Low dielectric resin composition and cured product thereof

Abstract

To provide a low-dielectric resin composition including a dielectric property-lowering agent composed of an epoxy-modified silicone resin with a low relative dielectric constant and low dielectric loss tangent.SOLUTION: A low-dielectric resin composition includes: a dielectric property-lowering agent composed of a siloxane compound represented by general formula (1), with the content of an ionic substance being less than 0.001 mass%, where the ionic substance is at least one selected from fluoride ions, chloride ions, bromide ions and iodide ions; and a resin. In the formula (1), each group is as defined in the specifications, and a, b, c, d, and e are each an integer ranging from 0 to 1, fulfilling the conditions 1≤a+b+c≤3 and 1≤a+b+c+d+e≤5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a low dielectric resin composition and a cured product thereof. [Background technology]

[0002] Thermosetting resins such as urethane resins, epoxy resins, silicone resins, urea resins, phenolic resins, unsaturated polyester resins, and melamine resins form crosslinked structures when heated alone or in the presence of a curing agent, resulting in infusible and insoluble resin compositions with a three-dimensional network structure. These resin compositions have excellent properties, such as interfacial properties, mechanical properties, insulating properties, adhesive properties, adhesion, weather resistance, impact resistance, corrosion resistance, water resistance, heat resistance, abrasion resistance, and chemical resistance, and are used in a wide range of fields and applications, including laminating agents, adhesives, sealants, insulating films, paints, medical materials, building materials, molding materials, automotive materials, textile materials, and electronic materials.

[0003] Among the above thermosetting resins, epoxy-modified silicone resins have an epoxy group and a siloxane structure, and therefore, when used, can improve multiple properties of the resin composition, such as interfacial properties, insulating properties, adhesive properties, and heat resistance. Known examples of such epoxy-modified silicone resins include bis[(3,4-epoxycyclohexyl)ethyl]polydimethylsiloxane and tetrakis[(3,4-epoxycyclohexyl)ethyl]tetramethylcyclotetrasiloxane (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-9086 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, in the field of information and communications, there has been a significant demand for ultra-high speed communication speeds due to the increase in the amount of information, the simultaneous connection of a huge number of devices due to the diversification of information, ultra-low latency for remote operation, etc., and technology that can process large volumes of electrical signals at high speed is required. To meet these demands, there has been an increase in the introduction of technology that increases the amount of electrical signals transmitted per unit time on transmission paths by using higher frequency bands than the current frequencies.

[0006] On the other hand, in high frequency bands, there is the problem of transmission loss, where the strength of the electrical signal is easily attenuated or delayed. Transmission loss is affected by conductor loss in the conductor parts of the electronic material that forms the transmission path, and dielectric loss in the resin parts, but in high frequency bands, the effect of dielectric loss becomes dominant. Dielectric loss is the loss that is converted into heat when an electrical signal flows through a resin part, and is expressed by the formula D=kf√εr·tanδ (D: dielectric loss, k: proportionality constant, f: frequency, εr: relative permittivity, tanδ: dielectric dissipation factor), and is proportional to the relative permittivity and dielectric dissipation factor of the resin. Therefore, in the above-mentioned information and communications field, there is a need for a technology for controlling the relative dielectric constant and dielectric loss tangent of resins used in high frequency bands.

[0007] However, the epoxy-modified silicone resin described in Patent Document 1 has a high relative permittivity and dielectric loss tangent due to the high polarity of the epoxy group, making it difficult to apply in high frequency bands. That is, when the siloxane structure of the epoxy-modified silicone resin is a low-molecular-weight oligosiloxane, the resin composition using this resin has a high proportion of epoxy groups in the molecule, and therefore a high relative dielectric constant and dielectric loss tangent, resulting in large transmission loss.When the siloxane structure is a high-molecular-weight polydimethylsiloxane, the resin composition is in a high-viscosity oil state, which causes problems such as the resin composition not curing. Therefore, there has been a demand for the development of an epoxy-modified silicone resin with a low relative dielectric constant and dielectric loss tangent, and further for the development of a low dielectric resin composition obtained by curing the same.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a low dielectric resin composition containing a dielectric reducing agent made of an epoxy-modified silicone resin having a low relative dielectric constant and dielectric dissipation factor, and a cured product thereof. [Means for solving the problem]

[0009] As a result of extensive research to achieve the above object, the present inventors have found that a siloxane compound represented by the following general formula (1) is an epoxy-modified silicone resin having a low relative dielectric constant and dielectric dissipation factor, and that when the content of an ionic substance in the siloxane compound is less than 0.001 mass%, the relative dielectric constant and dielectric dissipation factor of a resin composition cured using the siloxane compound decrease, thereby completing the present invention.

