Composition

Abstract

To achieve both excellent dielectric characteristics and long-term durability.SOLUTION: A composition contains (A) a curable hydrocarbon resin, (B) a phenolic antioxidant, (C) a thioether-based antioxidant, and (D) a phosphorus-based antioxidant. The total amount of substance of the components (B), (C) and (D) is in the range of 2-10 mmol based on 100 g of the mass of the component (A) in the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition. [Background technology]

[0002] As communication frequencies move into the gigahertz band and higher, there is a growing need for insulating materials with low dielectric properties. This is because transmission loss is known to be approximately equal to the sum of dielectric loss, which is proportional to the dielectric loss tangent, and conductor loss. Because it is difficult to reduce the dielectric constant and dielectric loss using existing materials such as epoxy resins, new materials are being developed. For example, Patent Document 1 discloses an electrical insulating material made of a graft or block copolymer consisting of olefin-based and styrene-based polymer segments.

[0003] Electrical insulating materials, also known as LDMs (Low Dielectric Macromonomers), are often used in electronic devices and are subject to continuous exposure to extremely high temperatures. They are also required to last for long periods without being easily replaceable. Despite this, there is a trend toward even lower dielectric constants and dielectric loss. While various additives are commercially available in the polymer material field that claim to prevent material aging, their application to LDM products is not straightforward due to their adverse effects on dielectric constant and dielectric loss.

[0004] For example, Patent Document 2 discloses a solar cell module that uses a so-called cross-copolymer as an encapsulant, and lists various additives as examples. However, at the time, the dielectric constant and dielectric loss levels required for current LDM products were not taken into consideration. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-060645 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-127544 Summary of the Invention [Problem to be solved by the invention]

[0006] A new challenge is to achieve the dielectric constant and dielectric loss levels required for current LDM products while also achieving long-term durability (especially durability under high temperature exposure), which was not possible with conventional technology. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention can provide the following aspects.

[0008] Aspect 1. (A) a curable hydrocarbon-based resin; (B) a phenolic antioxidant; (C) a thioether antioxidant; (D) Phosphorus-based antioxidants A composition comprising: A composition in which the total amount of substances of components (B), (C), and (D) is in the range of 2 to 10 mmol, based on 100 g of the mass of component (A) in the composition.

[0009] Aspect 2. The composition of Aspect 1, wherein, based on 100 g of the mass of component (A) in the composition, the amount of substance per phenol moiety of component (B) is in the range of 0.5 to 4 mmol, the amount of substance per thioether moiety of component (C) is in the range of 0.5 to 4 mmol, and the amount of substance per phosphite moiety of component (D) is in the range of 0.5 to 4 mmol.

[0010] Aspect 3. 3. The composition of any one of the preceding aspects, wherein the (A) component comprises an olefin-aromatic vinyl compound-aromatic polyene copolymer.

[0011] Aspect 4. A composition according to aspect 3, wherein the component (A) satisfies all of the following conditions (1) to (4): (1) The number average molecular weight of the copolymer is 500 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0 to 70% by mass. (3) The aromatic polyene monomer unit is one or more polyenes selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from the aromatic polyene monomer unit is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin monomer unit is one or more olefins selected from olefins having 2 to 20 carbon atoms, and the total of the olefin monomer unit, the aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100 mass%.

[0012] Aspect 5. The dielectric loss tangent value of the cured product of the composition in a measurement frequency range of 40 GHz, which is determined by a resonator method, is defined as X1; When the cured product of the composition is heated at 175°C for 24 hours and then the dielectric loss tangent value in the measurement frequency range of 40 GHz determined by the resonator method is X2, Aspect 5. The composition of any one of aspects 1 to 4, wherein the value of (X1 / X2) is 2 or less.

[0013] Aspect 6. A composition according to any one of Aspects 1 to 5, wherein component (B) has two or more aromatic rings in one molecule.

[0014] Aspect 7. Aspect 7. The composition of any one of aspects 1 to 6, wherein component (C) has an acyclic structure.

[0015] Aspect 8. Aspect 8. The composition according to any one of aspects 1 to 7, wherein component (D) has an aromatic ring in the molecule.

[0016] Aspect 9. A cured product of the composition according to any one of aspects 1 to 8.

[0017] Aspect 10. A laminate comprising a layer containing the composition according to any one of aspects 1 to 8 and a metal foil.

[0018] Aspect 11. A cured product of the laminate according to embodiment 10.

[0019] Aspect 12. A single-layer CCL, multi-layer CCL, single-layer FCCL, or multi-layer FCCL substrate comprising the cured body according to embodiment 11. [Effects of the Invention]

[0020] The composition according to the present invention has the effect of exhibiting excellent dielectric properties and long-term durability even in harsh environments. DETAILED DESCRIPTION OF THE INVENTION

[0021] In this specification, the term "sheet" also encompasses the concept of a film. Furthermore, the term "film" as used herein also encompasses the concept of a sheet. In this specification, the term "composition" encompasses the concept of a varnish. That is, a liquid composition is referred to as a varnish. The order of the steps included in the method disclosed herein may be freely changed in chronological order as long as the effect can be achieved. Numerical ranges in this specification include the lower and upper limits unless otherwise specified.

