JP7591876B2 - Unsaturated group-containing cyclic polyolefin - Google Patents

Description

The object of the present invention is to provide an unsaturated group-containing cyclic polyolefin that has excellent solubility in organic solvents, adhesion, and transparency.

In general, low molecular weight polyolefins such as polyethylene and polypropylene are lightweight, water resistant, chemical resistant, insulating, and easy to handle, and therefore are given shapes through various molding processes and are used as various industrial materials.
However, this low molecular weight polypropylene has a problem that it is sticky, causing blocking and making it difficult to handle (Patent Document 1 [Problems to be Solved by the Invention]).

In response to this, Patent Document 1 discloses a low molecular weight propylene-based polymer in which a mixture of specific polypropylene and polyethylene is thermally degraded to reduce its molecular weight, thereby reducing adhesion and suppressing the occurrence of blocking.

Japanese Patent Application Publication No. 3-84009

However, polyolefins have high crystallinity, which reduces their solubility in organic solvents. Furthermore, such crystallinity usually impairs the transparency of polyolefins, resulting in undesirable transparency and color development of the coating film. For this reason, studies are being conducted to reduce the crystallinity of polyolefins and improve their solubility.
Furthermore, polyolefins are also required to have the ability to be easily coated or laminated onto adherends.

However, the low molecular weight propylene polymer obtained in Patent Document 1 tends to have insufficient solubility in organic solvents, and therefore tends to have insufficient transparency. In addition, because of insufficient adhesion, the coating and lamination properties on the adherend tend to be insufficient.

The present invention has been made in view of these problems. That is, the present invention aims to provide an unsaturated group-containing cyclic polyolefin that has excellent solubility in organic solvents, adhesion, and transparency.

As a result of intensive research conducted by the present inventors to solve the above problems, they have found that the above problems can be solved by using a specific cyclic polyolefin and subjecting it to thermal degradation to reduce its molecular weight and to impart unsaturated groups.
That is, the present invention has the following features.

[1] An unsaturated group-containing cyclic polyolefin having a vinyl group and/or a vinylidene group in the molecular structure of the cyclic polyolefin, the cyclic polyolefin being a hydrogenated product of a polymer consisting of aromatic vinyl monomer units, or a hydrogenated block copolymer having a hydrogenated product of a polymer block consisting of aromatic vinyl monomer units and a hydrogenated product of a polymer block consisting of conjugated diene monomer units.

[2] The unsaturated group-containing cyclic polyolefin according to [1], having a weight average molecular weight of 1,000 to 40,000.
[3] The unsaturated group-containing cyclic polyolefin according to [1] or [2], wherein the total number of vinyl groups and vinylidene groups per 1,000 monomer units is 1 to 200.
[4] The unsaturated group-containing cyclic polyolefin according to any one of [1] to [3], wherein the number of vinylidene groups per 1,000 monomer units is 1 to 100.

[5] The unsaturated group-containing cyclic polyolefin according to any one of [1] to [4], wherein the hydrogenated polymer composed of aromatic vinyl monomer units has a hydrogenation level of 90% or more.
[6] The unsaturated group-containing cyclic polyolefin according to any one of [1] to [4], wherein the hydrogenated polymer block composed of the aromatic vinyl monomer units has a hydrogenation level of 90% or more.
[7] The method for producing an unsaturated group-containing cyclic polyolefin according to any one of [1] to [6], comprising thermally degrading the cyclic polyolefin in an inert gas at 300 to 400° C. for 0.5 to 10 hours.

[8] An organic solvent-unsaturated group-containing cyclic polyolefin mixture comprising an unsaturated group-containing cyclic polyolefin solution or an unsaturated group-containing cyclic polyolefin slurry, in which the unsaturated group-containing cyclic polyolefin according to any one of [1] to [6] is dissolved or suspended in an organic solvent at a concentration of 1 to 30 mass %.
[9] An unsaturated group-containing cyclic polyolefin-containing laminate, comprising the unsaturated group-containing cyclic polyolefin according to any one of [1] to [6] laminated on a substrate.
[10] A method for producing an unsaturated group-containing cyclic polyolefin-containing laminate, comprising applying the organic solvent-unsaturated group-containing cyclic polyolefin mixture according to [8] to a substrate, and then removing the solvent to obtain a laminate.

The unsaturated group-containing cyclic polyolefin of the present invention is soluble in an organic solvent, and when applied to a substrate such as a metal, glass, or plastic, it becomes a coating film having transparency and good adhesive strength, and a laminate can be obtained.
Furthermore, the solution or slurry of the present invention can be applied to substrates such as metals, glass, and plastics, and by removing the organic solvent, a coating film having transparency and good adhesive strength is formed.
Furthermore, since the unsaturated group-containing cyclic polyolefin and the laminate of the present invention are not subjected to chlorination or the like, no toxic gases are generated when burned.

The present invention will be described in detail below. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the contents of the following description as long as it does not deviate from the gist of the present invention.
In the following, when the expression "~" is used, it is used as an expression including the numerical values or physical property values before and after it.