[0010] That is, the present invention provides: 1. A low dielectric resin composition comprising a resin and a dielectric reducing agent comprising a siloxane compound represented by the following general formula (1), the content of an ionic substance being less than 0.001 mass %, the ionic substance being one or more ions selected from the group consisting of fluoride ions, chloride ions, bromide ions and iodide ions: [ka] [In the formula, R 1 are each independently represented by the following general formula (2): [ka] (In the formula, R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. represents a group represented by R 2 are each independently represented by the following general formula (3) or (4): [ka] (In the formula, R 5 represents a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. represents a group represented by R 3 are each independently a hydrogen atom, an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following general formula (5): [ka] (In the formula, R 1 , R 4 and R 5 has the same meaning as above, and f represents an integer of 0 to 10. represents a group represented by a, b, c, d, and e are each independently an integer of 0 to 1, and satisfy the conditions 1≦a+b+c≦3 and 1≦a+b+c+d+e≦5. 2. The low dielectric resin composition according to claim 1, further comprising a curing agent. 3. The low dielectric resin composition of 1 or 2, wherein the dielectric constant of the dielectric reducing agent is 4.0 ε or less at a frequency of 1 MHz. 4. The low dielectric resin composition of 1 or 2, wherein the dielectric loss tangent of the dielectric reducing agent is 0.002 tanδ or less at a frequency of 1 MHz. 5. The low dielectric resin composition of 1 or 2, wherein the resin is a thermosetting resin or a thermoplastic resin. 6. The low dielectric resin composition of 5, wherein the thermosetting resin is a urethane resin, an epoxy resin, a silicone resin, a urea resin, a phenolic resin, an unsaturated polyester resin, or a melamine resin. 7. The low dielectric resin composition of 5, wherein the thermoplastic resin is an acrylic resin, a polyamide resin, a polyimide resin, a polyurethane resin, a polyester resin, a polyvinyl chloride resin, a polycarbonate resin, a polyvinyl acetate resin, or a polystyrene resin. 8. A cured product obtained by curing the low dielectric resin composition of 1 or 2 to provide. [Effects of the Invention]

[0011] The dielectric reducing agent used in the present invention, which is made of a specific siloxane compound and has a low content of ionic substances, has a low relative dielectric constant and dielectric loss tangent, and can reduce the relative dielectric constant and dielectric loss tangent of a resin composition cured using this agent. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be specifically described below. [1] Low dielectric constant agents The dielectric lowing agent of the present invention comprises a siloxane compound represented by the following general formula (1), and has an ionic substance content of less than 0.001% by mass.

[0013] [ka]

[0014] In general formula (1), R 1 each independently represents a group represented by the following general formula (2):

[0015] [ka]

[0016] In general formula (2), R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, sec-hexyl, tert-hexyl, sec-heptyl, tert-heptyl, sec-octyl, tert-octyl, sec-nonyl, tert-nonyl, sec-decyl, and tert-decyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, butenyl, and methallyl; aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl. Among these, R 4As the group, an unsubstituted linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; an alkenyl group; an aryl group; or an aralkyl group is preferable, and from the viewpoint of easy availability of precursor raw materials in particular, an unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms; or an alkenyl group is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is even more preferable.

[0017] In general formula (1), R 2 each independently represents a group represented by the following general formula (3) or (4).

[0018] [ka]

[0019] In the general formula (3) and the general formula (4), R 5 represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkylene group may be linear, branched, or cyclic, and specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene; branched alkylene groups such as isopropylene, sec-butylene, tert-butylene, sec-pentylene, tert-pentylene, sec-hexylene, tert-hexylene, sec-heptylene, tert-heptylene, sec-octylene, and tert-octylene; and cyclic alkylene groups such as cyclopropylene, cyclopentylene, and cyclohexylene.

[0020] Some or all of the hydrogen atoms of these alkylene groups may be substituted with other substituents, and specific examples of these substituents include alkoxy groups having 1 to 3 carbon atoms, such as methoxy, ethoxy, and (iso)propoxy; halogen atoms, such as fluorine, chlorine, and bromine; aromatic hydrocarbon groups, such as phenyl; cyano, amino, ester, ether, carbonyl, acyl, and sulfide groups, and one or more of these may be used in combination. There are no particular limitations on the substitution positions of these substituents, and there are no limitations on the number of substituents. Furthermore, these alkylene groups may have one or more of ether groups, ester groups, carbonyl groups, sulfide groups, disulfide groups, etc. present in the molecular chain. Among these, R 5 As the alkylene group, an unsubstituted linear alkylene group having 1 to 8 carbon atoms is preferred, and from the viewpoint of easy availability of precursor materials, an unsubstituted linear alkylene group having 1 to 4 carbon atoms such as a methylene group or an ethylene group is more preferred.