[0022] The composition according to the present invention is characterized by containing (A) a curable hydrocarbon-based resin (hereinafter, may be simply referred to as "resin") and, relative to the curable hydrocarbon-based resin, predetermined amounts of (B) a phenol-based antioxidant and (C) a thioether-based antioxidant.

[0023] Component (A) may be any curable hydrocarbon resin having functional groups that can be thermally cured or cured in the presence of a radical polymerization initiator. The presence of component (A) allows the cured product of this composition to meet the heat resistance required for an electrical insulating material. The functional groups are not limited as long as they are thermally or radically curable, but are preferably at least one of the group consisting of vinyl, vinylene, and allyl groups. For example, component (A) may be a polyfunctional vinyl aromatic copolymer obtained by cationic polymerization, as described in International Publication Nos. 2018 / 181842 and 2017 / 115813; a polyphenylene ether resin having functional groups, such as SA-9000 from SABIC or OPE-2St from Mitsubishi Gas Chemical Company; a polyether (ketone) having functional groups; or a polymer or copolymer having a 1,2-polybutadiene structure, such as Cray Valley's "Ricon" brand. Further examples include olefin-aromatic vinyl compound-aromatic polyene copolymers obtained by single-site coordination polymerization. The component (A) may be a single component or a composition consisting of a plurality of components. Most preferably, the component (A) may comprise a polyfunctional vinyl aromatic copolymer or an olefin-aromatic vinyl compound-aromatic polyene copolymer, the constituent components of which are essentially carbon atoms and hydrogen atoms.

[0024] Component (A) most preferably contains an olefin-aromatic vinyl compound-aromatic polyene copolymer (hereinafter sometimes simply referred to as "copolymer"). The olefin-aromatic vinyl compound-aromatic polyene copolymer is a compound obtained by copolymerizing the monomers of an olefin, an aromatic vinyl compound, and an aromatic polyene. Component (A) may be a monomer, an oligomer, or a mixture thereof. Component (A) preferably satisfies all of the following conditions (1) to (4): (1) The number average molecular weight of the copolymer is 500 or more and 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 to 20 carbon atoms, and the content of aromatic vinyl compound monomer units is 0 to 70% by mass. (3) The aromatic polyene monomer unit is one or more polyenes selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from the aromatic polyene monomer unit is 1.5 or more and less than 20 per number average molecular weight. (4) The olefin monomer unit is one or more olefins selected from olefins having 2 to 20 carbon atoms, and the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is 100% by mass.

[0025] The olefin monomer may be one or more selected from α-olefins having 2 to 20 carbon atoms and cyclic olefins having 5 to 20 carbon atoms, and is a compound composed of carbon and hydrogen, substantially free of oxygen, nitrogen, and halogens. Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene. Examples of cyclic olefins having 5 to 20 carbon atoms include norbornene and cyclopentene. The olefin preferably used is a combination of ethylene with an α-olefin other than ethylene or a cyclic olefin, or ethylene alone. The amount of α-olefin other than ethylene added can be selected according to the desired molecular weight.

[0026] From the viewpoint of improving the peel strength from copper foil or copper wiring, the olefin monomer is ethylene alone, or the mass ratio of α-olefin components other than ethylene contained to the ethylene component can be preferably 1 / 7 or less, more preferably 1 / 10 or less. In this case, the content of α-olefin monomer components other than ethylene contained in the copolymer is more preferably 6% by mass or less, even more preferably 4% by mass or less, or the olefin is ethylene alone.

[0027] When the total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units is taken as 100% by mass, the content of the olefin monomer units in this copolymer may be preferably 20% by mass or more, more preferably 25% by mass or more, and most preferably 30% by mass or more. When the content of the olefin monomer units is 20% by mass or more, the toughness (elongation) and impact resistance of the final cured product are improved, and cracks during curing or during heat cycle testing of the cured product are less likely to occur. In this copolymer, the content of the olefin monomer units is preferably 90% by mass or less.

[0028] The aromatic vinyl compound monomer may be an aromatic vinyl compound having 8 to 20 carbon atoms, such as styrene, paramethylstyrene, paraisobutylstyrene, various vinylnaphthalenes, and various vinylanthracenes.