<Unsaturated Group-Containing Cyclic Polyolefin>
The present invention relates to an unsaturated group-containing cyclic polyolefin having a vinyl group and/or a vinylidene group in the molecular structure of the cyclic polyolefin.
The cyclic polyolefin refers to a hydrogenated product of a polymer composed of aromatic vinyl monomer units, or a hydrogenated block copolymer having a hydrogenated product of a polymer block composed of aromatic vinyl monomer units and a hydrogenated product of a polymer block composed of conjugated diene monomer units.

The "hydrogenated polymer block composed of aromatic vinyl monomer units" contained in the hydrogenated block copolymer may be referred to as "hydrogenated aromatic vinyl polymer block unit," and the "hydrogenated polymer block composed of conjugated diene monomer units" may be referred to as "hydrogenated conjugated diene polymer block unit."

The unsaturated group-containing cyclic polyolefin of the present invention is obtained by subjecting the cyclic polyolefin described below to thermal degradation treatment to reduce the molecular weight and impart unsaturated groups. The method for producing this unsaturated group-containing cyclic polyolefin is described below.

The lower limit of the weight average molecular weight (Mw) of the unsaturated group-containing cyclic polyolefin is preferably 1,000 or more, more preferably 3,000 or more. The upper limit of Mw is preferably 40,000 or less, more preferably 30,000 or less.
If the Mw of the unsaturated group-containing cyclic polyolefin is equal to or greater than the lower limit, the material strength and adhesiveness are not decreased, which is preferable, whereas if the Mw is equal to or less than the upper limit, the solubility in organic solvents is not decreased, which is preferable.
The Mw of the unsaturated group-containing cyclic polyolefin is determined by gel permeation chromatography (GPC), and the specific measurement method is as described in the Examples section.

The Mw of the unsaturated group-containing cyclic polyolefin can be controlled by the temperature and time of the thermal degradation treatment of the cyclic polyolefin.

<Unsaturated Group>
The unsaturated groups contained in the unsaturated group-containing cyclic polyolefin are vinyl groups and/or vinylidene groups, with vinylidene groups being preferred.
The unsaturated group-containing cyclic polyolefin of the present invention may contain an unsaturated group other than a vinyl group or a vinylidene group.

<Number of unsaturated groups>
The numbers of vinyl groups and vinylidene groups contained in the unsaturated group-containing cyclic polyolefin can be determined from the results of ¹ H-NMR measurement as follows.

(Number of vinyl groups/1,000 monomer units)=
[((total integrals of vinyl signals in the 4.9-5.1 ppm region and the 5.7-5.9 ppm region)/number of hydrogen atoms in vinyl groups)×1,000]
/ [(integral value of the signal originating from the main chain in the 0.2 to 3.0 ppm region)/number of hydrogen atoms in the monomer unit of the cyclic polyolefin)]

(Number of vinylidene groups/1,000 monomer units)=
[((sum of integrals of vinylidene signals at 4.69 ppm and 4.74 ppm)/number of hydrogen atoms in vinylidene groups)×1,000]
/ [(integral value of the signal originating from the main chain in the 0.2 to 3.0 ppm region)/number of hydrogen atoms in the monomer unit of the cyclic polyolefin)]

Here, the number of hydrogen atoms in the vinyl group is 3, and the number of hydrogen atoms in the vinylidene group is 2.
The number of hydrogen atoms in the monomer unit of the cyclic polyolefin is, for example, 14 in the case of a hydrogenated styrene unit, and 8 in the case of a hydrogenated butadiene unit. The ratio of the hydrogenated styrene unit to the hydrogenated butadiene unit is calculated by the measurement by carbon NMR described in the Examples section.

The number of unsaturated groups contained in the unsaturated group-containing cyclic polyolefin of the present invention, i.e., the number of vinyl groups per 1,000 monomer units and the number of vinylidene groups per 1,000 monomer units, are expressed as values rounded off to the nearest whole number.

The total number of vinyl groups and vinylidene groups per 1,000 monomer units is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, it is preferably 200 or less, and more preferably 150 or less.

The number of vinylidene groups per 1,000 monomer units is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, the number is preferably 100 or less, and more preferably 80 or less.
When the number of unsaturated groups in the unsaturated group-containing cyclic polyolefin is equal to or greater than the lower limit, the unsaturated group-containing cyclic polyolefin can exhibit sufficient solubility in organic solvents and adhesive properties, while when the number of unsaturated groups is equal to or less than the upper limit, the molecular weight does not become small and the material strength does not decrease.

<Hydrogenation Level of Hydrogenated Product of Unsaturated Group-Containing Cyclic Polyolefin>
When the cyclic polyolefin of the unsaturated group-containing cyclic polyolefin is a hydrogenated product of a polymer consisting of aromatic vinyl monomer units, the hydrogenation level indicates the proportion of aromatic vinyl monomer units saturated by hydrogenation, and is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more. Such a high level of hydrogenation is preferred for transparency.

When the cyclic polyolefin of the unsaturated group-containing cyclic polyolefin is the hydrogenated block copolymer, the hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation, and is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more. Such a high level of hydrogenation is preferred for transparency.
The hydrogenation level is determined using proton NMR.