[0021] In general formula (1), R 3 each independently represents a hydrogen atom, an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, or a group represented by the following general formula (5):

[0022] [ka]

[0023] In general formula (5), R 1 , R 4 and R 5 The substituents include the same as those exemplified above. Furthermore, f is an integer of 0 to 10, but is preferably an integer of 0 to 3, and more preferably 0, particularly from the viewpoint of easy availability of precursor materials.

[0024] Among these, R 3As the group, an unsubstituted linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; an alkenyl group; an aryl group; or an aralkyl group is preferable, and from the viewpoint of easy availability of precursor raw materials in particular, an unsubstituted linear or branched alkyl group having 1 to 3 carbon atoms; or an alkenyl group is more preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is even more preferable.

[0025] In general formula (1), a, b, c, d, and e are each independently an integer of 0 to 1 that satisfies 1≦a+b+c≦3 and 1≦a+b+c+d+e≦5. However, from the viewpoint of reducing the relative dielectric constant and the dielectric loss tangent in particular, the conditions of 1≦a+b+c≦1.1 and 1≦a+b+c+d+e≦5 are more preferable.

[0026] In general formula (1), R 1 and R 2 The combination of OR is considered to reduce the relative permittivity and dielectric loss tangent. 1 The silicon atom to which is bonded is R 2 is preferably in the range of 2 to 59 moles, more preferably 3 to 59 moles, and even more preferably 4 to 59 moles, per mole of silicon atom to which it is bonded.

[0027] The dielectric lowing agent of the present invention is usually produced by subjecting the corresponding hydrosiloxane compound and an epoxy compound having an alkenyl group to a hydrosilylation reaction in the presence of a platinum catalyst.

[0028] The hydrosiloxane compound can be appropriately selected from known siloxane compounds having a hydrogen atom in the molecule. Specific examples thereof include hexamethyltrisiloxane, heptamethyltrisiloxane, (trimethylsiloxy)hexamethyltrisiloxane, octamethyltetrasiloxane, nonamethyltetrasiloxane, (trimethylsiloxy)octamethyltetrasiloxane, decamethylpentasiloxane, undecamethylpentasiloxane, (trimethylsiloxy)decamethylpentasiloxane, dodecamethylhexasiloxane, tridecamethylhexasiloxane, (trimethylsiloxy)dodecamethylhexasiloxane, tetradecamethylheptasiloxane, pentadecamethylheptasiloxane, (trimethylsiloxy)tetradecamethylheptasiloxane, hexadecamethyloctasiloxane, heptadecamethyloctasiloxane, (trimethyl (siloxy)hexadecamethyloctasiloxane, octadecamethylnonasiloxane, nonadecamethylnonasiloxane, (trimethylsiloxy)octadecamethylnonasiloxane, eicosamethyldecasiloxane, heneicosamethyldecasiloxane, (trimethylsiloxy)eicosamethyldecasiloxane, docosamethylundecasiloxane, tricosamethylundecasiloxane, (trimethylsiloxy)docosamethylundecasiloxane, tetracosamethyldodecasiloxane, pentacosamethyldodecasiloxane, (trimethylsiloxy)tetracosamethyldodecasiloxane, hexacosamethyltridecasiloxane, heptacosamethyltridecasiloxane, (trimethylsiloxy)hexacosamethyltridecasiloxane, and the like. In particular, from the viewpoint of easy availability of precursor materials, hexamethyltrisiloxane, heptamethyltrisiloxane, and (trimethylsiloxy)hexamethyltrisiloxane are preferred.

[0029] The epoxy compound having an alkenyl group can be appropriately selected from known compounds having an alkenyl group and an epoxy group in the molecule. Specific examples thereof include epoxy compounds having a glycidyl ether structure, such as vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, butenyl glycidyl ether, hexenyl glycidyl ether, octenyl glycidyl ether, 2-ethylhexenyl glycidyl ether, and decenyl glycidyl ether; and epoxy compounds having a cycloalkene oxide structure, such as 1,2-epoxy-4-vinylcyclohexane, 1,2-epoxy-4-allylcyclohexane, 1,2-epoxy-4-(2-methylallyl)cyclohexane, 1,2-epoxy-4-butenylcyclohexane, 1,2-epoxy-4-hexenylcyclohexane, 1,2-epoxy-4-octenylcyclohexane, and 1,2-epoxy-4-decenylcyclohexane. In particular, from the viewpoint of easy availability of precursor raw materials, epoxy compounds having a glycidyl ether structure such as allyl glycidyl ether and octenyl glycidyl ether, and epoxy compounds having a cycloalkene oxide structure such as 1,2-epoxy-4-vinylcyclohexane and 1,2-epoxy-4-octenylcyclohexane are preferred.

[0030] The above-mentioned epoxy compound having an alkenyl group is usually produced by a method of reacting an epihalohydrin compound with an alcohol compound (epihalohydrin method), a method of oxidizing an olefin compound using a peracid compound (peracid compound oxidation method), or the like.

