

Example 34

(Step 1) In the same manner as in Example 16 except that 5-vinyl-2-norbornene was used in place of 5-Ethylidene-2-norbornene, the mole number of the repeating unit represented by Formula (Mw = 6050 g / mol, PDI = 2.11, yield: 53%).

(Step 2) In the same manner as in Step 2 of Example 16, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 6100 g / mol , PDI = 2.11, yield: 87%).

Example 35

(Step 1) In the same manner as in Step 1 of Example 17, except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, (Mw = 5800 g / mol, PDI = 2.10, yield: 57%).

(Step 2) In the same manner as in Step 2 of Example 17, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 2.7: 0.3: 7 was obtained (Mw = 5860 g / mol , PDI = 2.11, yield: 89%).

Example 36

(Step 1) In the same manner as in Example 18 except that 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene, the molar amount of the repeating unit represented by formula (2) (Mw = 5840 g / mol, PDI = 2.09, yield: 57%).

(Step 2) In the same manner as in Step 2 of Example 18, a copolymer in which the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) was 3.6: 0.4: 6 was obtained (Mw = 5900 g / mol , PDI = 2.10, yield 90%).

Example 37

(Step 1) In Step 1 of Example 1, 24.8 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene, and 1,2,3,4,4a, Except that the content was changed to 75.2 g of 8,8a-octahydro-2-methyl-1,4: 5,8-dimethanonapthlalene, 0.022 g of PdCl ₂ , 0.035 g of P (1-nap) _{3 and} 0.024 g of AgBF ₄ (Mw = 5100 g / mol, PDI = 1.97, yield: 48%) in a molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 3:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.15 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5300 g / mol, PDI = 1.99, yield: 88%).

Example 38

(Step 1) In Step 1 of Example 1, 34.0 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene and 1,2,3,4,4a, Except that the content was changed to 66.1 g of 8,8a-octahydro-2-methyl-1,4: 5,8-dimethanonapthlalene, 0.022 g of PdCl ₂ , 0.036 g of P (1-nap) _{3 and} 0.025 g of AgBF ₄ (Mw = 5150 g / mol, PDI = 1.97, yield: 48%) in a molar ratio of the repeating unit represented by the formula (2): repeating unit represented by the formula (3) was 4:

(Step 2) In the same manner as in Example 1 except that the content of mCPBA in Step 2 was changed to 1.57 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5300 g / mol, PDI = 1.97, yield: 88%).

Example 39

(Step 1) using the third embodiment instead of the 5-Ethylidene-2-norbornene in Step 1 5- (1'-Methylethenyl) -2 -norbornene 29.4g of and, 5-Ethoxy-2-norbornene 70.6g, PdCl 2 Except that the content was changed to 0.026 g, 0.041 g of P (1-nap) _{3 and} 0.028 g of AgBF ₄ in the same manner as in Example 1, to obtain a copolymer having a molar ratio of the repeating unit represented by Formula (Mw = 5300 g / mol, PDI = 2.00, yield: 49%).

(Step 2) In the same manner as in Example 3 except that the content of mCPBA was changed to 1.36 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5500 g / mol, PDI = 2.00, yield 84%).

Example 40

(Step 1) using the third embodiment instead of the 5-Ethylidene-2-norbornene in Step 1 5- (1'-Methylethenyl) -2 -norbornene 39.3g of and, 5-Ethoxy-2-norbornene 60.8g, PdCl 2 4 the molar ratio of the repeating unit represented by the formula 3:: 0.026 g, P ( 1-nap) 3 0.041 g, and the repeating units of the general formula (2) in the same manner except that the changed content as AgBF ₄ 6 0.029g of the copolymer (Mw = 5300 g / mol, PDI = 1.99, yield: 48%).

(Step 2) In the same manner as in Example 3 except that the content of mCPBA in Step 2 was changed to 1.82 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5520 g / mol, PDI = 1.99, yield 86%).

Example 41

(Step 1) using the above Example 5 Step 1 5-Ethylidene-2-norbornene instead of 5- (1'-Methylethenyl) -2- norbornene 25.7g in and, 5-Butoxy-2-norbornene 74.4g, PdCl 2 3 mole ratio of the repeating unit of formula 3:: 0.023 g, P ( 1-nap) 3 0.036 g, AgBF except for changing the content of 0.025g ₄ and a repeating unit of formula (2) in the same way 7 to the copolymer (Mw = 5600 g / mol, PDI = 2.00, yield 50%).