[0029] The content of aromatic vinyl compound monomer units in the copolymer may be 0% by mass or more and 70% by mass or less, preferably 10% by mass or more and 60% by mass or less. A content of aromatic vinyl compound monomer units of 70% by mass or less is preferable because the glass transition temperature of the cured product of the final resin composition is lower than near room temperature, improving toughness and elongation at low temperatures. A content of aromatic vinyl compound monomer units of 10% by mass or more improves the aromaticity of the copolymer, improving compatibility with flame retardants and fillers, preventing bleed-out of flame retardants, and improving filler loading. Furthermore, a content of aromatic vinyl compound monomer units of 10% by mass or more can also produce a cured product with high peel strength from copper foil or copper wiring.

[0030] The aromatic polyene monomer may be a polyene having 5 to 20 carbon atoms and containing multiple vinyl and / or vinylene groups in its molecule. Preferably, the aromatic polyene monomer is a compound having an aromatic vinyl structure, such as ortho-, meta-, or para-divinylbenzene or a mixture thereof, divinylnaphthalene, divinylanthracene, p-2-propenylstyrene, or p-3-butenylstyrene, and consisting essentially of carbon and hydrogen and substantially free of oxygen, nitrogen, or halogens. Also usable are bifunctional aromatic vinyl compounds, such as 1,2-bis(vinylphenyl)ethane (abbreviated as BVPE), as described in JP 2004-087639 A. Among these, ortho-, meta-, or para-divinylbenzene or a mixture thereof is preferred, with a mixture of meta- and para-divinylbenzene being most preferred. In this specification, these divinylbenzenes are sometimes collectively referred to as divinylbenzenes. Divinylbenzenes are preferred as aromatic polyenes because they provide high curing efficiency and are easy to cure during curing treatment.

[0031] The above-mentioned olefin, aromatic vinyl compound, and aromatic polyene monomers may also contain polar groups, such as olefins containing oxygen atoms, nitrogen atoms, etc., aromatic vinyl compounds containing oxygen atoms, nitrogen atoms, etc., or aromatic polyenes containing oxygen atoms, nitrogen atoms, etc. The total mass of these polar group-containing monomers is preferably 10 mass% or less of the total mass of the composition, more preferably 3 mass% or less, and most preferably no polar group-containing monomers are included. By keeping the total mass ratio of polar group-containing monomers at 10 mass% or less, the dielectric properties (low dielectric constant, low dielectric loss) of the cured body obtained by curing the composition can be improved.

[0032] Among the present copolymers, examples of embodiments that do not contain aromatic vinyl compound monomer units (olefin-aromatic polyene copolymers) include ethylene-divinylbenzene copolymer, ethylene-propylene-divinylbenzene copolymer, ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, and ethylene-1-octene-divinylbenzene copolymer.

[0033] Among the present copolymers, examples of embodiments containing aromatic vinyl compound monomer units (olefin-aromatic vinyl compound-aromatic polyene copolymers) include ethylene-styrene-divinylbenzene copolymer, ethylene-propylene-styrene-divinylbenzene copolymer, ethylene-1-hexene-styrene-divinylbenzene copolymer, ethylene-1-octene-styrene-divinylbenzene copolymer, etc.

[0034] The number average molecular weight (Mn) of the copolymer may be from 500 to 100,000, preferably from 500 to 50,000, further preferably from 500 to 20,000, and even more preferably from 500 to 10,000. When Mn is 100,000 or less, it becomes possible to obtain a viscosity appropriate for a varnish, and the effect of improving the handleability when using the composition is obtained.

[0035] The weight-average molecular weight (Mw) of the present copolymer may be preferably from 10,000 to 200,000, more preferably from 20,000 to 200,000, and even more preferably from 20,000 to 150,000. The value Mw / Mn obtained by dividing the weight-average molecular weight by the number-average molecular weight may preferably be in the range of 2.0≦Mw / Mn≦13.0, more preferably 2.0≦Mw / Mn≦12.0, and even more preferably 2.0≦Mw / Mn≦10.0.

[0036] The number average molecular weight and weight average molecular weight in this specification refer to values ​​measured as molecular weights converted into standard polystyrene by gel permeation chromatography (GPC). The measurement conditions for GPC in this specification are as follows: Measurement equipment: Viscotek GPCMax Column: TSK-GEL MultiporeHXL-M, φ7.8 x 300mm, 3 columns Column temperature: 40℃ Detector: RI Solvent: THF Flow rate: 1.0 ml / min Sample concentration: 0.2 wt / vol% Sample injection volume: 200 μL