[0031] In the epihalohydrin method, an organic halogen compound is used as a raw material, and therefore the epoxy compound produced contains ionic substances derived from the raw material. On the other hand, in the peroxy acid compound oxidation method, an organic halogen compound is not used as a raw material, and therefore the epoxy compound produced does not substantially contain ionic substances. As described above, the dielectric reducing agent of the present invention has an ionic substance content of less than 0.001 mass %. Therefore, from the viewpoint of reducing the ionic substance content, the epoxy compound having an alkenyl group is preferably one produced by a peroxy acid compound oxidation method. Furthermore, by reacting an epoxy compound having an alkenyl group produced by the peroxy acid compound oxidation method with a hydrosiloxane compound, the content of ionic substances contained in the dielectric lowing agent can be reduced.

[0032] In the method for producing a dielectric lowing agent of the present invention, the compounding ratio of the hydrosiloxane compound to the epoxy compound having an alkenyl group is not particularly limited, but from the viewpoints of reactivity and productivity, the ratio is preferably in the range of 1 to 20 moles, more preferably 1 to 10 moles, and even more preferably 1 to 5 moles of the hydrosiloxane compound per mole of the epoxy compound having an alkenyl group.

[0033] The platinum catalyst can be appropriately selected from known platinum (Pt) and complex compounds containing platinum as the central metal. Specific examples include alcohol solutions of chloroplatinic acid such as chloroplatinic acid and chloroplatinic (IV) acid in 2-ethylhexanol; toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes; dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum; dichlorocyclooctadiene platinum, etc. Also usable are catalysts in which platinum black or the like is supported on a carrier such as alumina, silica, or carbon. In particular, from the viewpoint of high reactivity, alcohol solutions of chloroplatinic acid such as a 2-ethylhexanol solution of chloroplatinic (IV) acid, and toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex are preferred.

[0034] The amount of platinum catalyst used is not particularly limited as long as it is an amount that exhibits the catalytic effect of the hydrosilylation reaction. From the viewpoints of reactivity and productivity, however, the amount of platinum metal is preferably in the range of 0.0000001 to 1 mol, more preferably 0.000001 to 0.1 mol, and even more preferably 0.00001 to 0.01 mol per 1 mol of the epoxy compound having an alkenyl group.

[0035] The reaction temperature for the hydrosilylation reaction is not particularly limited, but from the viewpoints of reactivity and productivity, it is preferably in the range of 50 to 200°C, more preferably 50 to 150°C, and even more preferably 50 to 100°C. The reaction time is not particularly limited, but is preferably in the range of 1 to 30 hours, more preferably 1 to 20 hours, and even more preferably 1 to 10 hours.

[0036] The hydrosilylation reaction proceeds without a solvent, but can also be carried out in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile and N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

[0037] The reaction mixture obtained in the hydrosilylation reaction contains the platinum catalyst used in the reaction. The platinum catalyst contained in the reaction solution will turn black, significantly worsening the appearance of the reaction solution, and may also cause the formation of ionic substances derived from the ligands of the platinum catalyst. Furthermore, if unreacted hydrosiloxane compound remains, there is a risk of dehydrogenation. For the above reasons, it is preferable to remove the platinum catalyst contained in the reaction mixture after the hydrosilylation reaction. There are no particular limitations on the method for removing the platinum catalyst contained in the reaction solution, and treatment means such as distillation, column chromatography, washing with water, extraction, filtration, adsorption with activated carbon or diatomaceous earth, etc. can be used.

[0038] The dielectric reducing agent of the present invention contains ionic substances derived from the above-mentioned raw materials. Specific examples of ionic substances include fluoride ions, chloride ions, bromide ions, and iodide ions. In the dielectric lowing agent of the present invention, the content of the ionic substance is less than 0.001% by mass, from the viewpoint of reducing the relative dielectric constant and the dielectric loss tangent, and is preferably in the range of 0.000001% by mass or more and less than 0.001% by mass, more preferably 0.00001% by mass or more and less than 0.001% by mass, and even more preferably 0.0001% by mass or more and less than 0.001% by mass.

[0039] The method for measuring the content of ionic substances is not particularly limited, and analytical means such as ion chromatography, high performance liquid chromatography, potentiometric titration, and fluorescence spectroscopy can be used.

[0040] [2] Low dielectric resin composition The low dielectric resin composition of the present invention contains the above-mentioned dielectric reducing agent and a resin. Specific examples of the resin include thermosetting resins such as urethane resin, epoxy resin, silicone resin, urea resin, phenol resin, unsaturated polyester resin, and melamine resin; and thermoplastic resins such as acrylic resin, polyamide resin, polyimide resin, polyurethane resin, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyvinyl acetate resin, and polystyrene resin. Among these, from the viewpoint of reactivity with the dielectric lowing agent, thermosetting resins are preferred, and epoxy resins and silicone resins are more preferred.