(Step 2) In the same manner as in Example 5 except that the content of mCPBA in Step 2 was changed to 1.19 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5700 g / mol, PDI = 2.02, yield: 87%).

Example 42

(Step 1) using the above Example 5 instead of the 5-Ethylidene-2-norbornene in Step 1 5- (1'-Methylethenyl) -2 -norbornene 35.0g of and, 5-Butoxy-2-norbornene 65.0g, PdCl 2 0.03 g of P (1-nap) _3, 0.037 g of P (1-nap) _{3 and} 0.025 g of AgBF ₄ was used in the same manner to obtain a copolymer having a molar ratio of the repeating unit represented by formula (Mw = 5700 g / mol, PDI = 2.01, yield 50%).

(Step 2) In the same manner as in Example 5 except that the content of mCPBA was changed to 1.62 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5750 g / mol, PDI = 2.01, yield: 86%).

Example 43

(Step 1) using Example 7 5-Ethylidene-2-norbornene instead of 5- (1'-Methylethenyl) -2- norbornene 29.4g in step 1 of and, 5-Methoxymethyl-2-norbornene 70.6g, PdCl 2 Except that the content was changed to 0.026 g, 0.041 g of P (1-nap) _{3 and} 0.028 g of AgBF ₄ in the same manner as in Example 1, to obtain a copolymer having a molar ratio of the repeating unit represented by Formula (Mw = 5800 g / mol, PDI = 2.01, yield: 51%).

(Step 2) In the same manner as in Example 7 except that the content of mCPBA was changed to 1.36 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5850 g / mol, PDI = 2.02, yield: 89%).

Example 44

(Step 1) using Example 7 5-Ethylidene-2-norbornene instead of 5- (1'-Methylethenyl) -2- norbornene 39.3g in step 1 of and, 5-Methoxymethyl-2-norbornene 60.7g, PdCl 2 4 the molar ratio of the repeating unit represented by the formula 3:: 0.026 g, P ( 1-nap) 3 0.041 g, and the repeating units of the general formula (2) in the same manner except that the changed content as AgBF ₄ 6 0.029g of the copolymer (Mw = 5800 g / mol, PDI = 2.00, yield: 53%).

(Step 2) In the same manner as in Example 7 except that the content of mCPBA was changed to 1.82 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5840 g / mol, PDI = 2.01, yield: 88%).

Example 45

(Step 1) 27.4 g of 5- (1'-Methylethenyl) -2-norbornene was used in place of 5-Ethylidene-2-norbornene in Step 1 of Example 11, ( ₃ ) was prepared in the same manner as in Example 1, except that the content was changed to 72.6 g of 2-norbornene, 0.024 g of PdCl ₂ , 0.038 g of P (1-nap) _{3 and} 0.027 g of AgBF ₄ , (Mw = 5150 g / mol, PDI = 2.03, yield: 52%).

(Step 2) In the same manner as in Example 11 except that the content of mCPBA in Step 2 was changed to 1.27 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5300 g / mol, PDI = 2.03, yield: 86%).

Example 46

(Step 1) In Step 1 of Example 11, 37.1 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene, 2-norbornene, 0.025 g of PdCl ₂ , 0.039 g of P (1-nap) _{3 and} 0.027 g of AgBF ₄ in the same manner as in Example 1, (Mw = 5100 g / mol, PDI = 2.05, yield: 51%).

(Step 2) In the same manner as in Example 11 except that the content of mCPBA in Step 2 was changed to 1.72 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5300 g / mol, PDI = 2.05, yield: 88%).

Example 47

(Step 1) In Step 1 of Example 13, 37.9 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene, and 62.1 g of 2-norbornene, 0.033 g of PdCl ₂ , 1-nap) ₃ and 0.037 g of AgBF ₄ , the same procedure was repeated to obtain a copolymer having a molar ratio of the repeating unit represented by the following formula (3): 3: 7 (Mw = 5900 g / mol, PDI = 2.12, yield 52%).

(Step 2) In the same manner as in Example 13 except that the content of mCPBA in Step 2 was changed to 1.76 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 6000 g / mol, PDI = 2.12, yield: 84%).