[0037] In the copolymer, the content of vinyl groups and / or vinylene groups (preferably vinyl groups) derived from aromatic polyene units may be 1.5 or more and less than 20, preferably 2 or more and less than 7, per number average molecular weight. When the content of vinyl groups and / or vinylene groups is 1.5 or more, crosslinking efficiency is high, and a cured product with sufficient crosslink density can be obtained. The content of vinyl groups derived from aromatic polyene units (divinylbenzene units) per number average molecular weight in the copolymer can be calculated by the number average molecular weight (Mn) calculated in terms of standard polystyrene determined by GPC (gel permeation chromatography) known to those skilled in the art, and 1 This can be obtained by comparing the vinyl group content derived from aromatic polyene units obtained by H-NMR measurement. For example, 1 By comparing the intensity of each peak area obtained by H-NMR measurement, if the content of vinyl groups derived from aromatic polyene units (divinylbenzene units) in the copolymer is 0.6% by mass, and the number average molecular weight converted to standard polystyrene by GPC measurement is 49,000, the molecular weight of vinyl groups derived from aromatic polyene units in the number average molecular weight is the product of these, 299, which is divided by the formula weight of the vinyl groups, 130, to obtain 2.3. In other words, the content of vinyl groups derived from aromatic polyene units per number average molecular weight in this copolymer is calculated to be 2.3. 1 The assignment of peaks obtained by H-NMR measurement is known from literature. 1 A method for determining the copolymer composition from a comparison of peak areas obtained by H-NMR measurement is also known. 1 The H-NMR measurement method was performed in a known quantitative mode. 13 It is also possible to improve the accuracy of the composition by adding data on the peak areas and ratios of the C-NMR spectrum. In this specification, the content of divinylbenzene units in the copolymer is determined based on the peak intensity ( 1This is determined from the content of vinyl groups derived from divinylbenzene units (measured by H-NMR). In other words, the content of divinylbenzene units is determined from the content of vinyl groups derived from divinylbenzene units, assuming that one vinyl group is derived from one divinylbenzene unit in the copolymer.

[0038] The phenolic antioxidant (component (B)) contained in this composition is a component that exerts a synergistic effect by providing the composition with excellent durability when used in a specified amount in combination with components (C) and (D) described below. A feature of the present invention is that simply combining different types of antioxidants without considering the amounts will not produce a significant effect in a composition containing a specific component (A) as the main component.

[0039] In a preferred embodiment, when the dielectric loss tangent of a cured product of the composition at a measurement frequency range of 40 GHz as determined by the resonator method is X1 and the dielectric loss tangent of a cured product of the composition at a measurement frequency range of 40 GHz as determined by the resonator method after heating at 175°C for 24 hours is X2, the value of (X1 / X2) may be 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. In other words, the composition can exhibit the effect of being less likely to lose its dielectric loss tangent even when heated (or when left standing for a long period of time equivalent to being heated).

[0040] More preferably, the synergistic effect of components (B), (C), and (D) can also be achieved such that the storage modulus does not deteriorate compared to before the addition of the antioxidant.

[0041] The amount of component (B), based on 100 g of the mass of component (A), is in the range of 0.5 to 4 mmol in terms of the amount of substance (molar equivalent) per phenolic moiety of component (B), more preferably in the range of 0.5 to 3 mmol, and even more preferably in the range of 0.5 to 2.5 mmol.

[0042] Component (B) refers to a compound having a phenol skeleton (moiety) and capable of terminating radical chain reactions. Component (B) may contain a monophenol-based antioxidant, a polyphenol-based antioxidant (such as a bisphenol-based antioxidant or a triphenol-based antioxidant), or a mixture thereof. Component (B) preferably contains a hindered phenol-based antioxidant (a compound having a bulky, sterically hindering substituent, such as a tert-butyl group, on the aromatic ring of the phenol moiety). From the viewpoint of improving heat durability, component (B) may have two or more aromatic rings per molecule.

[0043] Examples of monophenolic antioxidants include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearin-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl=(meth)acrylate, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl=(meth)acrylate, and 6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol. These are available, for example, under the trade names Sumilizer GS, Sumilizer GM, and Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.).

[0044] Examples of polyphenol antioxidants include 2,2-methylene-bis(4-methyl-6-tert-butylphenol), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzenepropionamide), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), and 6,6'-di-tert-butyl-4,4'-butylidene. Examples include di-m-cresol, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate], 2,2'-methylenebis(6-tert-butyl-p-cresol), and 4,4'-thiobis(6-tert-butyl-m-cresol). These are available, for example, under the trade names Sumilizer GA-80, Sumilizer MDP-S, and Sumilizer WX-R (manufactured by Sumitomo Chemical Co., Ltd.) As component (B), these may be used alone or in combination of two or more.

[0045] The thioether antioxidant (component (C)) contained in this composition refers to a compound that has a thioether skeleton (moiety) and has the effect of terminating radical chain reactions. The amount of component (C) is, based on 100 g of component (A), 0.5 to 4 mmol (molar equivalent) of the substance per thioether moiety of component (C), more preferably 0.5 to 3 mmol, and even more preferably 0.5 to 2.5 mmol.

[0046] Furthermore, based on 100 g of the mass of component (A) in the present composition, the total amount of component (B) and component (C) may be in the range of 1 to 10 mmol or 2 to 10 mmol, more preferably 2 to 8 mmol, and even more preferably 2 to 7 mmol.