[0041] Specific examples of urethane resins include moisture-curing urethane resins made from aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; polyol-curing urethane resins made from polyol and aromatic isocyanate or aliphatic isocyanate; and block urethane resins made from polyol and blocked isocyanate. These urethane resins may be used alone or in combination of two or more. Among these, moisture-curable urethane resins and polyol-curable urethane resins are preferred, with moisture-curable urethane resins being more preferred, particularly from the viewpoint of availability.

[0042] Specific examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, cyclic aliphatic type epoxy resins, long-chain aliphatic type epoxy resins, heterocyclic type epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins. These epoxy resins may be used alone or in combination of two or more. Among these, bisphenol A type epoxy resins, novolac type epoxy resins, and cycloaliphatic type epoxy resins are preferred, and bisphenol A type epoxy resins are more preferred, particularly from the viewpoint of availability.

[0043] Specific examples of silicone resins include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phenol-modified silicone, etc. These silicone resins may be used alone or in combination of two or more. Among these, from the viewpoint of easy availability, amino-modified silicone, epoxy-modified silicone, and methacryl-modified silicone are preferred, and epoxy-modified silicone is more preferred.

[0044] Specific examples of the phenolic resin include novolac-type phenolic resin, resol-type phenolic resin, rosin-modified phenolic resin, etc. These phenolic resins may be used alone or in combination of two or more. Among these, from the viewpoint of easy availability, novolac-type phenolic resin and resol-type phenolic resin are preferred, and resol-type phenolic resin is more preferred.

[0045] Specific examples of the unsaturated polyester resin include unsaturated acid type unsaturated polyester resin, aromatic saturated acid type unsaturated polyester resin, and aliphatic saturated acid type unsaturated polyester resin. These unsaturated polyester resins may be used alone or in combination of two or more. Among these, unsaturated acid type unsaturated polyester resins and aromatic saturated acid type unsaturated polyester resins are preferred, with unsaturated acid type unsaturated polyester resins being more preferred, particularly from the viewpoint of availability.

[0046] The amount of the dielectric lowing agent added to the resin is preferably in the range of 0.1 to 100% by mass, more preferably 0.2 to 80% by mass, and even more preferably 0.5 to 50% by mass, relative to the resin, from the viewpoint of sufficiently lowering the relative dielectric constant and the dielectric loss tangent.

[0047] The dielectric constant of the dielectric lowing agent is preferably 4.0ε or less, more preferably 3.8ε or less, even more preferably 3.6ε or less at a frequency of 1 MHz, and is preferably 4.4ε or less, more preferably 4.2ε or less, even more preferably 4.0ε or less at a frequency of 1 GHz.

[0048] The dielectric tangent of the dielectric lowing agent is preferably 0.002 tanδ or less, more preferably 0.001 tanδ or less, and even more preferably 0.0005 tanδ at a frequency of 1 MHz, and is preferably 0.2 tanδ or less, more preferably 0.1 tanδ or less, and even more preferably 0.05 tanδ or less at a frequency of 1 GHz.

[0049] There are no particular limitations on the method for measuring the relative dielectric constant and the dielectric loss tangent, and analytical means such as the coaxial probe method, transmission line method, free space method, cavity resonator method, parallel plate capacitor method, and inductance measurement method can be used.

[0050] The low dielectric resin composition of the present invention can be cured by adding a known curing agent. Specific examples of the curing agent include aliphatic amine-based curing agents, aromatic amine-based curing agents, modified amine-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, polyaminoamide-based curing agents, polymercaptan-based curing agents, cationic curing agents, and anionic curing agents. These curing agents may be used alone or in combination of two or more. Among these, particularly from the viewpoint of availability, aliphatic amine-based curing agents, aromatic amine-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, and polyaminoamide-based curing agents are preferred, and aliphatic amine-based curing agents, aromatic amine-based curing agents, imidazole-based curing agents, and acid anhydride-based curing agents are more preferred.

[0051] The amount of the curing agent added to the resin composition is preferably in the range of 0.2 to 2 mol, more preferably 0.5 to 1.5 mol, and even more preferably 0.8 to 1.2 mol per mol of epoxy groups in the resin composition, from the viewpoint of sufficient curing.

[0052] Furthermore, a known curing accelerator may be added to the low dielectric resin composition of the present invention in order to accelerate the curing reaction between the resin composition and the curing agent. Specific examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine and tributylphosphine; quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and tetrabutylphosphonium O,O-diethylphosphorodithioate; quaternary ammonium salts such as 1,8-diazabicyclo[5.4.0]undec-7-ene, a salt of 1,8-diazabicyclo[5.4.0]undec-7-ene with octylic acid, zinc octylate, and tetrabutylammonium bromide; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; amines such as 2,4,6-tris(dimethylaminomethyl)phenol and benzyldimethylamine; and inorganic fillers such as fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, magnesium silicate, and aluminum. These curing accelerators may be used alone or in combination of two or more. Among these, from the viewpoint of availability, organic phosphorus compounds, quaternary ammonium salts, imidazoles, and amines are particularly preferred, with quaternary ammonium salts, imidazoles, and amines being more preferred.