Example 48

(Step 1) In Step 1 of Example 13, 48.8 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene, 51.3 g of 2-norbornene, 0.032 g of PdCl ₂ , (1-nap) _{3 and} 0.035 g of AgBF ₄ , the same procedure was repeated to obtain a copolymer in which the molar ratio of the repeating unit represented by the formula (2): Formula 4 was 4: 6 (Mw = 5800 g / mol, PDI = 2.13, yield: 51%).

(Step 2) In the same manner as in Example 13 except that the content of mCPBA in Step 2 was changed to 2.26 g, the molar ratio of the repeating unit represented by Formula (1): the repeating unit represented by Formula (2): Formula 3 was 3.6: 0.4: 6 (Mw = 5850 g / mol, PDI = 2.14, yield: 84%).

Example 49

(Step 1) In Step 1 of Example 15, 24.4 g of 5- (1'-Methylethenyl) -2-norbornene was used instead of 5-Ethylidene-2-norbornene, and 75.6 g of 5- n -Hexyl- _{PdCl 2 0.022 g, P (1} -nap) 3 0.034 g, AgBF except for changing the content of 0.024g ₄ and a repeating unit of formula (2) in the same manner: the molar ratio of the repeating unit of formula (3) is 3: 7, the air (Mw = 6000 g / mol, PDI = 2.10, yield 52%).

(Step 2) In the same manner as in Example 15 except that the content of mCPBA in Step 2 was changed to 1.13 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 6100 g / mol, PDI = 2.10, yield: 88%).

Example 50

(Step 1) In Step 1 of Example 15, 33.4 g of 5- (1'-Methylethenyl) -2-norbornene was used in place of 5-Ethylidene-2-norbornene, 66.7 g of 5- n -Hexyl- Except that the content ratio of the repeating unit represented by formula (2): repeating unit represented by formula (3) was 4: 6 in the same manner, except that the content was changed to 0.022 g of PdCl ₂ , 0.035 g of P (1-nap) _{3 and} 0.024 g of AgBF ₄ (Mw = 6000 g / mol, PDI = 2.11, yield 52%).

(Step 2) In the same manner as in Example 15 except that the content of mCPBA was changed to 1.15 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 6050 g / mol, PDI = 2.11, yield 86%).

Example 51

(Step 1) Example 17 (from Step 1) in place of 5-Ethylidene-2-norbornene 5- (1'-Methylethenyl) -2- norbornene 27.7g use and, 5- n -butyl-2-norbornene 72.3g, _{PdCl 2 0.024 g, P (1} -nap) 3 0.039 g, AgBF except for changing the content of 0.027g ₄ and a repeating unit of formula (2) in the same manner: the molar ratio of the repeating unit of formula (3) is 3: 7, the air (Mw = 5800 g / mol, PDI = 2.10, yield: 54%).

(Step 2) In the same manner as in Example 17 except that the content of mCPBA in Step 2 was changed to 1.28 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 2.7: 0.3: 7 (Mw = 5850 g / mol, PDI = 2.11, yield: 85%).

Example 52

(Step 1) Example 17 (from Step 1) in place of 5-Ethylidene-2-norbornene 5- (1'-Methylethenyl) -2- norbornene 37.3g use and, 5- n -butyl-2-norbornene 62.7g, Except that the content ratio of the repeating unit represented by formula (2): repeating unit represented by formula (3) was changed to 0.025 g of PdCl ₂ , 0.039 g of P (1-nap) _{3 and} 0.027 g of AgBF ₄ (Mw = 5800 g / mol, PDI = 2.10, yield 56%).

(Step 2) In the same manner as in Example 17 except that the content of mCPBA in Step 2 was changed to 1.73 g, the molar ratio of the repeating unit represented by Formula (1): repeating unit represented by Formula (2) to the repeating unit represented by Formula (3) was 3.6: 0.4: 6 (Mw = 5900 g / mol, PDI = 2.10, yield: 88%).

Comparative Example 1

(Step 1) In Step 1 of Example 13, 83.7 g of 5-vinyl-2-norbornene was used instead of 5-Ethylidene-2-norbornene and 16.4 g of 2-norbornene, 300 g of Xylene, 0.031 g of PdCl ₂ , -nap) _{3 and} 0.034 g of AgBF ₄ , the copolymer was obtained in the same manner as in Example ₁ , except that the molar ratio of the repeating units of 5-vinyl-2-norbornene: 2-norbornene was 8: 2 (Mw = 3000 g / mol, PDI = 2.05, yield 40%).

