Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

• This disclosure relates to a curable resin and a method for producing the same, a curable resin composition, a prepreg, and a metal-clad laminate and a method for producing the same.
• Laminates used in printed circuit boards for high-speed communications are expected to offer even higher performance.
• the curable resins used in laminates are required to have not only electrical insulation but also heat resistance and practical properties such as adhesion to metal foil.
• Patent document 1 discloses a polymer containing an indane structure based on a specific diisoalkenyl arene, which has sufficient thermal and electronic properties.
• the present disclosure has been made in consideration of the above problems, and aims to provide a curable resin that has excellent adhesion to metal foil and good electrical properties and heat resistance, a method for producing the same, and a curable resin composition, a prepreg, and a metal-clad laminate that contain the curable resin, and a method for producing the same.
• the curable resin according to the present disclosure has at least an ⁇ -olefin structure represented by the following formula (1), has an iodine value of 70 or more, and has a weight average molecular weight Mw of 2,500 or more.
• each R 1 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group
• p1 represents a real number of 0 to 4
• * represents a bonding position.
• the curable resin may have an iodine value of 70 or more and 200 or less.
• the content of the ⁇ -olefin structure represented by the formula (1) may be 1.0 mmol/g or more.
• the content of the ⁇ -olefin structure represented by the formula (1) may be 1.0 mmol/g or more and 6.3 mmol/g or less.
• the following parameter FA which is represented by the content of the ⁇ -olefin structure shown in the formula (1), the content of the indane structure shown in the following formula (2), and the content of the inner olefin structure shown in the following formula (3), in the curable resin, may be 0.39 or more.
• each R2 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group, p2 represents a real number of 0 to 4, q1 represents a real number of 0 to 3, and * represents a bonding position.
• each R3 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group, p3 represents a real number of 0 to 4, and * represents a bonding position.
• the following parameter FI which is represented by the content of the ⁇ -olefin structure shown in the formula (1), the content of the indane structure shown in the formula (2), and the content of the inner olefin structure shown in the formula (3) in the curable resin, may be less than 0.58
• Any of the above curable resins may have a content of heteroatoms other than carbon atoms and hydrogen atoms of 3 mass % or less. Any of the above curable resins may not contain the heteroatom. Any of the above curable resins may have an olefin structure at the terminal of the molecular structure. Any of the above curable resins may further have a side chain olefin structure having an olefin structure in the side chain portion.
• the total content of the ⁇ -olefin structure, the olefin structure at the terminal of the molecular structure, and the side chain olefin structure having an olefin structure in a side chain portion may be 1.8 mmol/g or more.
• the content of the indane structure represented by the formula (2) may be 3.0 mmol/g or less.
• Any of the above curable resins may have a weight average molecular weight Mw of 5,000 or more and 500,000 or less.
• the method for producing a curable resin according to the present disclosure comprises polymerizing a compound having a plurality of isopropenyl groups in the presence of an acid catalyst at a reaction temperature of 10 to 75° C. to obtain a curable resin having at least the ⁇ -olefin structure shown in formula (1) above, an iodine value of 70 or more, and a weight average molecular weight Mw of 2,500 or more.
• the acid catalyst may be selected from the group consisting of a mixture of one or more of an ester compound, a ketone compound, and an ether compound with one or more of a Bronsted acid, a Lewis acid, an organic sulfonic acid, and an inorganic acid, as well as methanesulfonic acid, a BF3 complex, tin chloride, and toluenesulfonic acid.
• the aging temperature in the polymerization reaction of the compound having a plurality of isopropenyl groups may be 10 to 75° C., and the aging time may be 5 minutes to 72 hours.
• the curable resin composition according to the present disclosure contains any of the curable resins described above.
• the prepreg according to the present disclosure contains the above-mentioned curable resin composition.
• the metal-clad laminate according to the present disclosure includes a cured product of the curable resin composition and a metal foil.
• the metal-clad laminate may have a peel strength of the metal foil of 2.0 N/cm or more.
• the method for producing a metal-clad laminate according to the present disclosure involves laminating a prepreg containing the above-mentioned curable resin composition and a metal foil.
• the present disclosure provides a curable resin that has excellent adhesion to metal foil and good electrical properties and heat resistance, a method for producing the same, and a curable resin composition, a prepreg, and a metal-clad laminate that contain the curable resin, and a method for producing the same.
• the numerical range indicated using “to” includes the numerical values before and after “to” as the minimum and maximum values, respectively.
• the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range.
• the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
• curable resins used in laminates mounted on electrical and electronic components are required to have not only electrical properties but also heat resistance, as well as practical properties such as adhesion (adhesion) to metal foils and solubility in solvents.
• adhesion adhesion
• hydrocarbon resins and fluororesins composed of carbon atoms and hydrogen atoms have been used so far.
• examples of the hydrocarbon resins include polyfunctional vinyl aromatic polymers, cyclic polyolefin resins, vinyl aromatic compound-conjugated diene compound copolymers, and the like.
• examples of the fluororesins include polytetrafluoroethylene.
• these resins tend to have poor chemical interaction with metal foils and may have poor adhesion to metal foils.
• fluororesins which are thermoplastic resins, may have poor heat resistance.
• Patent Document 1 discloses a polymer based on a specific diisoalkenyl arene that is believed to contain a large amount of the above-mentioned indane structure as a resin with sufficient thermal and electronic properties.
• the present inventors have found that by using a curable resin having an ⁇ -olefin structure shown in the following formula (1), which further has an iodine value of a specific value or more and a weight-average molecular weight Mw of a specific value or more in a metal-clad laminate, it is possible to achieve excellent adhesion to the metal foil and good electrical properties and heat resistance without the need to separately add other additives.
• the present curable resin (hereinafter also referred to as the present curable resin) will be described in detail, but the present disclosure is not limited to this embodiment. Furthermore, any modification can be made without departing from the gist of the present disclosure.
• the present curable resin has at least an ⁇ -olefin structure shown in the following formula (1) as a unit structure, an iodine value of 70 or more, and a weight average molecular weight Mw of 2,500 or more.
• the present curable resin has the ⁇ -olefin structure in a range satisfying an iodine value of 70 or more, so that the resin can be given flexibility, and when laminated with a metal foil, the adhesiveness with the metal foil can be increased by the anchor effect, and the curability can also be improved.
• the present curable resin can be given excellent curability by having its Mw of 2,500 or more.
• the molecular structure in the curable resin can be identified using 1 H-NMR, 13 C-NMR, etc. Details will be described later.
• the present curable resin which will be described in detail later, can be a resin obtained by polymerizing a compound having a plurality of isopropenyl groups (e.g., a diisopropenyl compound) at a specific reaction temperature in the presence of an acid catalyst.
• a compound having a plurality of isopropenyl groups include 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene.
• These diisopropenyl compounds can be those produced by known methods.
• a diisopropenyl compound can be synthesized by intramolecular dehydration of a diol compound obtained by oxidizing a cumyl group and reducing it with hydrogen.
• a diisopropenyl compound can also be produced by adding propylene to an aromatic compound and subjecting it to a dehydrogenation reaction.
• the raw material monomer for producing the present curable resin may be a precursor of a compound having a plurality of isopropenyl groups (for example, a diisopropenyl compound precursor).
• R 1 's each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group
• p1 represents a real number of 0 to 4
• * represents a bonding position
• R 1 is a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms, and from the viewpoint of electrical properties, is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.