<Production of Unsaturated Group-Containing Cyclic Polyolefin>
The unsaturated group-containing cyclic polyolefin of the present invention can be produced by subjecting the cyclic polyolefin (a) to thermal degradation treatment.
For example, there is a method in which the cyclic polyolefin (a) is thermally degraded at 300 to 400° C. for 0.5 to 10 hours under nitrogen gas flow.

<Cyclic polyolefin (a)>
The cyclic polyolefin (a) used as the raw material for the unsaturated group-containing cyclic polyolefin of the present invention is a hydrogenated product of a polymer composed of aromatic vinyl monomer units, or a hydrogenated block copolymer having a hydrogenated product of a polymer block composed of aromatic vinyl monomer units and a hydrogenated product of a polymer block composed of conjugated diene monomer units.
Here, the "cyclic" in cyclic polyolefin refers to an alicyclic structure formed by hydrogenation of an aromatic ring contained in an aromatic vinyl monomer unit.

The hydrogenated polymer composed of aromatic vinyl monomer units is a hydrogenated aromatic vinyl polymer.
Examples of hydrogenated polymers composed of aromatic vinyl monomer units include hydrogenated polystyrene, hydrogenated styrene/α-methylstyrene copolymers, and hydrogenated styrene/vinylnaphthalene copolymers.
Among these, hydrogenated polystyrene is preferred.

The hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit which is a hydrogenated product of a polymer block composed of the aromatic vinyl monomer unit, and a hydrogenated conjugated diene polymer block unit which is a hydrogenated product of a polymer block composed of the conjugated diene monomer unit.
The hydrogenated block copolymer has at least two of the hydrogenated aromatic vinyl polymer block units and at least one of the hydrogenated conjugated diene polymer block units.

When the cyclic polyolefin (a) is a hydrogenated polymer composed of aromatic vinyl monomer units, the aromatic rings in the molecular structure and vinyl groups that may be formed at the molecular terminals are hydrogenated.
In other words, the molecular structure contains substantially no vinyl or vinylidene groups, which makes it possible to distinguish the polymer before and after thermal degradation.

When the cyclic polyolefin (a) is the hydrogenated block copolymer, the aromatic rings in the molecular structure, the vinylene groups and vinyl groups derived from the conjugated diene units in the molecular structure, and the vinyl groups that may be generated at the molecular terminals are hydrogenated.
That is, the molecular structure contains substantially no vinyl or vinylidene groups, which makes it possible to distinguish the polymer before and after thermal degradation.

From the viewpoints of transparency and material strength, the cyclic polyolefin (a) used in the present invention is preferably the above-mentioned hydrogenated block copolymer.

The term "block" refers to a copolymer polymerization segment that exhibits microphase separation from structurally or compositionally distinct polymerization segments of the copolymer. Thus, for example, "having at least two block units" means that the hydrogenated block copolymer has at least two copolymer polymerization segments that exhibit microphase separation from structurally or compositionally distinct polymerization segments.

The aromatic vinyl monomer that is the raw material for the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

ここでＲは、水素又はアルキル基、Ａｒはフェニル基、ハロフェニル基、アルキルフェニル基、アルキルハロフェニル基、ナフチル基、ピリジニル基又はアントラセニル基である。

Here, R is hydrogen or an alkyl group, and Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthracenyl group.

The alkyl group may be mono- or polysubstituted with functional groups such as halo, nitro, amino, hydroxy, cyano, carbonyl and carboxyl groups. The alkyl group preferably has 1 to 6 carbon atoms.
The above Ar is preferably a phenyl group or an alkylphenyl group, more preferably a phenyl group.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene (including all isomers, especially p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene (all isomers), and mixtures thereof.

The conjugated diene monomer serving as a raw material for the conjugated diene monomer unit may be any monomer having two conjugated double bonds.
Conjugated diene monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 pentadiene and the like, and mixtures thereof.

Polybutadiene, a polymer of 1,3-butadiene, can contain either a 1,2 configuration that upon hydrogenation gives the equivalent of a 1-butene repeat unit, or a 1,4 configuration that upon hydrogenation gives the equivalent of an ethylene repeat unit.

A preferred example of the hydrogenated aromatic vinyl polymer block unit is a unit derived from hydrogenated polystyrene, and a preferred example of the hydrogenated conjugated diene polymer block unit is a unit derived from hydrogenated polybutadiene.
A preferred embodiment of the hydrogenated block copolymer is a hydrogenated triblock or pentablock copolymer of styrene and butadiene, which preferably does not contain any other functional groups or structural modifiers.

The content of the hydrogenated aromatic vinyl polymer block unit is preferably 30 to 99 mol %, more preferably 40 to 90 mol %, based on the cyclic polyolefin (a).
When the ratio of the hydrogenated aromatic vinyl polymer block units is equal to or higher than the above lower limit, the rigidity does not decrease, and when it is equal to or lower than the above upper limit, the brittleness does not increase.