[0053] The amount of the curing accelerator added to the resin composition is preferably in the range of 0.001 to 1 mass %, more preferably 0.001 to 0.5 mass %, and even more preferably 0.001 to 0.1 mass %, relative to the curing agent in the resin composition, from the viewpoint of sufficient curing acceleration.

[0054] The method for curing the low dielectric resin composition of the present invention is not particularly limited as long as the resin composition is cured, and examples thereof include a method of heating a mixture of a dielectric low agent and a resin to cure it, a method of adding a curing agent and, if necessary, a curing accelerator to a mixture of a dielectric low agent and a resin to cure it, and a method of adding a mixture of a dielectric low agent and a resin to a curing agent to cure it. Examples of methods for obtaining a cured product of the resin composition include casting, injection, potting, dipping, drip coating, transfer molding, compression molding, and forming a laminate from a resin sheet or the like.

[0055] The conditions for curing the low dielectric resin composition of the present invention are not particularly limited as long as the conditions are such that the resin composition can be cured. From the viewpoint of productivity, the curing temperature is preferably in the range of 20 to 200°C, more preferably 50 to 150°C, and even more preferably 80 to 120°C. From the viewpoint of productivity, the curing time is preferably in the range of 1 to 10 hours, more preferably 1 to 5 hours, and even more preferably 1 to 3 hours, but may be appropriately set in relation to the above curing temperature.

[0056] The dielectric lowing agent of the present invention may be used as it is, but may also be diluted in a solvent before use. Specific examples of the solvent include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ketone solvents such as acetone and methyl isobutyl ketone; alcohol solvents such as methyl alcohol and ethyl alcohol; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile and N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more. Among these, from the viewpoint of compatibility with the dielectric lowing agent, hydrocarbon solvents, ketone solvents, alcohol solvents, ether solvents, and ester solvents are particularly preferred, and hydrocarbon solvents, ketone solvents, and alcohol solvents are more preferred.

[0057] When the dielectric lowing agent of the present invention is used by diluting it in a solvent, the concentration of the siloxane compound is not particularly limited. However, from the viewpoints of reactivity and productivity, the siloxane compound is preferably diluted in the above-mentioned solvent to a concentration in the range of 0.001 to 50 mass %, more preferably 0.1 to 50 mass %, and even more preferably 0.1 to 10 mass %.

[0058] [3] Dielectric reduction method, use as a dielectric reduction agent The dielectric lowering agent of the present invention is an epoxy-modified silicone resin with a low relative dielectric constant and dielectric loss tangent, and therefore can lower the relative dielectric constant and dielectric loss tangent of a resin composition cured using this agent. The low dielectric resin composition obtained using the dielectric reducing agent of the present invention is suitable as an electronic material for use in high frequency bands in the field of information and communications, such as an optical thin film, an adhesive, a laminate, an insulating film, an anti-reflection film, a sealant, a printed wiring board, etc. [Example]

[0059] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The purity of the fraction obtained by the distillation described below is a value measured under the gas chromatography measurement conditions described below, the content of ionic substances is measured under the titration conditions described below, and the values ​​of the relative dielectric constant and dielectric loss tangent are values ​​measured by dielectric constant measurement under the conditions described below. [Gas chromatography measurement conditions] Gas chromatograph: GC-2014 (Shimadzu Corporation) Packed column: Silicone SE-30 (GL Sciences, Inc.) Detector:TCD Detector temperature: 300℃ Inlet temperature: 300℃ Temperature program: 70°C (0 min) → 10°C / min → 300°C (10 min) Carrier gas: Helium (50 ml / min) Injection volume: 1μl [Titration conditions] Titrator: Automatic titrator COM-2000 (Hiranuma Sangyo Co., Ltd.) Titration reagent: 0.025N silver nitrate aqueous solution Titration solvent: Acetone-methanol mixed solution Method: Potentiometric titration Sample amount: 2g [Conditions for measuring the dielectric constant of low-dielectric materials (parallel plate capacitor method)] LCR meter: HP4284A (Keysight Technologies, Inc.) Liquid test fixture: HP16452A (Keysight Technologies, Inc.) Measurement atmosphere: Room temperature 24°C in air Frequency: 1MHz Standard material: air [Conditions for measuring the dielectric constant of low-dielectric agents (coaxial probe method)] Impedance analyzer: E4991B (Keysight Technologies, Inc.) Dielectric probe kit: N1501A-101 (Keysight Technologies, Inc.) Measurement atmosphere: Room temperature 24°C in air Frequency: 1GHz Standard materials: air, 1-butanol [Conditions for measuring the dielectric constant of resin compositions (parallel plate capacitor method)] LCR meter: E4980A (Keysight Technologies, Inc.) Dielectric test fixture: 16451B (Keysight Technologies, Inc.) Measurement atmosphere: Room temperature 25°C in air Frequency: 1KHz, 1MHz Standard material: air