• the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isopropenyl group, a t-butyl group, and an n-butyl group.
• the halogenated alkyl group is an alkyl group in which a hydrogen atom is substituted with a halogen atom, and examples of the halogen atom include F, Cl, Br, and I.
• the number of carbon atoms in the alkyl group is, for example, 1 to 10.
• p1 is a real number from 0 to 4, preferably from 0 to 3, and more preferably 0.
• the iodine value means the number of grams of iodine (I 2 ) that can be added (reacted) to 100 grams of the target sample (here, curable resin). Therefore, the larger this value is, the higher the degree of unsaturation in the sample, that is, the greater the number of unsaturated bonds (double bonds) in the structure. Since the above-mentioned ⁇ -olefin structure has a double bond in the structure, the value of the iodine value can be a guide to know the content ratio of the ⁇ -olefin structure in the curable resin. The iodine value can be determined by the Wiess method.
• the iodine value of the present curable resin is preferably, for example, the following values. That is, the iodine value of the present curable resin is, for example, 71 or more, 72 or more, 73 or more, 74 or more, 75 or more, 76 or more, 77 or more, 78 or more, 79 or more, 80 or more, 81 or more, 82 or more, 83 or more, 84 or more, 85 or more, 86 or more, 87 or more, 88 or more, 89 or more, 90 or more, 91 or more, 92 or more, 93 or more, more than 93, 94 or more, or 95 or more.
• the iodine value is preferably 200 or less. If the iodine value is 200 or less, it is easy to adjust the degree of polymerization, and it is easy to impart excellent heat resistance and curability. From the same viewpoint, the iodine value is preferably, for example, the following values. That is, the iodine value is, for example, 195 or less, 190 or less, 185 or less, 180 or less, 175 or less, 170 or less, 165 or less, 160 or less, 155 or less, or 150 or less.
• the weight average molecular weight Mw of the present curable resin is 2,500 or more, and is preferably, for example, the following values. That is, the weight average molecular weight Mw of the present curable resin is, for example, 2,550 or more, 2,600 or more, 2,650 or more, 2,700 or more, 2,750 or more, 2,800 or more, 2,850 or more, 2,900 or more, 2,950 or more, 3,000 or more, 3,100 or more, 3,200 or more, 3,300 or more, 3,400 or more, 3,500 or more, 3,600 or more, 3,700 or more, 3,800 or more, 3,900 or more, 4,000 or more, 4,100 or more, 4,200 or more, 4,300 or more, 4,400 or more, 4,500 or more, 4,600 or more, 4,700 or more, 4,800 or more, 4,900 or more, 5,000 or more, 5,100 or more, 5,200 or more, 5,300 or more, 5,400 or more, 5,500 or more, 5,600 or more, 5,700 or more, 5,800 or more, 5,000 or more, 5,100 or
• the weight average molecular weight Mw of the present curable resin is preferably, for example, the following value from the viewpoint of solvent solubility. That is, the weight average molecular weight Mw of the curable resin is, for example, 500,000 or less, 450,000 or less, 400,000 or less, 350,000 or less, 300,000 or less, 250,000 or less, 200,000 or less, 190,000 or less, 180,000 or less, 170,000 or less, 160,000 or less, 150,000 or less, 140,000 or less, 130,000 or less, 120,000 or less, 110,000 or less, or 100,000 or less. The method for measuring the weight average molecular weight will be described later.
• the number average molecular weight Mn of the present curable resin is preferably 700 or more, and more preferably 1,000 or more.
• the number average molecular weight Mn of the present curable resin is preferably 5,000 or less. The method for measuring the number average molecular weight will be described later.
• the content of the ⁇ -olefin structure represented by the above formula (1) in the present curable resin is preferably, for example, the following value from the viewpoint of electrical properties, heat resistance, and metal foil adhesion: That is, the ⁇ -olefin content (content ratio) is, for example, 1.0 mmol/g or more, 1.1 mmol/g or more, 1.2 mmol/g or more, 1.3 mmol/g or more, 1.4 mmol/g or more, 1.5 mmol/g or more, 1.6 mmol/g or more, 1.7 mmol/g or more, 1.8 mmol/g or more, 1.9 mmol/g or more, or 2.0 mmol/g or more.
• the content of the ⁇ -olefin structure in the curable resin is preferably, for example, the following value: That is, the ⁇ -olefin content is, for example, 6.3 mmol/g or less, 6.2 mmol/g or less, 6.1 mmol/g or less, 6.0 mmol/g or less, 5.9 mmol/g or less, 5.8 mmol/g or less, 5.7 mmol/g or less, 5.6 mmol/g or less, 5.5 mmol/g or less, 5.4 mmol/g or less, 5.3 mmol/g or less, 5.2 mmol/g or less, 5.1 mmol/g or less, or 5.0 mmol/g or less.
• the present curable resin can be a polymer of a diisopropenyl compound, as will be described in detail later.
• the present curable resin can contain, as unit structures, an olefin structure located at the end of the molecular structure (terminal olefin structure), a side chain olefin structure having an olefin structure in the side chain portion, an indane structure shown in formula (2) described later, an inner olefin structure shown in formula (3) described later, and other structures.
• the present curable resin preferably has either one or both of the terminal olefin structure and the side chain olefin structure.
• the adhesion to the metal foil is further improved, and a higher metal peel strength (peel strength) can be imparted.
• the total content of the above ⁇ -olefin structure, the olefin structure at the end of the molecular structure (terminal olefin structure), and the side chain olefin structure having an olefin structure in the side chain portion in the present curable resin is preferably as follows.
• the total content of these three structures is preferably, for example, the following value. That is, the three-structure content is, for example, 1.8 mmol/g or more, 1.9 mmol/g or more, 2.0 mmol/g or more, 2.1 mmol/g or more, 2.2 mmol/g or more, or 2.3 mmol/g or more.
• the total content of these three structures in the present curable resin is preferably, for example, the following value from the viewpoint of heat resistance and curability.
• the content of the three structures is, for example, 6.5 mmol/g or less, 6.4 mmol/g or less, 6.3 mmol/g or less, 6.2 mmol/g or less, 6.1 mmol/g or less, 6.0 mmol/g or less, 5.9 mmol/g or less, 5.8 mmol/g or less, 5.7 mmol/g or less, 5.6 mmol/g or less, 5.5 mmol/g or less, 5.4 mmol/g or less, 5.3 mmol/g or less, 5.2 mmol/g or less, 5.1 mmol/g or less, or 5.0 mmol/g or less.
• the total content of the terminal olefin structure and the side chain olefin structure in the present curable resin is preferably, for example, the following value from the viewpoint of peel strength. That is, the two-structure content is, for example, 0.1 mmol/g or more, 0.11 mmol/g or more, 0.12 mmol/g or more, 0.13 mmol/g or more, 0.14 mmol/g or more, 0.15 mmol/g or more, 0.16 mmol/g or more, 0.17 mmol/g or more, 0.18 mmol/g or more, 0.19 mmol/g or more, 0.2 mmol/g or more, 0.25 mmol/g or more, 0.3 mmol/g or more.