The content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 70 mol %, more preferably 10 to 60 mol %, based on the cyclic polyolefin (a).
When the ratio of the hydrogenated conjugated diene polymer block units is equal to or higher than the above lower limit, the brittleness does not deteriorate, and when it is equal to or lower than the above upper limit, the rigidity does not decrease.

Hydrogenated block copolymers are produced by hydrogenation of block copolymers including triblock, multiblock, tapered block and star block copolymers such as SBS, SBSBS, SIS, SISIS, and SISBS (where S is polystyrene, B is polybutadiene, and I is polyisoprene).

The hydrogenated block copolymer contains a segment of aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units. And, between these two hydrogenated aromatic vinyl polymer block units, there is at least one hydrogenated conjugated diene polymer block unit.

The block copolymers that make up the hydrogenated block copolymer before hydrogenation may contain additional blocks, which may be attached at any position along the triblock polymer backbone. Thus, linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymers may be branched, with the polymer chains attached at any position along the copolymer backbone.

The lower limit of Mw of the hydrogenated block copolymer is preferably 10,000 or more, more preferably 20,000 or more, and the upper limit of Mw is preferably 300,000 or less, more preferably 200,000 or less.
When the Mw is equal to or higher than the lower limit, the mechanical strength does not decrease, and when it is equal to or lower than the upper limit, the solubility of the resulting unsaturated group-containing cyclic polyolefin in organic solvents is improved.
The Mw herein is determined by GPC measurements.

When the cyclic polyolefin (a) is a hydrogenated polymer of aromatic vinyl monomer units, the hydrogenation level indicates the proportion of aromatic vinyl monomer units that are saturated by hydrogenation, and is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more. Such a high level of hydrogenation is preferred for transparency.

When the cyclic polyolefin (a) is a hydrogenated block copolymer, its hydrogenation level is preferably 90% or more of hydrogenated aromatic vinyl polymer block units and 95% or more of hydrogenated conjugated diene polymer block units; more preferably 95% or more of hydrogenated aromatic vinyl polymer block units and 99% or more of hydrogenated conjugated diene polymer block units; still more preferably 98% or more of hydrogenated aromatic vinyl polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units; particularly preferably 99.5% or more of hydrogenated aromatic vinyl polymer block units and 99.5% or more of hydrogenated conjugated diene polymer block units.
Such a high level of hydrogenation is preferred for developing transparency.

The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit refers to the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation, and the hydrogenation level of the hydrogenated conjugated diene polymer block unit refers to the proportion of the conjugated diene polymer block unit saturated by hydrogenation.
The hydrogenation level is determined using proton NMR.

The melt flow rate (MFR) of the cyclic polyolefin (a) is usually 0.1 g/10 min or more, preferably 0.5 g/10 min or more from the viewpoint of the molding method and the appearance of the molded product, and usually 200 g/10 min or less, preferably 100 g/10 min or less, more preferably 50 g/10 min or less from the viewpoint of material strength.
The MFR was measured in accordance with ISO R1133 at a measurement temperature of 230° C. and a measurement load of 2.16 kg.

The cyclic polyolefin (a) may be used alone or in combination of two or more kinds.
As the cyclic polyolefin (a), commercially available products can be used, and a specific example thereof is XELAS (registered trademark) manufactured by Mitsubishi Chemical Corporation.

<Organic Solvent-Unsaturated Group-Containing Cyclic Polyolefin Mixture>
The unsaturated group-containing cyclic polyolefin of the present invention can be dissolved or suspended in an organic solvent to form a solution or a slurry, and a mixture of the organic solvent and the unsaturated group-containing cyclic polyolefin (organic solvent-unsaturated group-containing cyclic polyolefin mixture) can be obtained.
The term "solution" used herein refers to a state in which the unsaturated group-containing cyclic polyolefin is dissolved in an organic solvent, that is, a state in which the unsaturated group-containing cyclic polyolefin is molecularly dispersed in the organic solvent.
The term "slurry" refers to a suspension in which particles of the unsaturated group-containing cyclic polyolefin are mixed in an organic solvent.
Generally, polyolefins have poor solubility in organic solvents, and even if they do dissolve, they gel and are not suitable for coating. However, the unsaturated group-containing cyclic polyolefin of the present invention exhibits unique properties in this respect.

The organic solvents in which the unsaturated group-containing cyclic polyolefin of the present invention can be dissolved are aromatic solvents, aliphatic solvents and alicyclic solvents.
Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, and bromonaphthalene. Examples of aliphatic solvents include hexane, heptane, octane, nonane, and decane. Examples of alicyclic solvents include cyclopentane, cyclohexane, cycloheptane, and cyclodecane.
These may be used alone or in combination of two or more.
Among these, toluene and cyclohexane are preferred from the viewpoints of ease of handling and distillation.

In addition, organic solvents other than those mentioned above can be added to the extent that they do not impair the effects of the present invention. Examples of other organic solvents that can be used include ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and benzophenone; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; phenols such as phenol, cresol, and naphthol; ethers such as ethylene glycol monomethyl ether; and amides such as N,N-dimethylformamide and N,N-dimethylacetamide.