(Step 2) A copolymer having an epoxy conversion of 94% was obtained (Mw = 3250 g / mol, PDI = 2.05, yield 88%) in the same manner, except that the content of mCPBA was changed to 4.52 g in the step 2 of Example 13 %).

Comparative Example 2

(Step 1) A 250 ml Schlenk flask was charged with 74.9 g of 5-vinyl-2-norbornene, 25.2 g of 2-norbornene and 250 g of xylene. The temperature was heated to 130 while purging with N ₂ . 0.032 g of Palladium dichloride (PdCl ₂ ), 0.050 g of Tricyclohexylphosphine (P (Cy) ₃ ) and 0.035 g of Silver tetrafluoroborate (AgBF ₄ ) were added to 6 ml of dichloromethane and reacted with stirring at 130 ° C for 16 hours. After the reaction, the reaction product was poured into an excess amount of methanol to obtain a white polymer precipitate. The precipitate was filtered with a glass funnel and dried in a vacuum oven at 30 ° C. for 24 hours to obtain a copolymer having a molar ratio of repeating units of 5-vinyl-2-norbornene: 2-norbornene of 7: 3 (Mw = 5500 g / mol, PDI = 2.00, yield 60%).

(Step 2) A copolymer having an epoxy conversion of 100% (Mw = 5650 g / mol, PDI = 2.50, yield 88%) was obtained in the same manner, except that the content of mCPBA was changed to 4.30 g in the step 2 of Example 1 %).

Comparative Example 3

(Step 1) In Step 1 of Example 13, a mixture of 92.0 g of 5-Ethylidene-2-norbornene and 8.0 g of 2-norbornene, 150 g of Xylene, 0.030 g of PdCl ₂ , 0.048 g of P (Cy) _{3 and} 0.033 g of AgBF ₄ (Mw = 24000 g / mol, PDI = 3.00) was obtained in the same manner as in Example 1, except that the reaction was carried out at 80 占 폚 and the reaction was conducted at 80 占 폚. , Yield: 76%).

(Step 2) A copolymer having an epoxy conversion of 90% was obtained (Mw = 24500 g / mol, PDI = 3.00, yield 90%) in the same manner, except that the content of mCPBA was changed to 4.30 g in the step 2 of Example 13 %).

Comparative Example 4

(Step 1) In Step 1 of Example 7, 8.81 g of 5-vinyl-2-norbornene, 91.2 g of 5- (Methoxymethyl) -2-norbornene, 300 g of Xylene, 0.031 g of PdCl ₂ , A copolymer having a molar ratio of 1: 9 of the repeating unit represented by the general formula (2): (3) was obtained in the same manner, except that the content was changed to 0.049 g of P (1-nap) _{3 and} 0.034 g of AgBF ₄ = 5000 g / mol, PDI = 2.05, yield: 40%).

(Step 2) A copolymer having an epoxy conversion of 54% was obtained (Mw = 5100 g / mol, PDI = 2.05, yield 88%) in the same manner, except that the content of mCPBA was changed to 0.5 g in the step 2 of Example 7 %).

Comparative Example 5

(Step 1) In Step 1 of Example 7, 67.0 g of 5-vinyl-2-norbornene, 33.0 g of 5- (Methoxymethyl) -2-norbornene, 300 g of Xylene, 0.031 g of PdCl ₂ , Except that the content was changed to 0.049 g of P (1-nap) _{3 and} 0.034 g of AgBF ₄ to obtain a copolymer in which the molar ratio of the repeating unit of formula (3) was 7: 3 (Mw = 5100 g / mol, PDI = 2.05, yield: 42%).

(Step 2) A copolymer having an epoxy conversion of 95% was obtained (Mw = 5100 g / mol, PDI = 2.05, yield 88%) in the same manner, except that the content of mCPBA was changed to 7.2 g in the step 2 of Example 7 %).

Comparative Example 6

(Step 1) In Step 1 of Example 7, 88.7 g of 5-vinyl-2-norbornene, 11.3 g of 5- (Methoxymethyl) -2-norbornene, 300 g of Xylene, 0.032 g of PdCl ₂ , Except that the content was changed to 0.050 g of P (1-nap) _{3 and} 0.035 g of AgBF ₄ to obtain a copolymer in which the molar ratio of the repeating unit of formula (3) was 9: 1 (Mw = 5100 g / mol, PDI = 2.05, yield: 45%).