• the total content of the terminal olefin structure and the side chain olefin structure in the present curable resin is preferably, for example, the following value from the viewpoint of heat resistance and curability. That is, the content of the two structures is, for example, 6.0 mmol/g or less, 5.9 mmol/g or less, 5.8 mmol/g or less, 5.7 mmol/g or less, 5.6 mmol/g or less, 5.5 mmol/g or less, 5.4 mmol/g or less, 5.3 mmol/g or less, 5.2 mmol/g or less, 5.1 mmol/g or less, 5.0 mmol/g or less, 4.9 mmol/g or less, 4.8 mmol/g or less, 4.7 mmol/g or less, 4.6 mmol/g or less, 4.5 mmol/g or less, 4.4 mmol/g or less, 4.3 mmol/g or less, 4.2 mmol/g or less, 4.3
• the total content of these three structures in the present curable resin may consist of two of the three structures, or may consist of one (for example, an ⁇ -olefin structure).
• the present curable resin may have only one of the above three structures (for example, an ⁇ -olefin structure), only two of the structures, or all three of the structures.
• the present curable resin can be a polymer having an ⁇ -olefin structure, a terminal olefin structure, a side chain olefin structure, and, if necessary, an indane structure, an inner olefin structure, and other structures as repeating units.
• the above-mentioned terminal olefin structure refers to an olefin structure located at the end of a molecular structure, and the structure is not particularly limited, but can be represented, for example, by the following formula (4).
• A represents a polymer chain and may contain at least one structure selected from the group consisting of the ⁇ -olefin structure shown in formula (1) above, the side chain olefin structure shown in formula (5) below, the indane structure shown in formula (2) below, and the inner olefin structure shown in formula (3) below.
• A contains at least the ⁇ -olefin structure shown in formula (1) above.
• the terminal olefin structure may be a structure represented by the following formula (4-1).
• a 1 represents a polymer chain and may contain at least one structure selected from the group consisting of the ⁇ -olefin structure shown in formula (1) above, the side chain olefin structure shown in formula (5) below, the indane structure shown in formula (2) below, and the inner olefin structure shown in formula (3) below.
• A contains at least the ⁇ -olefin structure shown in formula (1) above.
• R 4 each independently represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms
• p4 represents a real number from 0 to 4.
• R 4 is a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms, and from the viewpoint of electrical properties, is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.
• the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isopropenyl group, a t-butyl group, and an n-butyl group.
• each R 5 independently represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group
• p5 represents a real number of 0 to 4
• * represents a bonding position.
• R 5 is a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms, and from the viewpoint of electrical properties, is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.
• the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isopropenyl group, a t-butyl group, and an n-butyl group.
• each R2 independently represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms
• p2 represents a real number of 0 to 4
• q1 represents a real number of 0 to 3
• * represents a bonding position.
• R 2 is a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms, and from the viewpoint of electrical properties, is preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms.
• the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isopropenyl group, a t-butyl group, and an n-butyl group.
• R3 's each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group
• p3 represents a real number of 0 to 4
• * represents a bonding position.
• the halogenated alkyl group is an alkyl group in which a hydrogen atom is substituted with a halogen atom, and examples of the halogen atom include F, Cl, Br, and I.
• the number of carbon atoms in the alkyl group is, for example, 1 to 10.
• p3 is a real number of 0 to 4, preferably 0 to 3, and more preferably 0.
• the indane structure has a good balance of aromaticity and aliphaticity, improving solvent solubility and compatibility with other polymers and imparting excellent heat resistance.
• the content of indane structures in this curable resin is high, there is a tendency for adhesion to metal foil to decrease, so it is preferable that the content of indane structures in this curable resin (hereinafter also referred to as indane content) is less than that of ⁇ -olefin structures, and is preferably, for example, the following value: That is, the indan content in the present curable resin is, for example, 4.0 mmol/g or less, 3.9 mmol/g or less, 3.8 mmol/g or less, 3.7 mmol/g or less, 3.6 mmol/g or less, 3.5 mmol/g or less, 3.4 mmol/g or less, 3.3 mmol/g or less, 3.2 mmol/g or less, 3.1 mmol/g or less, 3.0 m
• the present curable resin diisopropenyl compound homopolymer
• a diisopropenyl compound as a raw material monomer
• the iodine value described above is small, it is considered that the content of the above-mentioned indane structure is high.
• the inner olefin structure improves electrical properties and heat resistance and imparts good curability, but the ⁇ -olefin structure contributes more to curability. Therefore, it is preferable that the content of the ⁇ -olefin structure ( ⁇ -olefin content) in this curable resin is greater than the content of the inner olefin structure (hereinafter also referred to as the inner olefin content).
• the following parameter FA which is represented by the above-mentioned ⁇ -olefin content, inner olefin content, and indane content, is preferably 0.39 or more.
• FA [ ⁇ -olefin structure content] / ([inner olefin structure content] + [indan structure content] + [ ⁇ -olefin structure content]) If the FA is 0.39 or more, a curable resin having excellent adhesion to metal foil, electrical properties and heat resistance can be easily produced.
• FA is, for example, 0.40 or more, 0.41 or more, 0.42 or more, 0.43 or more, 0.44 or more, 0.45 or more, 0.46 or more, 0.47 or more, 0.48 or more, 0.49 or more, 0.50 or more, 0.51 or more, 0.52 or more, 0.53 or more, 0.54 or more, 0.55 or more, 0.56 or more, 0.57 or more, 0.58 or more, 0.59 or more, 0.60 or more, 0.61 or more, 0.62 or more, 0.63 or more, 0.64 or more, 0.65 or more, 0.66 or more, 0.67 or more, 0.68 or more, 0.69 or more, 0.70 or more, 0.71 or more, 0.72 or more, 0.73 or more, 0.74 or more, or 0.75 or more. From the same viewpoint, the FA is preferably, for example, equal to or less than 0.95.
• the following parameter FI which is represented by the above-mentioned ⁇ -olefin content, inner olefin content, and indane content, is preferably less than 0.58.
• FI [content of indane structure] / ([content of inner olefin structure] + [content of indane structure] + [content of ⁇ -olefin structure] / 2)
• the FI is less than 0.58, a curable resin having excellent adhesiveness to metal foil can be easily produced.
• the FI is, for example, 0.579 or less, 0.575 or less, 0.57 or less, 0.56 or less, 0.55 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, 0.50 or less, 0.49 or less, 0.48 or less, 0.47 or less, 0.46 or less, 0.45 or less, 0.44 or less, 0.43 or less, 0.42 or less, 0.41 or less, 0.40 or less, 0.39 or less, 0.38 or less, 0.37 or less, 0.36 or less, 0.35 or less, 0.34 or less, 0.33 or less, 0.32 or less, 0.31 or less, 0.30 or less, 0.29 or less, 0.28 or less, 0.27 or less, 0.26 or less, 0.25 or less. From the same viewpoint, the FI is, for example, preferably 0.15 or more.
• the blending ratio of insoluble components is preferably 5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.
• the solvent include methyl ethyl ketone and toluene.
• the dielectric loss tangent of this curable resin at a frequency of 10 GHz is preferably 0.004 or less, more preferably 0.0015 or less, even more preferably 0.001 or less, and particularly preferably 0.0008 or less.
• the method for measuring the dielectric loss tangent will be described later.
• the glass transition temperature (Tg) of the (cured product) refers to the glass transition temperature of the cured product obtained by curing the curable resin according to the present disclosure or the curable resin composition according to the present disclosure.
• the cured product exhibits a good glass transition temperature and a preferable heat resistance.
• the glass transition temperature of the cured product is preferably 110°C or higher, more preferably 125°C or higher, even more preferably 140°C or higher, and particularly preferably 160°C or higher. The method for measuring the glass transition temperature will be described later.