[0047] Examples of component (C) include dialkylthiodipropionates (di(tridecyl) 3,3'-thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, etc.), pentaerythritol tetra(β-alkylthiopropionic acid) esters, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], etc. These may be used as component (C) alone or in combination of two or more.

[0048] From the viewpoint of enhancing the synergistic effect with component (B), component (C) preferably has an acyclic structure.

[0049] In a preferred embodiment, the composition may further contain (D) a phosphorus-based antioxidant. The amount of component (D) is preferably 0.5 to 4 mmol, more preferably 0.5 to 3 mmol, and even more preferably 0.5 to 2.5 mmol, per 100 g of component (A) in the composition. Furthermore, the total amount of components (B), (C), and (D) is preferably 2 to 10 mmol, more preferably 2 to 8 mmol, and even more preferably 2 to 7 mmol, per 100 g of component (A) in the composition.

[0050] By blending three types of antioxidants in the specified amounts, a synergistic effect is further exerted, resulting in extremely excellent dielectric properties. In particular, even a slight difference in the dielectric tangent (on the order of 0.0001) has a large effect, so even a slight decrease can have a significant effect.

[0051] Examples of the component (D) include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-Ethylhexyl phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite Examples include erythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tetratridecyl-4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)diphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, and bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite.

[0052] From the viewpoint of enhancing the synergistic effect of the three antioxidants, it is preferable that component (D) has an aromatic ring in the molecule.

[0053] The present composition may further contain optional additional components such as those exemplified below, as long as the effects of the composition are not impaired.

[0054] <Curing agent> As a curing agent that can be used in the present composition, a known curing agent that can be used for the polymerization or curing of conventional aromatic polyenes or aromatic vinyl compounds may be used. Examples of such curing agents include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators, but preferably radical polymerization initiators can be used. Preferred are organic peroxides, azo-based polymerization initiators, etc., and can be freely selected depending on the application and conditions. A catalog listing organic peroxides can be found on the NOF Corporation website, for example https: / / www.nof.co.jp / business / chemical / chemical-product01 It can be downloaded from. Organic peroxides are also listed in catalogs from Fujifilm Wako Pure Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd. Curing agents are available from these companies. Also, known photopolymerization initiators that use light, ultraviolet light, or radiation can be used as curing agents. Examples of curing agents that use photopolymerization initiators include photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators. Such photopolymerization initiators are available, for example, from Tokyo Chemical Industry Co., Ltd. Furthermore, curing by radiation or electron beams themselves is also possible. It is also possible to perform crosslinking and curing by thermal polymerization of the raw materials contained in the composition without using a curing agent.

[0055] There are no particular restrictions on the amount of curing agent used, but generally, 0.01 to 10 parts by mass per 100 parts by mass of the composition is preferred. The composition preferably excludes the curing agent and solvent. When using a curing agent such as a peroxide or azo-based polymerization initiator, the curing process should be carried out at an appropriate temperature and time, taking into account its half-life. The conditions for this can be determined arbitrarily depending on the curing agent, but a temperature range of approximately 50°C to 200°C is generally appropriate.

[0056] <Solvent> An appropriate solvent may be added to the composition as needed. The solvent is used to adjust the viscosity and fluidity of the composition. Volatile solvents are preferred, such as cyclohexane, toluene, ethylbenzene, acetone, and isopropanol. The amount of solvent used is preferably 10 parts by mass or less per 100 parts by mass of copolymer, from the viewpoint of moldability and handling of the composition as a thermoplastic resin before curing. Furthermore, from the viewpoint of removal during and after curing, it is more preferable that substantially no solvent is used. "Substantially no solvent" preferably means 5 parts by mass or less, more preferably 1 part by mass or less, and most preferably 0 parts by mass. When used as a varnish, it is preferable to add an appropriate solvent to the composition. The solvent is used to adjust the viscosity and fluidity of the composition as a varnish. A solvent with a high boiling point at atmospheric pressure, i.e., low volatility, results in a uniform thickness of the applied film; therefore, a solvent with a boiling point above a certain level is preferred. A preferred boiling point is generally 100°C or higher at atmospheric pressure, preferably 130°C to 300°C. Suitable solvents for such varnishes include toluene, xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. The amount of the solvent used is preferably in the range of 10 to 2000 parts by mass per 100 parts by mass of the composition.