(Step 2) A copolymer having an epoxy conversion of 97% (Mw = 5350 g / mol, PDI = 2.06, yield 90%) was obtained in the same manner as in Step 7 of Example 7 except that the content of mCPBA was changed to 7.2 g %).

<Experimental Example>

40 g of the cyclic olefin-based copolymer prepared in Examples and Comparative Examples, 60 g of cyanate ester resin (Nanozine-375, Nanoco) and 0.4 g of initiator (Dicumyl peroxide, Sigma-aldrich) were dissolved in cyclohexanone solvent in an amount of 50% The resulting varnish was melted to prepare a varnish.

50 g of an inorganic filler (SC2050-HMN, Admatechs) and 21 g of cyclohexanonole as a solvent were placed in a ball mill and ball milled for 2 hours to disperse the inorganic filler. The slurry was prepared by mixing the inorganic filler with the previously prepared varnish. The thus prepared slurry was impregnated with glass fiber (L-1067, UNITIKA) and then dried by hot air to prepare a prepreg. Two sheets of the prepared prepregs were laminated, and then a copper foil having a thickness of 35 μm was placed on both sides of the copper foil. The copper foil was laminated and heated at 220 ° C. for 90 minutes using a press to produce a circuit board having a thickness of 170 μm. The cyclic olefin-based copolymers used in each of Production Examples and Comparative Production Examples are shown in Table 1 below.

Experimental Example The copolymer used Experimental Example The copolymer used Production Example 1 Example 31 Comparative Preparation Example 1 Comparative Example 1 Production Example 2 Example 32 Comparative Production Example 2 Comparative Example 2 Production Example 3 Example 35 Comparative Production Example 3 Comparative Example 3 Production Example 4 Example 36 Comparative Production Example 4 Comparative Example 4 Production Example 5 Example 25 Comparative Preparation Example 5 Comparative Example 5 Production Example 6 Example 26 Comparative Preparation Example 6 Comparative Example 6 Production Example 7 Example 27 Production Example 8 Example 28

Then, the glass transition temperature (Tg), the copper bonding strength, the dielectric constant and the dielectric loss coefficient of the resin composition were measured with the substrate prepared above.

The glass transition temperature was measured by DSC of TA instruments, and the adhesive strength of the copper foil to the specimen was measured as 90 ° peel strength. Specifically, the peel strength was measured by preparing a sample of a layered product in which a copper foil having a thickness of 35 mu m and a substrate were sequentially formed, cutting the layered sample as a physical stimulus into a rectangular shape having a width of 10 mm and then using a tensile strength meter of ZWICK (Peeling strength) when the copper foil is cut off at an angle of 90 deg. And a speed of 50 mm / min from the substrate layer by grasping the end portion of the cut copper foil.

The dielectric constant (Dk) and dielectric loss factor (Df) of the specimen were measured at 10GHz using a Vector network analyzer (agilent tech). Then, the dielectric constant values of the cyclic olefin-based copolymers of Examples and Comparative Examples were calculated using the content of each component and a known dielectric constant value.

The measurement results are summarized in Tables 2 to 5 below.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Glass transition temperature (캜) 264 266 257 259 Copper bond strength
(35 [mu] m, kgf / cm) 0.65 0.66 0.65 0.67 permittivity 3.28 3.29 3.20 3.22 Discrete Permittivity of Copolymer 2.51 2.53 2.48 2.51 Dielectric loss factor 0.0050 0.0052 0.0044 0.0045

Comparative Preparation Example 1 Comparative Production Example 2 Comparative Production Example 3 Glass transition temperature (캜) 269 268 243 Copper bond strength
(35 [mu] m, kgf / cm) 0.69 0.69 0.68 permittivity 3.43 3.45 3.50 Discrete Permittivity of Copolymer 2.79 2.81 3.06 Dielectric loss factor 0.0073 0.0075 0.0085

Production Example 5 Production Example 6 Production Example 7 Production Example 8 Glass transition temperature (캜) 270 272 270 269 Copper bond strength
(35 [mu] m, kgf / cm) 0.80 0.82 0.85 0.86 permittivity 3.29 3.32 3.30 3.32 Discrete Permittivity of Copolymer 2.53 2.55 2.54 2.55 Dielectric loss factor 0.0050 0.0052 0.0049 0.0051