The concentration of the unsaturated group-containing cyclic polyolefin in the above solution or slurry is preferably 1 to 30% by mass.
When the concentration of the unsaturated group-containing cyclic polyolefin is equal to or higher than the lower limit, the solution viscosity is appropriate and suitable for coating work, whereas when the concentration is equal to or lower than the upper limit, the solution viscosity is appropriate and gelation does not occur.
The concentration of the unsaturated group-containing cyclic polyolefin in the solution or slurry is more preferably from 5 to 20% by mass.

<Other ingredients>
The solution or slurry of the unsaturated group-containing cyclic polyolefin of the present invention may contain components other than those listed above for the purpose of further improving its functionality.
Such other components include thermosetting resins, photocurable resins, curing accelerators, ultraviolet absorbers, antioxidants, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, inorganic fillers, and organic fillers.

Furthermore, a resin component or an elastomer component may be contained within a range that does not impair the effects of the present invention.
Examples of such resin components include polyethylene resins, polypropylene resins, ethylene/α-olefin copolymer resins, propylene/α-olefin copolymer resins, ethylene/vinyl acetate copolymer resins, ethylene/acrylic acid ester copolymer resins, ethylene/(meth)acrylic acid copolymer resins, polystyrene resins, polyvinyl chloride resins, polyester resins, polyamide resins, ethylene/vinyl alcohol copolymers, acrylic resins, petroleum resins, styrene/conjugated diene block copolymer resins, epoxy resins, and polyphenylene ether resins.
Examples of the elastomer component include olefin-based elastomers, styrene-based elastomers, polyester-based elastomers, urethane-based elastomers, acrylic-based elastomers, and nylon-based elastomers.

The other components may be added to the unsaturated group-containing cyclic polyolefin of the present invention by a kneading method commonly used for melt-kneading of thermoplastic resins, or may be dissolved in an organic solvent together with the unsaturated group-containing cyclic polyolefin and mixed.
The content of other resin components and elastomer components is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, of the total components.

<Laminate of Unsaturated Group-Containing Cyclic Polyolefin>
The unsaturated group-containing cyclic polyolefin of the present invention has good adhesive strength to substrates such as metals, glass and plastics, gives a non-sticky adhesive surface, and can give a laminate with metals, glass or plastics.
There is no particular restriction on the lamination method, and any known lamination method such as heat pressing, melt extrusion molding, or insert injection molding can be used.

Alternatively, a laminate can be obtained by applying the organic solvent-unsaturated group-containing cyclic polyolefin mixture of the present invention to a metal or the like, and then removing the solvent.
The coating method can be a bar coater, a blade coater, a die coater, a gravure roll coater, a spray coater, etc., or a brush coater. The coating thickness can be adjusted as necessary, but is usually preferably 1 to 100 μm.
After coating, the solvent can be removed by distillation from the coated surface. Usually, this is preferably done by blowing hot air, but it is also possible to combine a vacuum treatment with heating, or to simultaneously perform a press.

Examples of substrates that are the coated materials from which the above-mentioned laminate is obtained include metals and alloys such as copper, aluminum, iron, stainless steel, nickel, zinc, titanium, and tungsten; glasses such as glass plates, glass fiber mats, glass fiber cloths, and glass wool; and plastics such as polyethylene, polypropylene, polybutene, ethylene/α-olefin copolymers, propylene/α-olefin copolymers, ethylene/acrylic acid ester copolymers, ethylene/vinyl monomer copolymers, polyamides, and ethylene/vinyl acetate copolymers (EVOH).
These may be in the form of a plate, a film, or other shapes, may be made of a single material or may be composite, and may be single-layered or laminated.

Of these substrates, copper is preferred for electronic components such as circuit boards in terms of electrical conductivity and economy, iron and stainless steel are preferred for handrails and plywood in terms of economy and rigidity, aluminum is preferred for battery packaging and other applications in terms of light weight and processability, and polyamide and EVOH are preferred for food packaging in terms of gas barrier properties.

<Applications>
The unsaturated group-containing cyclic polyolefin of the present invention has the effects of being transparent, having excellent solubility in organic solvents, and having excellent adhesion to metals, glass, and plastics, and further, a solution containing the same also has excellent adhesion to metals, glass, and plastics.
For this reason, it can be applied in various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electric and electronic parts, and is particularly useful as insulating casting, laminating materials, sealing materials, etc. in the electric and electronic fields.

Examples of applications of the unsaturated group-containing cyclic polyolefin of the present invention or a solution or slurry using the same include copper foil laminates, flexible printed circuit boards, multilayer printed wiring boards, and laminates for electric and electronic circuits such as capacitors; adhesives such as film adhesives and liquid adhesives; semiconductor encapsulation materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, and heat dissipation substrates.