[0057] Depending on the composition and blending ratio, the present composition can also be made into a viscous liquid varnish. For example, a sufficient amount of solvent and / or an appropriate amount of liquid monomer can be used to produce a varnish. When used as a varnish, it is preferable to add an appropriate solvent to the present composition. The solvent is used to adjust the viscosity and flowability of the composition as a varnish. A solvent with a high boiling point at atmospheric pressure, i.e., low volatility, is advantageous in that it results in a uniform thickness of the applied film. Therefore, a solvent with a boiling point above a certain level is preferred. A preferred boiling point at atmospheric pressure is generally 100°C or higher, preferably 110°C to 300°C. Examples of solvents suitable for such varnishes include xylene, mesitylene, ethylbenzene, limonene, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether. The amount used is preferably in the range of 10 to 2000 parts by mass per 100 parts by mass of the present composition. A varnish-like composition can also be produced using a polymerization liquid containing the present copolymer obtained by polymerization. For example, the polymerization solution may be concentrated or residual monomers may be removed, and if necessary, solvents, other resin components, various additives, etc. may be added to adjust the component concentrations and solution viscosity, etc., to produce the polymer.

[0058] The varnish can be applied to or impregnated into a substrate, and the solvent can be removed by drying or the like to form an uncured or semi-cured molded article. Generally, this molded article is in the form of a sheet, film, or tape.

[0059] <Curing> The composition can be cured by a known method, taking into consideration the curing conditions (temperature, time, pressure) of the curing agent contained therein. When the curing agent used is a peroxide, the curing conditions can be determined by taking into consideration the half-life temperature and the like disclosed for each peroxide.

[0060] The present invention can also provide a laminate comprising a layer containing the above-described composition and a metal foil. Specifically, the composition can be used as various insulating materials for wiring, preferably for high-frequency signal wiring, such as coverlays, solder resists, build-up materials, interlayer insulating agents, bonding sheets, interlayer adhesives, and bump sheets for flip-chip bonders. Furthermore, the composition can be used as an electrical insulating layer or adhesive layer for substrates such as single-layer or multilayer printed circuit boards, flexible printed circuit boards, CCL (copper clad laminate), and FCCL (flexible copper clad laminate) substrates.

[0061] <Viscosity> In this specification, the viscosity of the composition is determined in accordance with JIS Z 8803:2011 when prepared as a 50% by mass toluene solution. The viscosity of the composition at 25°C is measured at a shear rate of 1 s -1 The viscosity may be 100,000 cP or less, preferably 10,000 cP or less or 9,000 cP or less, further preferably 8,000 cP or less, and even more preferably 5,000 cP or less. The lower limit of the viscosity is not particularly limited, but may be, for example, 500 cP or more, preferably 1,000 cP or more. When the viscosity is in this range, the effect of improving the handleability of the varnish can be obtained.

[0062] <Manufacturing method> The composition containing the copolymer described above can be obtained by subjecting a raw material solution prepared by mixing the olefin monomer, aromatic vinyl compound monomer, and aromatic polyene monomer in an appropriate solvent to a single-site coordination polymerization reaction. In another embodiment, a step of polymerizing in liquid monomer without using a solvent may be employed instead. In another embodiment, the vinyl aromatic copolymer may be obtained by a cationic polymerization reaction.

[0063] Usable solvents include saturated aliphatic or aromatic hydrocarbons or halogenated hydrocarbons, either alone or in mixtures, such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, ethylbenzene, xylene, mesitylene, limonene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform, etc. Preferably, mixed alkane solvents, cyclohexane, toluene, ethylbenzene, etc. can be used as the solvent.

[0064] Although the copolymer can be produced without using a chain transfer agent, a chain transfer agent may be used to reduce the molecular weight. Examples of such a chain transfer agent include known chain transfer agents used with so-called single-site coordination polymerization catalysts, such as hydrogen, alkyl aluminums such as triisobutylaluminum, and 9-BBN, as described in Chung TC: Macromolecules, 26, 3467 (1993).

[0065] The equipment capable of producing the present composition may be, for example, a single tank polymerization vessel or a plurality of connected tanks, or a linear or loop pipe polymerization vessel or a plurality of connected tanks. The pipe polymerization vessel may be equipped with various known mixers such as a dynamic or static mixer or a static mixer that also serves as a heat remover, or various known coolers such as a cooler equipped with a thin tube for heat removal. It may also be equipped with a batch-type prepolymerization vessel. Furthermore, a gas-phase polymerization process may be employed.

[0066] The polymerization temperature is preferably 0 to 200°C. A temperature of 0°C or higher is industrially advantageous because the polymerization rate is fast, while a temperature of 200°C or lower has the effect of making the transition metal compound less susceptible to decomposition. Industrially, a temperature of 30 to 160°C is more preferable, and 50 to 160°C is particularly preferable. The pressure during polymerization is generally preferably 1 to 100 atmospheres, more preferably 1 to 30 atmospheres, and industrially, most preferably 1 to 10 atmospheres.