• the present curable resin exhibits the above-mentioned glass transition temperature even when heat-cured at the heat-curing temperature used in producing substrate materials such as prepregs.
• the heat-curing temperature is at least 250° C.
• the cured product exhibiting the above-mentioned heat resistance may be a product obtained by curing a composition containing the present curable resin (a curable resin composition according to the present disclosure) as described above.
• the composition will be described later.
• the present curable resin may be composed of one type of polymer satisfying the present embodiment, or may be composed of multiple polymers.
• the above-mentioned various physical properties such as the content ratio of the insoluble component in the solvent, the glass transition temperature, and the dielectric loss tangent are values for a mixture (curable resin) of these multiple polymers.
• the method for producing a curable resin according to the present disclosure involves polymerizing a compound having a plurality of isopropenyl groups (e.g., a diisopropenyl compound) in the presence of an acid catalyst at a reaction temperature of 10 to 75° C. to obtain a curable resin having at least the ⁇ -olefin structure shown in the above-mentioned formula (1), an iodine value of 70 or more, and a weight average molecular weight Mw of 2,500 or more.
• a compound having a plurality of isopropenyl groups e.g., a diisopropenyl compound
• an acid catalyst at a reaction temperature of 10 to 75° C.
• the present curable resin may have the above-mentioned terminal olefin structure, side chain olefin structure, indane structure shown in formula (2), and inner olefin structure shown in formula (3).
• each of these structures is generated by a reaction between molecules having an isopropenyl group in the raw material, and the indane structure is dominant in equilibrium theory (thermodynamics), and the ⁇ -olefin structure is dominant kinetically. Therefore, the blending ratio of each structure contained in the present curable resin can be controlled by reaction conditions such as the type of catalyst and temperature conditions. That is, one method for obtaining a predetermined structure in the present curable resin is, for example, a method of using a catalyst mixture of a Lewis acid and a Lewis base at a predetermined temperature.
• the compound having multiple isopropenyl groups is a compound having two or more isopropenyl groups in one molecule.
• the compound can be one produced by a conventionally known method, for example, diisopropenylbenzenes such as 1,3-diisopropenylbenzene and 1,4-diisopropenylbenzene.
• the compound can also be a precursor thereof (for example, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol).
• the present curable resin may be a homopolymer of a compound having a plurality of isopropenyl groups, or a copolymer using a plurality of compounds including the compound.
• the other compounds include monovinyl compounds and divinyl compounds. More specifically, examples of the other compounds include ⁇ -olefin compounds such as ⁇ -methylstyrene, ⁇ -methylstyrene dimer, and diphenylethylene, monoisopropenyl compounds, and cyclic dienes.
• the monoisopropenyl compounds can be used as terminators that stop the propagation reaction.
• a structure such as a phenol structure, an aromatic amine structure, an aromatic ether structure, a maleimide structure, etc. may be introduced into the present curable resin.
• a structure such as a phenol structure, an aromatic amine structure, an aromatic ether structure, a maleimide structure, etc.
• it is preferable to introduce it into the structure by utilizing an electrophilic substitution reaction with a cation generated from an isopropenyl group of the raw material during the polymerization reaction.
• the present curable resin does not necessarily need to contain heteroatoms other than carbon and hydrogen atoms.
• the moisture content of the raw materials used to obtain the present curable resin, such as monomers, is preferably 500 ppm or less from the viewpoint of reactivity. If necessary, the raw materials can be dehydrated using molecular sieves, alumina, etc.
• Examples of the acid catalyst used in the polymerization reaction include the following inorganic acids, solid acids, organic sulfonic acids, Lewis acids, and Bronsted acids. Note that one acid may correspond to multiple types of inorganic acids, solid acids, organic sulfonic acids, Lewis acids, and Bronsted acids.
• Inorganic acids e.g., sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid
• Solid acids for example, activated clay, acid clay, silica alumina, zeolite, sulfonated carbon, strongly acidic ion exchange resin, heteropoly hydrochloric acid, tungstic acid
• Organic sulfonic acids for example, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, perfluoroalkanesulfonic acids such as CF3SO3H , C2F5SO3H and C6F5SO3H ;
• Lewis acids for example, AlCl3 , TiCl4 , SnCl4 , B ( C6F5 ) 3 , BF3 and Lewis bases and their complexes, methylalumoxanes, metallocene halides and
• Lewis base acting as a promoter component for example, one or more compounds selected from the group consisting of ester compounds, thioester compounds, ketone compounds, amine compounds, ether compounds, thioether compounds, and phosphine compounds shown below can be used.
• Ester compounds for example, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, phenyl acetate, methyl propionate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, Thioester compounds: for example, methyl mercaptopropionic acid, ethyl mercaptopropionic acid, Ketone compounds: for example, methyl ethyl ketone, methyl isobutyl ketone, benzophenone, Amine compounds: for example, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Ether compounds: for example, diethyl ether, methyl tert-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydr
• the present production method from the viewpoint of easily producing an ⁇ -olefin structure (and a terminal olefin structure and a side chain olefin structure) and easily controlling the molecular weight, it is preferable to use a combination (mixture) of one or more of the above-mentioned ester compounds, the above-mentioned ketone compounds and the above-mentioned ether compounds and one or more of the above-mentioned acid catalysts.
• the acid catalyst include the above-mentioned Bronsted acids, Lewis acids, organic sulfonic acids and inorganic acids.
• the acid catalyst it is also preferable to use one selected from the group consisting of methanesulfonic acid, BF3 complex, tin chloride and toluenesulfonic acid as the acid catalyst.
• the amount of the co-catalyst relative to the acid catalyst is not particularly limited since it may vary depending on the reaction conditions, but it is preferable that the amount of the co-catalyst is 1 mole or more relative to 1 mole of the acid catalyst.
• a catalyst mixture of a Lewis acid e.g., BF3.O ( C2H5 ) 2
• a Lewis base e.g., isopropyl acetate
• the present curable resin having a specific structure, a specific iodine value, and a specific Mw can be easily produced.
• the polymerization reaction can be carried out in a solvent.
• the solvent include the following: non-polar organic solvents such as hexane, decane, dodecane, cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and trimethylbenzene; chlorine-based organic solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, and perchloroethane; and aromatic compounds such as halogenated benzenes, nitrobenzene, and trifluoromethylbenzene.
• the above ester compounds, ketone compounds, and ether compounds can also be used as solvents.
• the reaction temperature in the polymerization reaction is preferably 10 to 75°C. If the reaction temperature is 10°C or higher, the reaction is easily completed within an appropriate time. Furthermore, if the reaction temperature is 75°C or lower, it is easy to suppress the formation of indane structures and inner olefin structures, and it is easy to form ⁇ -olefin structures, terminal olefin structures, and side chain olefin structures.
• the reaction temperature and reaction time in the polymerization reaction respectively mean the temperature and time from when the addition of the raw materials to the reaction system is started and the polymerization reaction of the added raw materials is started to when the polymerization reaction is completed.
• the reaction time starts when the polymerization reaction of some of the raw materials starts among all the raw materials.
• the aging temperature is preferably 10 to 75°C.
• the present curable resin contained in this composition has excellent compatibility, other curable resins can be used in combination as necessary.