<Conductive Metal Layer-Containing Unsaturated Group-Containing Cyclic Polyolefin Laminate>
The unsaturated group-containing cyclic polyolefin of the present invention and a solution or slurry using the same can also be suitably used as a laminate containing a conductive metal layer, such as the above-mentioned laminate for electric and electronic circuits.
This laminate containing a conductive metal layer is obtained by laminating a layer containing the unsaturated group-containing cyclic polyolefin of the present invention and a conductive metal layer, and so long as it is a laminate of a layer containing the unsaturated group-containing cyclic polyolefin of the present invention and a conductive metal layer, it includes laminates such as circuits having capacitors in addition to the above-mentioned electric/electronic circuits.
In addition, the conductive metal layer-containing unsaturated group-containing cyclic polyolefin laminate may have layers made of two or more kinds of unsaturated group-containing cyclic polyolefins, and it is sufficient that the unsaturated group-containing cyclic polyolefin of the present invention is used in at least one layer. Also, two or more kinds of conductive metal layers may be formed.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various physical properties were measured by the following methods.
In the following description, "parts" means "parts by mass" and "%" means "% by mass".

<Molecular weight>
・Apparatus: Tosoh Corporation GPC HLC-832GPC/HT
Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength: 3.42 μm)
Column: Showa Denko K.K. AD806M/S x 3 (The columns were calibrated using Tosoh monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288, each 0.5 mg/mL solution), and the elution volume and the logarithm of the molecular weight were approximated by a cubic equation.)
・Measurement temperature: 135℃
・Concentration: 20mg/10mL
・Injection volume: 0.2mL
Solvent: o-dichlorobenzene Flow rate: 1.0 mL/min

<Polymer block ratio>
[Measurement by Carbon NMR]
Apparatus: Bruker "AVANCE 400 Spectrometer"
Solvent: o-dichlorobenzene- _h4 /p-dichlorobenzene- _d4 mixed solvent Concentration: 0.3 g/2.5 mL
・Measurement: ^13C -NMR
・Resonance frequency: 400MHz
・Number of times accumulated: 3600
Flip angle: 45 degrees Data acquisition time: 1.5 seconds Pulse repetition time: 15 seconds Measurement temperature: 100°C
・^1H irradiation: Complete decoupling

<Hydrogenation Level of Hydrogenated Aromatic Vinyl Polymer Block Unit and Hydrogenated Conjugated Diene Polymer Block Unit>
[Measurement by proton NMR]
Apparatus: Bruker "AVANCE 400 Spectrometer"
Solvent: Tetrachloroethane Concentration: 0.045 g/1.0 mL
・Measurement: ^1H -NMR
・Resonance frequency: 400MHz
Flip angle: 45 degrees Data acquisition time: 4 seconds Pulse repetition time: 10 seconds Number of integrations: 64
Measurement temperature: 80°C
Hydrogenation level of hydrogenated aromatic vinyl polymer block unit: integral value reduction rate of 6.8 to 7.5 ppm Hydrogenation level of hydrogenated conjugated diene polymer block unit: integral value reduction rate of 5.7 to 6.4 ppm

<Unsaturated Group of Unsaturated Group-Containing Cyclic Polyolefin>
[Measurement by proton NMR]
Apparatus: Bruker "AVANCE 400 Spectrometer"
Solvent: Tetrachloroethane Concentration: 0.045 g/1.0 mL
・Measurement: ^1H -NMR
・Resonance frequency: 400MHz
Flip angle: 45 degrees Data acquisition time: 4 seconds Pulse repetition time: 10 seconds Number of integrations: 64
Measurement temperature: 80°C

<Unsaturated Group of Polypropylene Having Unsaturated Group>
[Measurement by proton NMR]
Apparatus: Bruker "AVANCE 400 Spectrometer"
Solvent: Tetrachloroethane Concentration: 0.045 g/1.0 mL
・Measurement: ^1H -NMR
・Resonance frequency: 400MHz
Flip angle: 45 degrees Data acquisition time: 4 seconds Pulse repetition time: 10 seconds Number of integrations: 64
Measurement temperature: 80°C

<Number of vinyl groups per 1,000 polypropylene monomer units>
Number of vinyl groups/1,000 polypropylene monomer units =
[((total integrals of vinyl signals in the 4.9-5.1 ppm region and the 5.7-5.9 ppm region)/number of hydrogen atoms in vinyl groups)×1,000]
/ [(integral value of the signal originating from the main chain in the 0.2 to 3.0 ppm region)/number of hydrogen atoms in the monomer unit of polypropylene=6)]

<Number of vinylidene groups per 1,000 polypropylene monomer units>
Number of vinylidene groups/1,000 polypropylene monomer units =
[((sum of integrals of vinylidene signals at 4.69 ppm and 4.74 ppm)/number of hydrogen atoms in vinylidene groups)×1,000]
/ [(integral value of the signal originating from the main chain in the 0.2 to 3.0 ppm region)/number of hydrogen atoms in the monomer unit of polypropylene=6)]

<Physical Properties>
<Transparency>
A flat plate having a thickness of 2 mm, a width of 50 mm and a length of 80 mm was formed by press molding at a molding temperature of 200 to 250° C. Using this plate, the haze was measured according to the measurement method described in JIS K7105 (1981).
The measured haze value was used to evaluate transparency.
The haze value is preferably 20% or less, more preferably 10% or less, and the lower the haze value, the better the transparency.