[0060] [1] Synthesis of low dielectric constant agents [Example 1-1] Synthesis of 1,1,1,3,5,5,5-heptamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]trisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 124.2 g (1.000 mol) of 1,2-epoxy-4-vinylcyclohexane and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.000010 mol as platinum atoms) and heated to 50°C. After the internal temperature stabilized, 222.5 g (1.000 mol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 10 hours, and the mixture was stirred at that temperature for 2 hours. After cooling to room temperature, the resulting reaction mixture was distilled to yield 338.7 g of a colorless, transparent fraction with a boiling point of 116-117°C / 0.2 kPa. Analysis of the resulting fraction by gas chromatography confirmed that the purity of the 1,1,1,3,5,5,5-heptamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]trisiloxane was 99.9% (0.977 mol, yield 97.7%).

[0061] [Example 1-2] Synthesis of a mixture of 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane and 1,1,1,3,5,5,5-heptamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]trisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 114.1 g (1.000 mol) of allyl glycidyl ether and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.000010 mol as platinum atoms) and heated to 50°C. After the internal temperature stabilized, 222.5 g (1.000 mol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 10 hours, and the mixture was stirred at that temperature for 2 hours. After cooling to room temperature, the resulting reaction mixture was distilled to yield 252.5 g of a colorless, transparent fraction with a boiling point of 105-110°C / 0.4 kPa. Analysis of the resulting fraction by gas chromatography confirmed that the purity of the mixture, consisting of 1,1,1,3,5,5,5-heptamethyl-3-[3-(glycidyloxy)propyl]trisiloxane and 1,1,1,3,5,5,5-heptamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]trisiloxane, was 99.9% (0.750 mol, yield 75.0%).

[0062] [Example 1-3] Synthesis of 1,1,1,5,5,5-hexamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]-3-(trimethylsiloxy)trisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 124.2 g (1.000 mol) of 1,2-epoxy-4-vinylcyclohexane and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.000010 mol as platinum atoms) and heated to 50°C. After the internal temperature stabilized, 296.7 g (1.000 mol) of 1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiloxane was added dropwise over 10 hours, and the mixture was stirred at that temperature for 2 hours. After cooling to room temperature, 2.0 g of activated carbon was added to the resulting reaction mixture and stirred at that temperature for 2 hours. After stirring, the activated carbon was removed by filtration and the mixture was concentrated under reduced pressure at 100°C and 0.1 kPa to yield 391.4 g of a colorless, transparent solution. Analysis of the resulting solution by gas chromatography confirmed that the purity of 1,1,1,5,5,5-hexamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]-3-(trimethylsiloxy)trisiloxane was 99.9% (0.930 mol, yield 93.0%).

[0063] [Examples 1-4] Synthesis of a mixture of 1,1,1,5,5,5-hexamethyl-3-(3-glycidyloxypropyl)-3-(trimethylsiloxy)trisiloxane and 1,1,1,5,5,5-hexamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]-3-(trimethylsiloxy)trisiloxane A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 114.1 g (1.000 mol) of allyl glycidyl ether and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.000010 mol as platinum atoms) and heated to 50°C. After the internal temperature stabilized, 296.7 g (1.000 mol) of 1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiloxane was added dropwise over 10 hours, and the mixture was stirred at that temperature for 2 hours. After cooling to room temperature, 2.0 g of activated carbon was added to the resulting reaction mixture and stirred at that temperature for 2 hours. After stirring, the activated carbon was removed by filtration and the mixture was concentrated under reduced pressure at 100°C and 0.1 kPa, yielding 299.9 g of a colorless, transparent solution. Analysis of the resulting solution by gas chromatography confirmed that it was a mixture of 1,1,1,5,5,5-hexamethyl-3-(3-glycidyloxypropyl)-3-(trimethylsiloxy)trisiloxane and 1,1,1,5,5,5-hexamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]-3-(trimethylsiloxy)trisiloxane with a purity of 99.9% (0.730 mol, yield 73.0%).