• the other curable resin any known resin can be used as appropriate, for example, modified polyphenylene ether (PPE) resin, soluble divinylbenzene polymer, vinylbenzyl ether resin, maleimide resin, triazine ether, or other curable resins having heterocyclic ether bonds in the main chain can be used.
• PPE polyphenylene ether
• soluble divinylbenzene polymer vinylbenzyl ether resin
• maleimide resin triazine ether
• triazine ether triazine ether
• the crosslinking agent By adding the above-mentioned crosslinking agent to the present curable resin and curing it, a cured composition with good properties can be obtained.
• the crosslinking agent include compounds having reactive functional groups in the molecule, such as styryl groups (St groups), maleimide groups, allyl groups, and (meth)acrylic groups. From the viewpoint of reactivity with the present curable resin, the reactive functional group is preferably a styryl group.
• the crosslinking agent is preferably a vinyl compound such as 1,2-bis(vinylphenyl)ethane (BVPE), a fluorene compound having a vinylbenzyl group, an indene compound having a vinylbenzyl group, or divinylbenzene, as described in Japanese Patent No. 3681170, and more preferably BVPE.
• the crosslinking agent may be a mixture of two or more types or a compound (polymer) having a repeating unit, and for example, a vinyl compound represented by the following formula (6), a vinyl compound represented by the following formula (7), or a compound having a vinylbenzyl ether group can be used.
• X1 represents a hydrocarbon group having 6 or more carbon atoms containing at least one type selected from an aromatic cyclic group and an aliphatic cyclic group; n1 represents an integer of 1 to 10.
• X2 represents one or more of (a) to (h) in formula (8) below.
• the plurality of X2 may be the same as or different from each other.
• A2 represents a methylene group or an oxygen atom
• Q represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.
• the plurality of Q's may be the same as or different from each other.
• R represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group.
• the plurality of R's may be the same as or different from each other.
• l and m each represent an integer of 0 to 3
• n2 represents a repeating unit, l ⁇ n2 ⁇ 20
• p represents a repeating unit, 1.1 ⁇ p ⁇ 20.
• Compounds having a vinylbenzyl ether group can be synthesized, for example, by reacting a phenolic resin such as a biphenyl aralkyl type phenolic resin, an aralkyl phenolic resin, or a naphthol aralkyl resin with chloromethylstyrene in the presence of an alkaline catalyst.
• a phenolic resin such as a biphenyl aralkyl type phenolic resin, an aralkyl phenolic resin, or a naphthol aralkyl resin with chloromethylstyrene in the presence of an alkaline catalyst.
• the crosslinking agent may be, for example, a compound obtained by reacting a compound having fluorene or indene in its partial skeleton with a halogenated compound having St group such as chloromethylstyrene in the presence of an alkali catalyst.
• a phase transfer catalyst may be used, and the solvent is preferably an aprotic organic solvent or a solvent containing an aprotic organic catalyst.
• the crosslinking agent may be a compound shown in the following formula (9) obtained by reacting a compound having fluorene in its partial skeleton with chloromethylstyrene.
• R 10 represents a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group
• X 10 represents an integer of 0 to 4.
• trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene and styrene-butadiene copolymers (polyfunctional vinyl compounds), polyfunctional aromatic copolymers obtained by copolymerizing divinylbenzene with a styrene derivative, and vinylbenzyl compounds such as styrene and divinylbenzene having vinylbenzyl groups in the molecule may be used.
• TAIC triallyl isocyanurate
• polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule polyfunctional acrylate compounds having two or more acrylic groups in the molecule
• vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene and styrene-butadiene
• those having two or more carbon-carbon double bonds in the molecule are preferable.
• Specific examples include trialkenyl isocyanurate compounds, polyfunctional acrylate compounds, polyfunctional methacrylate compounds, polyfunctional aromatic copolymers, and divinylbenzene compounds. It is believed that the use of these will more suitably form crosslinks by the curing reaction, and the heat resistance of the cured product of this composition can be further improved.
• the crosslinking agents exemplified above may be used alone or in combination of two or more.
• a crosslinking agent a compound having two or more carbon-carbon unsaturated double bonds in the molecule and a compound having one carbon-carbon unsaturated double bond in the molecule may be used in combination.
• Specific examples of compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).
• the average number of carbon-carbon unsaturated double bonds (number of terminal double bonds) per molecule of the crosslinking agent varies depending on the weight-average molecular weight of the crosslinking agent, but from the viewpoint of the heat resistance of the cured product, it is preferably 1 or more, and more preferably 2 or more. Also, from the viewpoints of reactivity, storage stability, and flowability of the composition, the number of terminal double bonds per molecule of the crosslinking agent is preferably 20 or less, and more preferably 18 or less.
• the number of terminal double bonds of the crosslinking agent is preferably 1 to 4 when the weight average molecular weight of the crosslinking agent is less than 500 (e.g., 100 or more and less than 500), taking into consideration the weight average molecular weight of the crosslinking agent.
• the number of terminal double bonds of the crosslinking agent is preferably 3 to 20 when the weight average molecular weight of the crosslinking agent is 500 or more (e.g., 500 or more and 5000 or less). In each case, if the number of terminal double bonds is equal to or more than the lower limit of the above range, the crosslinking agent is likely to have good reactivity, and it is easy to impart an appropriate crosslinking density to the cured product of the resin composition, and it is easy to improve heat resistance and Tg. On the other hand, if the number of terminal double bonds is equal to or less than the upper limit of the above range, it is easy to prevent the composition from gelling.
• the number of terminal double bonds of the crosslinking agent can be determined from the specifications of the product used.
• the number of terminal double bonds here refers to the average number of double bonds per molecule of all crosslinking agents present in 1 mole of crosslinking agent.
• the cured product of the curable resin composition containing the present curable resin and a compound having a styryl group or a maleimide group exhibits heat resistance.
• the glass transition temperature (Tg) of the cured product is preferably 110°C or higher, more preferably 125°C or higher, even more preferably 140°C or higher, and particularly preferably 160°C or higher.
• the flame retardant examples include halogen-based flame retardants such as bromine-based flame retardants and phosphorus-based flame retardants.
• halogen-based flame retardants such as bromine-based flame retardants and phosphorus-based flame retardants.
• each flame retardant may be used alone or in combination of two or more kinds.
• silica As the filler, silica, hollow silica, etc. can be used. From the viewpoint of dielectric properties, it is preferable that the number of silanol groups in the filler is small. Furthermore, the hollowness of silica allows the composition to have a low dielectric constant. Silica that has been surface-modified can also be used. Specifically, silica that has been treated with a functional group containing a carbon-carbon unsaturated double bond and/or trimethylsilylation can be used.
• elastomer examples include styrene-based elastomers, such as styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, and hydrogenated styrene (butadiene/isoprene)-styrene copolymers.
• styrene-based elastomers such as styrene-butadiene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, hydrogenated styrene-isoprene-styren
• the present composition may contain, as necessary, acenaphthylene, indene, derivatives thereof, and known maleimide compounds.
• the content of these compounds may be 75% by mass or less based on the present curable resin.
• the composition may contain a fluororesin.
• the fluororesin may have a functional group from the viewpoint of improving adhesiveness.
• the prepreg according to the present disclosure contains the present curable resin described above.
• the present prepreg can be produced, for example, by the following method. Specifically, first, a curable resin composition containing the present curable resin described above and other additives described above (elastomer, curing agent such as crosslinking agent, etc.) as necessary is mixed and stirred to prepare a resin varnish. Next, a fibrous material is immersed in the resin varnish and dried to obtain a prepreg.