[0067] Any process can be used to recover the copolymer from the reaction system after the polymerization is complete, and preferably, the steam stripping method or crumb foaming method, which are known as methods for recovering raw rubber, can be used. In laboratories, a method in which the copolymer is precipitated in a large amount of methanol, known as the methanol precipitation method, is generally convenient. Alternatively, without recovering the copolymer, the solvent and residual monomers can be removed in whole or in part from the polymerization solution by evaporation using a rotary evaporator, film evaporator, or the like, and the resulting solution can be diluted with a solvent and used as a varnish. [Example]

[0068] The copolymers shown in Table 1 were obtained by appropriately changing the monomer amounts, ratios, polymerization pressure, and polymerization temperature with reference to the production methods described in WO 00 / 37517, JP 2009-161743 A, and JP 2010-280771 A. The total of the olefin monomer units, aromatic vinyl compound monomer units, and aromatic polyene monomer units was set to 100% by mass. Table 1 also shows the number average molecular weights of the copolymers. The molecular weights were measured as described above.

[0069] <Vinyl group unit content> The content of vinyl group units derived from ethylene, styrene, and divinylbenzene in the copolymer is determined by: 1 The H-NMR was performed based on the peak area intensity assigned to each compound. The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane, and the measurement was carried out at 23°C.

[0070] Each example and comparative example was prepared using copolymers P-1 to P-3 according to the composition shown in Table 2. The amount of antioxidant is shown as the amount of substance (mmol equivalent) per functional group site when 100 parts by mass of the copolymer is taken as 100 g.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Table 3]

[0074] The main raw materials were as follows: Divinylbenzene (meta-para mixed product, divinylbenzene purity 81%) manufactured by Nippon Steel Chemical & Material Co., Ltd. The curing agent used was Perhexyne 25B (2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3) manufactured by NOF Corporation. Toluene (commercially available) was used as the solvent.

[0075] The components (B) used are as follows: 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (ADEKA Corporation "ADEKA STAB AO-80", molecular weight 741)

[0076] The component (C) used is as follows: 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate] (ADEKA Corporation "ADEKA STAB AO-412S", molecular weight 1162) Di(tridecyl) 3,3'-thiodipropionate (ADEKA Corporation "ADEKA STAB AO-503", molecular weight 543)

[0077] The component (D) used is as follows: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADEKA "ADEKA STAB PEP-36", molecular weight 633)

[0078] <Preparation of varnish and cured sheet> Using a vessel equipped with a heating and cooling jacket and a stirring blade, P-1 (ethylene-styrene-divinylbenzene copolymer) obtained in Synthesis Example and a solvent (toluene) were heated to approximately 60°C and stirred to dissolve the copolymer. Furthermore, the antioxidant and curing agent were added in the amounts shown in Tables 2 and 3, in proportions by weight per 100 parts by weight of the resin component, dissolved, and mixed by stirring to obtain a varnish-like composition. The amount of antioxidant shown in the tables is based on 100 g of copolymer. The resulting composition was poured into a silicone mold (frame length 7 cm, width 7 cm, thickness 0.5 mm, 1.0 mm, or 2.0 mm) on a Teflon® sheet placed on a glass plate, air-dried, and then further dried in a vacuum dryer at 60°C for at least 3 hours to obtain an uncured sheet. Furthermore, a Teflon sheet and a SUS mold were placed under a load of 5 MPa in a press, and the sheet was heat treated at 120°C for 30 minutes, 150°C for 30 minutes, and then 200°C for 120 minutes. The Teflon sheet and the SUS mold were then removed to obtain a hardened sheet.

[0079] <Measurement of dielectric loss (dielectric dissipation factor)> The dielectric loss tangent was measured at 23°C and 40 GHz using a cavity resonator perturbation method (Agilent Technologies 8722ES Network Analyzer, Keysight Technologies 40 GHz Split Cylinder Resonator) on a 0.2 mm x 25 mm x 30 mm sample cut from the sheet. To confirm the material's resistance to high-temperature thermal oxidation degradation, the sheet was left at 175°C in an air atmosphere for 24 hours, after which the dielectric loss tangent was measured. The ratio of the dielectric loss tangent before heating (X1) to the dielectric loss tangent after heating (X2) (see "Rate of change in dielectric loss tangent before and after heating" in the table) of X1 / X2 (the ratio of the dielectric loss tangent before and after heating) was considered to be 1.2 or less, indicating no degradation; between 1.2 and 2.0, degradation was within the acceptable range; and over 2.0, degradation was considered to have occurred.