[0064] [2] Performance evaluation of low dielectric constant agents The 1,1,1,3,5,5,5-heptamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]trisiloxane obtained in Example 1-1 was titrated using potentiometric titration, and the content of ionic substances was confirmed to be 0.00005% by mass. The mixture of 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane and 1,1,1,3,5,5,5-heptamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]trisiloxane obtained in Example 1-2 was titrated using potentiometric titration, confirming that the ionic substance content was 0.00008% by mass. The 1,1,1,5,5,5-hexamethyl-3-[2-(3,4-epoxy)-cyclohexylethyl]-3-(trimethylsiloxy)trisiloxane obtained in Example 1-3 was titrated using potentiometric titration, and the content of ionic substances was confirmed to be 0.00005% by mass. The mixture of 1,1,1,5,5,5-hexamethyl-3-(3-glycidyloxypropyl)-3-(trimethylsiloxy)trisiloxane and 1,1,1,5,5,5-hexamethyl-3-[1-methyl-2-(glycidyloxy)ethyl]-3-(trimethylsiloxy)trisiloxane obtained in Example 1-4 was titrated using potentiometric titration, confirming that the ionic substance content was 0.00008% by mass. The siloxane compound obtained in Example 1-1 was measured for relative permittivity and dielectric loss tangent by measuring the permittivity using the parallel plate capacitor method and the coaxial probe method. The results are shown in Table 1.

[0065] [Table 1]

[0066] The siloxane compound obtained in Example 1-1 had 2 moles of trialkylsilyl groups per mole of silicon atoms bonded to epoxy groups, and it was confirmed that the excess trialkylsilyl groups resulted in an epoxy-modified silicone resin with a low relative dielectric constant and dielectric dissipation factor.

[0067] [3] Preparation of resin composition [Example 2-1] To 100 parts by mass of bisphenol A epoxy resin JER828 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 190 g / mol), 5 parts by mass of the siloxane compound obtained in Example 1-1 and 10 parts by mass of triethylenetetramine as a curing agent were added at room temperature, and the mixture was heated at 100° C. for 2 hours. After cooling to room temperature, a cured resin composition was prepared.

[0068] [Example 2-2] A cured resin composition was prepared in the same manner as in Example 2-1, except that the amount of the siloxane compound was changed to 10 parts by mass.

[0069] [Comparative Example 2-1] A cured resin composition was prepared in the same manner as in Example 2-1, except that no siloxane compound was used.

[0070] [4] Performance evaluation of resin compositions The resin compositions prepared in Examples 2-1 and 2-2 and Comparative Example 2-1 were measured for their relative permittivity and dielectric loss tangent by measuring the permittivity using a parallel plate capacitor method. The results are shown in Table 2.

[0071] [Table 2]

[0072] As shown in Table 2, it was confirmed that the resin compositions of Examples 2-1 and 2-2, which were cured using the siloxane compound obtained in Example 1-1, had low relative dielectric constants and low dielectric loss tangents.

Claims

1. A low dielectric resin composition comprising a resin and a low dielectric agent comprising a siloxane compound represented by the following general formula (1), the content of an ionic substance being less than 0.001 mass %, the ionic substance being one or more ions selected from the group consisting of fluoride ions, chloride ions, bromide ions and iodide ions: 【Chemical Formula 1】 [In the formula, R 1 are each independently represented by the following general formula (2): 【Chemistry 2】 (In the formula, R 4 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. represents a group represented by R 2 are each independently represented by the following general formula (3) or (4): 【Chemistry 3】 (In the formula, R 5 represents a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. represents a group represented by R 3 are each independently a hydrogen atom, an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following general formula (5): 【Chemistry 4】 (In the formula, R 1 , R 4 and R 5 has the same meaning as above, and f represents an integer of 0 to 10. represents a group represented by a, b, c, d, and e are each independently an integer of 0 to 1, and satisfy the following conditions: 1≦a+b+c≦3, 1≦a+b+c+d+e≦5.

2. The low dielectric resin composition according to claim 1, further comprising a curing agent.

3. 3. The low dielectric resin composition according to claim 1, wherein the dielectric constant of the dielectric reducing agent is 4.0 ε or less at a frequency of 1 MHz.

4. 3. The low dielectric resin composition according to claim 1, wherein the dielectric loss tangent of the dielectric reducing agent is 0.002 tan δ or less at a frequency of 1 MHz.

5. 3. The low dielectric resin composition according to claim 1, wherein the resin is a thermosetting resin or a thermoplastic resin.

6. 6. The low dielectric resin composition according to claim 5, wherein the thermosetting resin is a urethane resin, an epoxy resin, a silicone resin, a urea resin, a phenolic resin, an unsaturated polyester resin, or a melamine resin.

7. 6. The low dielectric resin composition according to claim 5, wherein the thermoplastic resin is an acrylic resin, a polyamide resin, a polyimide resin, a polyurethane resin, a polyester resin, a polyvinyl chloride resin, a polycarbonate resin, a polyvinyl acetate resin, or a polystyrene resin.

8. A cured product obtained by curing the low dielectric resin composition according to claim 1 or 2.

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