<Solubility>
Each of 100 mL test tubes was charged with 2.5 g and 5 g of polymer and 50 mL (43.1 g) of toluene and sealed with a rubber stopper.
The test tube was immersed in a water bath adjusted to 60° C. and stirred by hand for 10 seconds every 5 minutes to dissolve the polymer over 1 hour, thereby preparing a 5.8% toluene solution and an 11.6% toluene solution of the polymer.
The state of the solution was visually confirmed. Completely dissolved was marked with a circle, and those that did not dissolve but precipitated or gelled were marked with a cross. Dissolved solutions were considered to be good.

<Solution Stability>
The solution obtained above was left at room temperature (25° C.) for 24 hours, and the state of the solution was visually confirmed. Those that were dissolved were marked with ◯, and those that precipitated or gelled were marked with ×. Those that were dissolved were considered to be good.

<Adhesiveness>
For those with a solubility of ◯, a drop of the solution adjusted to 60° C. was dropped with a dropper onto a metal plate (aluminum plate: JIS H4000 A5052P, thickness 1 mm × width 70 mm × length 150 mm, stainless steel plate: JIS G4305 SUS304 BA, thickness 0.5 mm × width 70 mm × length 150 mm) whose surface had been wiped with acetone to degrease, and the solution was coated with a wire bar coater to a thickness of 50 μm.
The coated surface was blown with hot air using a dryer for 10 seconds to remove the solvent, and then left to stand for 15 hours at room temperature (25°C) to stabilize, after which 3M Scotch (registered trademark) mending tape No. 810 was attached to the coated surface and then peeled off, and the state of the coating film was observed to evaluate adhesion.
The specimens with no peeling of the coating film were rated as ◯, and the specimens with peeling of the coating film were rated as X. The specimens with no peeling of the coating film had good adhesion.

<Ingredients>
[Cyclic polyolefin (a)]
〇a-1:
Mitsubishi Chemical Corporation Zelas (registered trademark) MC930
・Density (ASTM D792): 0.94g/ ^cm3
MFR (230°C, 2.16 kg): 1 g/10 min. Hydrogenated aromatic vinyl polymer block unit: hydrogenated polystyrene with a content of 65 mol% and a hydrogenation level of 99.5% or more. Hydrogenated conjugated diene polymer block unit: hydrogenated polybutadiene with a content of 35 mol% and a hydrogenation level of 99.5% or more. Block structure: pentablock structure, total hydrogenation level: 99.5% or more. Mw: 75,000.
Total number of vinyl groups and vinylidene groups/1,000 monomer units=0
Number of vinyl groups/1,000 monomer units = 0
Number of vinylidene groups/1,000 monomer units = 0

Example 1
[Unsaturated Group-Containing Cyclic Polyolefin (A)]
・A-1:
A reaction vessel was charged with 100 parts of cyclic polyolefin a-1 under a nitrogen atmosphere, and while supplying nitrogen to the gas phase, the mixture was heated and melted with a mantle heater, and thermally degraded at 360°C for 70 minutes with stirring to obtain A-1. The analytical results of the obtained A-1 were as follows.
Hydrogenated aromatic vinyl polymer block unit hydrogenation level 99.5% or more Mw: 8700
Total number of vinyl groups and vinylidene groups/1,000 monomer units=34
Number of vinyl groups/1,000 monomer units = 0
Number of vinylidene groups/1,000 monomer units = 34

The transparency, solubility and solution stability were evaluated according to the above-mentioned evaluation items. In addition, the adhesiveness was evaluated using the solution used for the solubility evaluation.
The results are shown in Table 1.

<Comparative Example 1>
Except for using a-1 instead of A-1, various evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 2>
[Polypropylene having unsaturated groups (b)]
b-1:
Sanyo Chemical Industries, Ltd. Viscol (registered trademark) 660-P
The polypropylene b-1 does not have an alicyclic structure in its molecular structure and is not a cyclic polyolefin.
・Mw: 7000
Total number of vinyl groups and vinylidene groups/1,000 mono-units = 20
Number of vinyl groups/1,000 monomer units = 0
Number of vinylidene groups/1,000 monomer units = 20

Various evaluations were carried out in the same manner as in Example 1, except that b-1 was used instead of A-1. The results are shown in Table 1.

<Results>
From Table 1, it is clear that Example 1, which corresponds to the present invention, is excellent in transparency, solubility, solution stability and adhesiveness.
In contrast, Comparative Example 1 had poor solution stability due to its high molecular weight, and had poor adhesiveness due to the lack of an unsaturated group in its molecular structure.
Since Comparative Example 2 was not a cyclic polyolefin, it had poor transparency and solubility and could not be coated.

The unsaturated group-containing cyclic polyolefin of the present invention is excellent in solubility in organic solvents, adhesiveness, and transparency.
For this reason, it can be applied in various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electric and electronic parts, and can be particularly suitably used as insulating casting, laminating materials, sealing materials, etc. in the electric and electronic fields.