[0080] <Measurement of storage modulus> Measurements were taken using a dynamic viscoelasticity measuring device (RSA-G2, Rheometrics) at a frequency of 1 Hz and a temperature range of 20°C to +300°C. Measurement samples (3mm x 40mm) were cut out from a film approximately 0.2mm thick and measured to determine the storage modulus. The main measurement parameters involved in the measurement are as follows: Measurement frequency 1Hz Heating rate: 3°C / min Sample measurement length: 13 mm Test Type = Dynamic Temperature Ramp (DTempRamp) Initial Static Force 5.0g Auto Tension Sensitivity 1.0g Max Auto Tension Rate 0.033mm / s Max Applied Strain 1.5% Min Allowed Force 1.0g Distortion 0.1%

[0081] The storage modulus at 25°C was evaluated according to the following criteria to determine whether the addition of an antioxidant caused a deterioration in the storage modulus ("Deterioration in DMA storage modulus at 25°C" in the table). If the storage modulus of a sample without added antioxidant (before heating) was set to 1, a deterioration was noted if the storage modulus of a sample with added antioxidant was 0.8 or higher, and a deterioration was noted if it was less than 0.8.

[0082] <Appearance evaluation> To confirm the high-temperature thermal oxidative degradation resistance of the material, the sheet was left at 175°C in an air atmosphere for 24 hours, and then the change in color of the sheet was visually evaluated ("Discoloration after heating" in the table).

[0083] The above evaluation results are also shown in Tables 2 and 3. In all of the Examples, the storage modulus did not deteriorate, there was no discoloration after heating, and the dielectric loss tangent after heating did not deteriorate either.

[0084] On the other hand, in Comparative Example 1, in which no antioxidant was added, not only did the product discolor upon heating but it was also severely damaged and was therefore unsuitable for practical use.

[0085] Comparative Example 2, in which no antioxidant was added, discolored upon heating and the dielectric loss tangent was significantly deteriorated.

[0086] In Comparative Examples 3 to 5, in which only component (B) was used as the antioxidant, discoloration occurred when heated.

[0087] In Comparative Example 6, in which only component (D) was used as the antioxidant, the dielectric tangent was significantly deteriorated by heating.

[0088] In Comparative Example 7, in which only component (C) was used as the antioxidant, the dielectric loss tangent was significantly deteriorated by heating.

[0089] In Comparative Example 8, in which antioxidants (B) and (C) were used but the total amount of the substances was small, the dielectric tangent was significantly deteriorated by heating.

[0090] In Comparative Example 9, in which antioxidants (B), (C), and (D) were used but the total amount of the substances was small, the dielectric loss tangent was significantly deteriorated by heating.

[0091] In Comparative Example 10, in which antioxidants (B) and (C) were used but the total amount of the substances was too large, the dielectric loss tangent was too high both before and after heating.

Claims

1. (A) Curable hydrocarbon resin and (B) Phenolic antioxidants, (C) Thioether-based antioxidants and A composition comprising, When the mass of component (A) in the above composition is based on 100 g, the total amount of substance of components (B) and (C) is in the range of 1 to 10 mmol. A composition in which, based on 100 g of the mass of component (A) in the composition, the amount of substance per phenol moiety of component (B) is in the range of 0.5 to 4 mmol, and the amount of substance per thioether moiety of component (C) is in the range of 0.5 to 4 mmol.

2. The composition according to claim 1, wherein component (A) comprises an olefin-aromatic vinyl compound-aromatic polyene copolymer or an olefin-aromatic polyene copolymer.

3. The composition according to claim 2, wherein component (A) satisfies all of the following conditions (1) to (4). (1) The number-average molecular weight of the copolymer is between 500 and 100,000. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having 8 or more carbon atoms and 20 or fewer carbon atoms, and the content of aromatic vinyl compound monomer units is 0% by mass or more and 70% by mass or less. (3) The aromatic polyene monomer unit is one or more selected from polyenes having 5 to 20 carbon atoms and having multiple vinyl groups and / or vinylene groups in the molecule, and the content of vinyl groups and / or vinylene groups derived from the aromatic polyene monomer unit is 1.5 or more but less than 20 per number average molecular weight. (4) The olefin monomer units are one or more selected from olefins having 2 or more carbon atoms and 20 or fewer carbon atoms, and the total of the olefin monomer units, the aromatic vinyl compound monomer units and the aromatic polyene monomer units is 100% by mass.

4. Let X1 be the value of the dielectric loss tangent of the cured body of the above composition in the measurement frequency range of 40 GHz, which is determined by the resonator method. When the cured body of the above composition is heated at 175°C for 24 hours, and the value of the dielectric loss tangent in the measurement frequency range of 40 GHz, determined by the resonator method, is denoted as X2, The composition according to any one of claims 1 to 3, wherein the value of (X1 / X2) is 2 or less.

5. (B) The composition according to any one of claims 1 to 3, wherein component (B) has two or more aromatic rings in one molecule.

6. The composition according to any one of claims 1 to 3, wherein component (C) has an acyclic structure.

7. A cured body of the composition according to any one of claims 1 to 3.

8. A laminate comprising a layer containing the composition according to any one of claims 1 to 3 and a metal foil.

9. A cured laminate according to Claim 8.

10. A single-layer CCL, multi-layer CCL, single-layer FCCL, or multi-layer FCCL substrate comprising the cured body described in Claim 9.

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