Comparative Production Example 4 Comparative Preparation Example 5 Comparative Preparation Example 6 Glass transition temperature (캜) 250 271 271 Copper bond strength
(35 [mu] m, kgf / cm) 0.30 0.68 0.68 permittivity 3.28 3.39 3.44 Discrete Permittivity of Copolymer 2.51 2.75 2.79 Dielectric loss factor 0.0040 0.0075 0.0080

The cyclic olefin-based copolymer containing a repeating unit containing an epoxy group, a repeating unit containing a vinyl group or an ethylidene group and a repeating unit containing an aliphatic functional group of the present invention has a sole dielectric constant of 2.6 or less and a dielectric loss coefficient of 0.007 or less And exhibits very good low dielectric properties. In the case of the prepreg used as the insulating layer, the lower the dielectric constant and the dielectric loss factor value are, the better the characteristics are, and the higher the insulating property is, the higher the transmission loss is in the high frequency region, thereby adversely affecting the performance, durability and yield I can go crazy.

Further, it can be confirmed from the above Experimental Example that the cyclic olefin-based copolymer exhibits a high copper bonding strength of 0.6 kgf / cm or more. If the adhesive strength of the copper foil is less than 0.6 kgf / cm, it may be difficult to manufacture the product because it is easily peeled off when the CCL is manufactured using the prepreg and the copper foil, and reliability is not ensured even if the product is manufactured.

However, the dielectric property, the glass transition temperature, or the bonding strength may be lowered when the repeating units not including all of the above three repeating units or the repeating units containing an epoxy group are out of the above range.

Particularly, the cyclic olefin-based copolymers of Examples 25 to 28 used in Production Examples 5 to 8 contain repeating units containing an ether functional group or a heterocyclic functional group, and thus have a high glass transition temperature of 268 DEG C or higher, 0.80 kgf / cm, it was confirmed that excellent dielectric properties were satisfied. Thus, it was confirmed that by including a specific functional group, it is possible to realize a remarkably high copper foil bonding strength while maintaining a low dielectric property.

On the other hand, to compare the viscosities according to the molecular weights, the viscosities measured by Toki's TV-25 viscometer against the varnishes obtained in Production Examples 5 to 8 are shown in Table 6 below.

division Viscosity (cps) The varnish of Preparation Example 5 680 The varnish of Preparation Example 6 680 The varnish of Preparation Example 7 660 The varnish of Preparation Example 8 660

As shown in Table 6, the varnishes obtained in Production Examples 5 to 8, including the cyclic olefin-based copolymer having a molecular weight of 2,500 g / mol to 10,000 g / mol, can maintain a low viscosity of 1000 cps or less, It is easy to manufacture legs.

Claims (16)

A repeating unit represented by the following general formula (1) is preferably added to all the repeating units represented by the following formulas (1) to (3), wherein the repeating unit includes a repeating unit represented by the following formula And from 15 mol% to 60 mol% of the cyclic olefin-based copolymer:
[Chemical Formula 1]

In Formula 1,
p is an integer of 0 to 4,
R ₁ to R ₄ each independently represent hydrogen, an epoxy group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₁ and R ₂ , R ₃ and R ₄ , To form an epoxy group, provided that when R ₁ to R ₄ are all hydrogen,
(2)

In Formula 2,
q is an integer of 0 to 4,
R ₅ to R ₈ are each independently a hydrogen or a vinyl group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₅ and R ₆ , R ₇ and R ₈ , To form an alkylidene group, with the proviso that when R ₅ to R ₈ are both hydrogen,
(3)

In Formula 3,
r and m are each independently an integer of 0 to 4,
Each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S;
The method according to claim 1,
And a weight average molecular weight (GPC measurement) of 2,500 to 10,000 g / mol.
The method according to claim 1,
Wherein R is a substituted or unsubstituted C _1-20 ether; Or a C _2-60 heterocyclic ring containing at least one of substituted or unsubstituted O, N, Si and S, cyclic olefin-based copolymer.
The method according to claim 1,
In the general formula R 3 is a C _1-20 alkyl group, a cyclic olefin-based copolymer substituted with C _1-20 alkoxy.
The method according to claim 1,
Wherein R in the general formula (3) is a functional group represented by the following general formula (7):
(7)