• the fibrous material into which the resin varnish is soaked it is preferable to use glass cloth of any composition from the viewpoints of processability and electrical properties, and it is more preferable to use quartz cloth from the viewpoint of electrical properties.
• the metal-clad laminate according to the present disclosure includes a cured product of the present curable resin and a metal foil.
• the present laminate is obtained by bonding a prepreg containing the present curable resin and a metal foil. More specifically, the present laminate can be produced by bonding a metal foil (e.g., copper foil) to both sides of the prepreg impregnated with the present curable resin by lamination or the like, for example, under heating and pressure.
• the metal foil peel strength of the metal-clad laminate obtained by pressurizing and heating the prepreg obtained using this curable resin and laminating it with metal foil is preferably 2.0 N/cm or more, and more preferably 2.5 N/cm or more, from the viewpoint of practical application.
• the problem according to the present disclosure can also be solved by the following embodiments.
• the above-mentioned embodiment and the following embodiments may overlap in content. That is, the composition, configuration, and physical properties of the curable resin, curable resin composition, prepreg, and metal-clad laminate according to these embodiments may all be the same (may overlap with other embodiments).
• the procedure and content of the method for producing a curable resin and the method for producing a metal-clad laminate according to these embodiments may be (as a result) the same (may overlap with other embodiments).
• the preferred forms of the curable resin, curable resin composition, prepreg, and metal-clad laminate, the method for producing a curable resin, and the method for producing a metal-clad laminate in the following embodiments are also similar to the above-mentioned embodiments, so the description will be omitted here.
• Examples 1 to 11 and Examples 19 to 29 described in the examples described later can also be examples of the following embodiments, and Examples 12 to 18 and Examples 30 to 37 can also be comparative examples of the following embodiments.
• A-2 The curable resin according to (A-1) above, having an iodine value of 70 or more and 200 or less.
• A-3) The curable resin according to (A-1) or (A-2), wherein the total content of the ⁇ -olefin structure, the terminal olefin structure, and the side chain olefin structure is 1.8 mmol/g or more.
• (A-4) The curable resin according to any one of (A-1) to (A-3) above, which has the ⁇ -olefin structure and has a content of the ⁇ -olefin structure of 1.0 mmol/g or more.
• (A-5) The curable resin according to (A-4) above, wherein the content of the ⁇ -olefin structure is 1.0 mmol/g or more and 6.3 mmol/g or less.
• (A-6) The curable resin according to any one of (A-1) to (A-5), wherein the following parameter FA, which is represented by the content of the ⁇ -olefin structure in the curable resin, the content of the indane structure shown in the above formula (2), and the content of the inner olefin structure shown in the above formula (3), is 0.39 or more.
• FI [content of indane structure] / ([content of inner olefin structure] + [content of indane structure] + [content of ⁇ -olefin structure] / 2)
• A-8) The curable resin according to any one of (A-1) to (A-7) above, in which the content of heteroatoms other than carbon atoms and hydrogen atoms is 3 mass% or less.
• A-9) The curable resin according to (A-8), which does not contain the heteroatom.
• A-10) The curable resin according to any one of (A-1) to (A-9) above, wherein the content of the indane structure is 3.0 mmol/g or less.
• (A-11) The curable resin according to any one of (A-1) to (A-10) above, having a weight average molecular weight Mw of 5,000 or more and 500,000 or less.
• (A-12) A method for producing a curable resin, comprising polymerizing a compound having a plurality of isopropenyl groups in the presence of an acid catalyst at a reaction temperature of 10 to 75° C. to obtain a curable resin having at least one of the ⁇ -olefin structure, the terminal olefin structure, and the side chain olefin structure, and having an iodine value of 70 or more and a weight average molecular weight Mw of 2,500 or more.
• (A-13) The method for producing a curable resin according to (A-12) above, wherein the acid catalyst is selected from the group consisting of a mixture of one or more of an ester compound, a ketone compound, and an ether compound with one or more of a Bronsted acid, a Lewis acid, an organic sulfonic acid, and an inorganic acid, as well as methanesulfonic acid, a BF3 complex, tin chloride, and toluenesulfonic acid.
• the acid catalyst is selected from the group consisting of a mixture of one or more of an ester compound, a ketone compound, and an ether compound with one or more of a Bronsted acid, a Lewis acid, an organic sulfonic acid, and an inorganic acid, as well as methanesulfonic acid, a BF3 complex, tin chloride, and toluenesulfonic acid.
• A-14 The method for producing a curable resin according to (A-12) or (A-13), wherein the aging temperature in the polymerization reaction of the compound having a plurality of isopropenyl groups is 10 to 75° C., and the aging time is 5 minutes to 72 hours.
• a curable resin composition comprising the curable resin according to any one of (A-1) to (A-11) above.
• A-16 A prepreg comprising the curable resin composition described in (A-15) above.
• A-17 A metal-clad laminate comprising a cured product of the curable resin composition described in (A-15) above and a metal foil.
• A-18 The metal-clad laminate according to (A-17), wherein the peel strength of the metal foil is 2.0 N / cm or more.
• a method for producing a metal-clad laminate comprising laminating a prepreg containing the curable resin composition described in (A-15) above and a metal foil.
• (B-1) A curable resin having at least one structure selected from the group consisting of an ⁇ -olefin structure, a terminal olefin structure, and a side chain olefin structure represented by the above-mentioned formula (1), and having a total content of these structures of 1.8 mmol/g or more.
• (B-2) The curable resin according to (B-1) above, having an iodine value of 70 or more.
• (B-3) The curable resin according to (B-2) above, having an iodine value of 70 or more and 200 or less.
• (B-4) The curable resin according to any one of (B-1) to (B-3) above, having a weight average molecular weight Mw of 2,500 or more.
• (B-8) The curable resin according to any one of (B-1) to (B-7), wherein the following parameter FA, which is represented by the content of the ⁇ -olefin structure in the curable resin, the content of the indane structure shown in the above formula (2), and the content of the inner olefin structure shown in the above formula (3), is 0.39 or more.
• FI [content of indane structure] / ([content of inner olefin structure] + [content of indane structure] + [content of ⁇ -olefin structure] / 2)
• B-10) The curable resin according to any one of (B-1) to (B-9), in which the content of heteroatoms other than carbon atoms and hydrogen atoms is 3 mass% or less.
• B-11) The curable resin according to (B-10) above, which does not contain the heteroatom.
• B-12 The curable resin according to any one of (B-1) to (B-11) above, in which the content of the indane structure is 3.0 mmol/g or less.
• (B-13) A method for producing a curable resin, comprising polymerizing a compound having a plurality of isopropenyl groups in the presence of an acid catalyst at a reaction temperature of 10 to 75° C. to obtain a curable resin having at least one structure selected from the ⁇ -olefin structure, terminal olefin structure, and side chain olefin structure represented by the above formula (1), and having a total content of these structures of 1.8 mmol/g or more.
• (B-14) The method for producing a curable resin according to (B-13) above, wherein the acid catalyst is selected from the group consisting of a mixture of one or more of an ester compound, a ketone compound, and an ether compound with one or more of a Bronsted acid, a Lewis acid, an organic sulfonic acid, and an inorganic acid, as well as methanesulfonic acid, a BF3 complex, tin chloride, and toluenesulfonic acid.