Claims (17)

A method for producing an unsaturated group-containing cyclic polyolefin having a vinyl group and/or a vinylidene group in the molecular structure of the cyclic polyolefin, comprising the steps of:
the cyclic polyolefin is a hydrogenated block copolymer having only a hydrogenated product of a polymer composed of aromatic vinyl monomer units, or a hydrogenated product of a polymer block composed of aromatic vinyl monomer units and a hydrogenated product of a polymer block composed of conjugated diene monomer units;
The cyclic polyolefin is thermally degraded in an inert gas at 300 to 400° C. for 0.5 to 10 hours. The method for producing the unsaturated group-containing cyclic polyolefin according to claim 1, wherein the weight average molecular weight is 1,000 to 40,000. The method for producing an unsaturated group-containing cyclic polyolefin according to claim 1 or 2, wherein the total number of vinyl groups and vinylidene groups per 1,000 monomer units is 1 to 200. The method for producing an unsaturated group-containing cyclic polyolefin according to any one of claims 1 to 3, wherein the number of vinylidene groups per 1,000 monomer units is 1 to 100. The method for producing an unsaturated group-containing cyclic polyolefin according to any one of claims 1 to 4, wherein the hydrogenated polymer of the aromatic vinyl monomer units has a hydrogenation level of 90% or more. The method for producing an unsaturated group-containing cyclic polyolefin according to any one of claims 1 to 4, wherein the hydrogenated polymer block composed of the aromatic vinyl monomer units has a hydrogenation level of 90% or more. An unsaturated group-containing cyclic polyolefin laminate, comprising a substrate and an unsaturated group-containing cyclic polyolefin having a vinyl group and/or a vinylidene group in the molecular structure of the cyclic polyolefin, the substrate being laminated thereon,
the cyclic polyolefin is a hydrogenated block copolymer having only a hydrogenated product of a polymer composed of aromatic vinyl monomer units, or a hydrogenated product of a polymer block composed of aromatic vinyl monomer units and a hydrogenated product of a polymer block composed of conjugated diene monomer units ;
A laminate containing an unsaturated group-containing cyclic polyolefin having a weight average molecular weight of 1,000 to 40,000 . 8. The unsaturated group-containing cyclic polyolefin-containing laminate according to claim 7 , wherein the total number of vinyl groups and vinylidene groups per 1,000 monomer units is 1 to 200. 9. The unsaturated group-containing cyclic polyolefin-containing laminate according to claim 7 or 8 , wherein the number of vinylidene groups per 1,000 monomer units is 1 to 100. 10. The unsaturated group-containing cyclic polyolefin-containing laminate according to any one of claims 7 to 9 , wherein the hydrogenated polymer of the aromatic vinyl monomer unit has a hydrogenation level of 90% or more. 10. The unsaturated group-containing cyclic polyolefin-containing laminate according to any one of claims 7 to 9 , wherein the hydrogenated polymer block composed of aromatic vinyl monomer units has a hydrogenation level of 90% or more. A method for producing an unsaturated group-containing cyclic polyolefin-containing laminate, comprising applying an organic solvent-unsaturated group-containing cyclic polyolefin mixture to a substrate, and then removing the solvent to obtain a laminate, comprising the steps of:
The organic solvent-unsaturated group-containing cyclic polyolefin mixture is a mixture consisting of an unsaturated group-containing cyclic polyolefin solution or an unsaturated group-containing cyclic polyolefin slurry, in which an unsaturated group-containing cyclic polyolefin is dissolved or suspended in an organic solvent at a concentration of 1 to 30 mass %,
The unsaturated group-containing cyclic polyolefin has a vinyl group and/or a vinylidene group in the molecular structure of the cyclic polyolefin,
A method for producing a laminate containing an unsaturated group-containing cyclic polyolefin, wherein the cyclic polyolefin is a hydrogenated block copolymer containing only a hydrogenated product of a polymer consisting of aromatic vinyl monomer units, or a hydrogenated product of a polymer block consisting of aromatic vinyl monomer units and a hydrogenated product of a polymer block consisting of conjugated diene monomer units. The method for producing an unsaturated group-containing cyclic polyolefin-containing laminate according to claim 12 , wherein the weight average molecular weight is 1,000 to 40,000. The method for producing an unsaturated group-containing cyclic polyolefin-containing laminate according to claim 12 or 13 , wherein the total number of vinyl groups and vinylidene groups per 1,000 monomer units is 1 to 200. The method for producing an unsaturated group-containing cyclic polyolefin-containing laminate according to any one of claims 12 to 14 , wherein the number of vinylidene groups per 1,000 monomer units is 1 to 100. The method for producing an unsaturated group-containing cyclic polyolefin-containing laminate according to any one of claims 12 to 15 , wherein the hydrogenated polymer of the aromatic vinyl monomer unit has a hydrogenation level of 90% or more. The method for producing an unsaturated group-containing cyclic polyolefin-containing laminate according to any one of claims 12 to 15 , wherein the hydrogenated product of the polymer block composed of aromatic vinyl monomer units has a hydrogenation level of 90% or more.