In Formula 7,
At least one of A ₁ and A ₂ is O, N, Si, or S, and the others are carbon,
t is an integer of 1 or more,
"* &Quot; forms a bond to the same carbon atom.
The method according to claim 1,
The cured product of the cyclic olefin-based copolymer has a copper foil adhesive strength of 0.6 kgf / cm or more.
The method according to claim 1,
The cured product of the cyclic olefin-based copolymer has a dielectric constant of 2.6 or less at 10 GHz.
The method according to claim 1,
Wherein the cured product of the cyclic olefin-based copolymer has a dielectric loss coefficient of 0.007 or less at 10 GHz.
Polymerizing a monomer represented by the following formula (4) and a monomer represented by the following formula (5) in the presence of a ligand comprising a prodrug of a Group 10 transition metal, an anion co-catalyst coordinating to the metal of the procatalyst, and a Group 15 element; And
And subjecting the polymer to epoxidation by reacting with a peroxide. The process for producing the cyclic olefin-based copolymer as claimed in claim 1,
[Chemical Formula 4]

In Formula 4,
q is an integer of 0 to 4,
R ₅ to R ₈ are each independently a hydrogen or a vinyl group substituted or unsubstituted with alkyl having 1 to 4 carbon atoms, or a combination of at least one selected from the group consisting of R ₅ and R ₆ , R ₇ and R ₈ , To form an alkylidene group, with the proviso that when R ₅ to R ₈ are both hydrogen,
[Chemical Formula 5]

In Formula 5,
r and m are each independently an integer of 0 to 4,
Each R is independently hydrogen; halogen; Substituted or unsubstituted C _1-20 alkyl; A substituted or unsubstituted C _1-20 ether; Substituted or unsubstituted C _1-20 alkoxy; Or a C _2-60 heterocycle containing one or more of substituted or unsubstituted O, N, Si and S;
10. The method of claim 9,
Wherein R is a substituted or unsubstituted C _1-20 ether; Or a substituted or unsubstituted C _2-60 heterocyclic ring containing at least one of O, N, Si and S;
10. The method of claim 9,
Wherein R is a C _1-20 alkyl group substituted with C _1-20 alkoxy.
10. The method of claim 9,
Wherein R in formula (5) is a functional group represented by the following formula (7): &lt; EMI ID =
(7)

In Formula 7,
At least one of A ₁ and A ₂ is O, N, Si, or S, and the others are carbon,
t is an integer of 1 or more,
"* &Quot; forms a bond to the same carbon atom.
10. The method of claim 9,
The precursor of the Group 10 transition metal is PdCl ₂ (Palladium dichloride), PdBr ₂ (Palladium dibromide) [(Allyl) Pd (Cl)] ₂ (Allylpalladiumchloride dimer), (CH ₃ CO ₂ ) ₂ Pd (Palladium acetate), [CH ₃ COCH═C (O-) CH ₃ ] ₂ Pd ), [PdCl (NB) O (CH ₃ )] ₂ , dibenzylideneacetone ₂ Pd, dibenzylideneacetone ₃ Pd ₂ (Tris (dibenzylideneacetone) dipalladium), Pd (NO 3) 2 (Palladium nitrate), and _{NiBr (NP (CH 3) 3} ) 4 , including at least one element selected from the group consisting of, a cyclic olefin copolymer of Gt;
10. The method of claim 9,
The ligand comprising the Group 15 element is selected from the group consisting of (2-hydroxyphenyl) diphenylphosphine, tri (furan-2-yl) phosphine, bis (diphenylphosphino) methane, bis (Para-tolyl) phosphine, tri-1-naphthylphosphine, tributylphosphine, tetra (ortho-tolyl) phosphine, (Diphenylphosphino) ethane, tributylphosphine, triphenylphosphine oxide, and 1,2- (di &lt; RTI ID = 0.0 & Phenylphosphino) -butane. The method for producing a cyclic olefin-based copolymer according to claim 1,
10. The method of claim 9,
Wherein the peroxide is at least one selected from the group consisting of peroxy peroxide, peroxyacetic acid, peroxy peroxide, perphthalic acid, perpropionic acid, perbutyric acid, trifluoro peroxyacetic acid and hydrogen peroxide .
10. The method of claim 9,
Wherein the molar ratio of the polymer to the organic peroxy acid in the step of epoxidation is 1: 0.1 to 1: 5.