• the acid catalyst is selected from the group consisting of a mixture of one or more of an ester compound, a ketone compound, and an ether compound with one or more of a Bronsted acid, a Lewis acid, an organic sulfonic acid, and an inorganic acid, as well as methanesulfonic acid, a BF3 complex, tin chloride, and toluenesulfonic acid.
• (B-15) The method for producing a curable resin according to (B-13) or (B-14), wherein the aging temperature in the polymerization reaction of the compound having a plurality of isopropenyl groups is 10 to 75° C., and the aging time is 5 minutes to 72 hours.
• (B-16) A curable resin composition comprising the curable resin according to any one of (B-1) to (B-12) above.
• (B-17) A prepreg comprising the curable resin composition described in (B-16) above.
• (B-18) A metal-clad laminate comprising a cured product of the curable resin composition described in (B-16) above and a metal foil.
• Examples 1 to 11 and 19 to 29 are working examples of the present disclosure, and Examples 12 to 18 and 30 to 37 are comparative examples.
• Peaks were assigned by two-dimensional NMR and DEPT methods. Specifically, the baseline of each peak was drawn in 13 C-NMR, and the content (mmol/g) of each structure in 1 g of the target substance (curable resin) was calculated from the amount (g) of the measurement target (curable resin) using the area a (area from 16.8 to 18.2 ppm), the area b (area from 59.1 to 60.2 ppm) assigned to the carbon of the indane structure, the area c (area from 114.3 to 118.1 ppm) assigned to the carbon of the ⁇ -olefin structure, the terminal olefin structure, and the side chain olefin structure, the area d (area from 21.6 ppm to 22.3 ppm) assigned to the carbon of the terminal olefin structure and the side chain olefin structure, the area e (area from 1.4 to 2.5 ppm), and the amount f (grams) of hexamethyl
• FA [ ⁇ -olefin structure content] / ([inner olefin structure content] + [indan structure content] + [ ⁇ -olefin structure content])
• FI [content of indane structure] / ([content of inner olefin structure] + [content of indane structure] + [content of ⁇ -olefin structure] / 2)
• iodine value measurement method The iodine value of the measurement object (curable resin) was measured by a method conforming to JIS K 0070. Specifically, the measurement object was reacted with Wiess reagent (iodine monochloride-acetic acid solution) and allowed to stand in a dark place, and then the excess iodine monochloride was titrated with sodium thiosulfate to calculate the iodine value.
• Wiess reagent iodine monochloride-acetic acid solution
• the column used was a combination of guard column "HXL-L” (trade name) manufactured by Tosoh Corporation, "SuperH-RC” (trade name) manufactured by Tosoh Corporation, "TSKgel SuperHZ2000” (trade name) manufactured by Tosoh Corporation, “TSKgel SuperHZ2500” (trade name) manufactured by Tosoh Corporation, “TSKgel SuperHZ3000” (trade name) manufactured by Tosoh Corporation, and “TSKgel SuperHZ4000” (trade name) manufactured by Tosoh Corporation.
• the measurement was performed using a developing solvent: tetrahydrofuran, a flow rate: 1.0 ml/min, a column temperature: 40°C, a detector: RI (differential refractometer), and a calibration curve using monodisperse polystyrene.
• a developing solvent tetrahydrofuran
• a flow rate 1.0 ml/min
• a column temperature 40°C
• RI differential refractometer
• RI differential refractometer
• the above film-like cured product was prepared as follows. That is, 10 parts by mass of each of the resins obtained from Examples 1 to 18 described below and 2 parts by mass of BVPE were dissolved in 12 parts by mass of toluene. The obtained toluene solution was then poured between PTFE spacers, sandwiched between polyimide films, held between SUS plates, and held in a vacuum press at a pressure of 2 MPa and 200° C. for 2 hours to cure, thereby obtaining a film-like cured product.
• Example 1 In a 1L glass reaction vessel equipped with a stirring blade and a fluororesin-coated thermocouple under N2 flow, 480 g of paraxylene, 4.80 g (33.8 mmol) of boron trifluoride/diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid catalyst, 6.91 g (67.6 mmol) of propyl acetate as a cocatalyst, and maintained at 25 ° C. for 2 hours.
• paraxylene 4.80 g (33.8 mmol) of boron trifluoride/diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acid catalyst
• 6.91 g (67.6 mmol) of propyl acetate as a cocatalyst
• the aqueous phase in the reaction vessel was discarded, and the reaction vessel was washed three times with 300 ml of ion-exchanged water to obtain a resin solution.
• 2200 g of methanol was added to another 6 L flask, and the resin solution was gradually added to reprecipitate the resin.
• a resin cake was obtained by filtration.
• the resin cake was redispersed in 2200 g of methanol, washed, and filtered twice, and the obtained resin was vacuum dried at 60° C. to obtain 107.9 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method.
• the molecular weight of the obtained curable resin was Mn: 1,770, Mw: 7,090.
• the iodine value of the curable resin was 131.
• the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated. It was confirmed by 13 C-NMR that the obtained curable resin contained an ⁇ -olefin structure.
• the measurement results for the curable resin of Example 1 are shown in Table 1.
• Example 2 The same procedure as in Example 1 was carried out except that 0.96 g (6.76 mmol) of boron trifluoride/diethyl ether complex, 1.38 g (13.5 mmol) of propyl acetate, the reaction temperature and aging temperature were set to 37.5° C., and the aging time was set to 25 minutes, to obtain 112.7 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method. As a result, the molecular weight of the obtained curable resin was Mn: 2,260 and Mw: 19,130. The iodine value of the curable resin was 124.
• each structure in the obtained curable resin is as follows. When the curable resin was dissolved in toluene to a concentration of 60 mass %, no insoluble matter was generated. Content of each structure: ⁇ -olefin structure: 1.97 mmol/g, indane structure: 0.53 mmol/g, inner olefin structure: 0.16 mmol/g, terminal and side chain olefin structures: 0.96 mmol/g.
• Example 3 The same procedure as in Example 1 was carried out except that 0.96 g (6.76 mmol) of boron trifluoride/diethyl ether complex, 1.38 g (13.5 mmol) of propyl acetate, reaction temperature and aging temperature were set to 37.5° C., and aging time was set to 45 minutes, to obtain 110.3 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated.
• Example 4 The same procedure as in Example 1 was carried out except that 2.0 g (14.1 mmol) of boron trifluoride/diethyl ether complex, 2.87 g (28.1 mmol) of propyl acetate, and aging time were changed to 60 minutes, to obtain 98.1 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60 mass%, no insoluble matter was generated.
• Example 5 The same procedure as in Example 1 was carried out except that the aging time was 120 minutes, and 99.1 g of a curable resin was obtained.
• the structure analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60 mass%, no insoluble matter was generated.
• Example 6 The same procedure as in Example 1 was carried out except that the reaction temperature and aging temperature were 55° C. and the aging time was 90 minutes, and 111.0 g of a curable resin was obtained.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated.
• Example 7 The same procedure as in Example 1 was carried out except that 0.96 g (0.67 mmol) of boron trifluoride/diethyl ether complex, 3.45 g (33.8 mmol) of propyl acetate, the reaction temperature and aging temperature were 45° C., and the aging time was 270 minutes, to obtain 103.2 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated.
• Example 8 The same procedure as in Example 1 was carried out except that 0.96 g (6.76 mmol) of boron trifluoride/diethyl ether complex, 1.38 g (13.5 mmol) of propyl acetate, the reaction temperature and aging temperature were 45° C., and the aging time was 210 minutes, to obtain 102.8 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated.
• Example 9 The same procedure as in Example 1 was carried out except that 2.0 g (14.1 mmol) of boron trifluoride/diethyl ether complex, 2.87 g (28.1 mmol) of propyl acetate, the reaction temperature and aging temperature were 45° C., and the aging time was 210 minutes, to obtain 111.6 g of a curable resin.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were performed according to the above-mentioned method. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60% by mass, no insoluble matter was generated.
• Example 10 The same procedure as in Example 1 was carried out except that the amount of propyl acetate used was 17.1 g (167.4 mmol) and the maturation time was 180 minutes, and 99.6 g of a curable resin was obtained.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60 mass%, no insoluble matter was generated.
• Example 11 The same procedure as in Example 1 was carried out except that the amount of propyl acetate used was 17.1 g (167.4 mmol) and the maturation time was 240 minutes, and 99.8 g of a curable resin was obtained.
• the structural analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows. When the curable resin was dissolved in toluene to a concentration of 60 mass%, no insoluble matter was generated.
• Example 12 The same procedure as in Example 1 was carried out except that the reaction temperature and aging temperature were 75° C. and the aging time was 60 minutes, to obtain 109.1 g of a curable resin.
• the structure analysis, iodine value measurement, and molecular weight measurement of the obtained resin were carried out according to the above-mentioned methods. The results are as follows. Molecular weight: Mn: 2,700, Mw: 15,530, Iodine value: 65, Content of each structure: ⁇ -olefin structure: 1.61 mmol/g, indane structure: 2.00 mmol/g, inner olefin structure: 0.65 mmol/g, terminal and side chain olefin structures: 0.07 mmol/g.
• Example 13 Under N2 flow, 500g of paraxylene and 17.5g of paratoluenesulfonic acid monohydrate were added to a 1L glass flask equipped with a thermometer and a stirrer, and the temperature was set to 60°C. While maintaining the reaction temperature at 60°C, 250g of 1,3-diisopropenylbenzene (manufactured by TCI) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was aged at a ripening temperature of 60°C for 1 hour. After cooling, 160g of water was added to dissolve the catalyst and removed. The mixture was repeatedly washed with 160g of water until it became neutral.
• TCI 1,3-diisopropenylbenzene
• the structure analysis, iodine value measurement, and molecular weight measurement of the obtained resin were performed according to the above-mentioned method.
• the molecular weight of the obtained resin was Mn: 390, Mw: 570, and the iodine value was 210.
• the obtained resin was analyzed by NMR, a peak of an isopropenyl group was confirmed in the region of 4.70-5.40 ppm in the 1 H-NMR chart.
• Example 14 In a glass flask equipped with a thermometer and a stirrer under N2 flow, 520 g of toluene and 3 g of activated clay were placed and heated to an internal temperature of 70 ° C. while stirring. Then, 150 g of 1,3-diisopropenylbenzene (TCI) was dropped at a controlled dropping rate so that the internal temperature did not exceed 80 ° C. After dropping, the mixture was stirred until the internal temperature dropped to 70 ° C. Then, 150 g of 1,3-diisopropenylbenzene (TCI) was similarly dropped, and the mixture was allowed to react for another 2 hours after the drop was completed.
• TCI 1,3-diisopropenylbenzene
• Example 15 In a glass flask equipped with a thermometer and a stirrer under N2 flow, 125 g of 1,3-diisopropenylbenzene (manufactured by TCI), 125 g of toluene, and 12.5 g of activated clay were charged, the internal temperature was raised to 30°C, and the reaction was carried out for 2 hours, followed by reaction at 45°C for 1 hour, 60°C for 1 hour, and 70°C for 1.5 hours. After cooling, the activated clay was removed by filtration, and the solvent was distilled off under heating and reduced pressure to obtain 104.0 g of a curable resin.
• TCI 1,3-diisopropenylbenzene
• Example 16 The same procedure as in Example 1 was carried out except that 0.24 g (1.7 mmol) of boron trifluoride/diethyl ether complex, 0.34 g (3.33 mmol) of propyl acetate, reaction temperature and aging temperature were 45° C., and aging time was 240 minutes, to obtain 88.4 g of a curable resin.
• the structure analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows.
• Example 17 The same procedure as in Example 1 was carried out except that propyl acetate was not used, the reaction temperature and aging temperature were set to 45° C., and the aging time was set to 120 minutes, to obtain 97.5 g of a curable resin.
• the structure analysis, iodine value measurement, and molecular weight measurement of the obtained curable resin were carried out according to the above-mentioned methods. The results are as follows.
• Example 18 In a 1L glass flask equipped with a thermometer and a stirrer under N2 flow, 194.6 g of cyclohexane and 0.35 g of trifluoromethanesulfonic acid were added to bring the temperature to 45°C, and while maintaining the temperature at 45°C, 30.7 g of 1,3-diisopropenylbenzene (manufactured by TCI) was added over 30 minutes. The temperature was then maintained at 40°C for 1 hour. A 5% by mass aqueous solution of sodium bicarbonate was added to terminate the reaction, and 28.7 g of a curable resin was obtained.
• the structure of the obtained curable resin was analyzed, the iodine value was measured, and the molecular weight was measured according to the methods described above. The results are as follows. Molecular weight: Mn: 3,940, Mw: 64,590, Iodine value: 12, Content of each structure: ⁇ -olefin structure: 1.94 mmol/g, indane structure: 4.45 mmol/g, inner olefin structure: 0.12 mmol/g, terminal and side chain olefin structures: 0.01 mmol/g.
• metal-clad laminates were produced using compositions containing each of the resins obtained in Examples 1 to 18 according to the following procedure, and the laminates were evaluated.
• Resins Resins obtained in Examples 1 to 18 (corresponding to Examples 19 to 36), modified polyphenylene ether (PPE, SA-9000, manufactured by SABIC Innovative Plastics) (corresponding to Example 37), Elastomer: Tuftec H1043 (product name, manufactured by Asahi Kasei), Crosslinker: 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene (BVPE, manufactured by Linchuan Chemical) Initiator: 2,3-dimethyl-2,3-diphenylbutane, Inorganic filler: spherical silica EQ2410-SCM (trade name, manufactured by Zhejiang Third Age Material Technology Co. Ltd.), Flame retardant: ethylene bis(pentabromophenyl), trade name: SAYTEX 8010 (manufactured by Albemarle).
• PPE modified polyphenylene ether
• SA-9000 manufactured by SABIC Innovative Plastics
• Elastomer Tuftec
• the cured products of the curable resins described in Examples 1 to 11 had high Tg, and the copper foil peel strength (peel strength) of the copper foil peel laminates for evaluation made using the resins was 2.0 N/cm or more, and the adhesiveness to the metal foil was excellent.
• the copper foil peel strength of the copper foil peel laminate (Example 30) made using the resin of Example 12 was low.
• the dielectric loss tangent (Df) was high due to the influence of heteroatoms, and favorable results were not obtained.
• Examples 32 to 36 which used the resins of Examples 14 to 18, good results were not obtained compared to the results of Examples 19 to 29, which used the resins described in Examples 1 to 11.
• this composition is compatible with various materials and can be used to make varnish without separation, has good adhesion to metal foil, a low dielectric tangent, and is heat resistant, providing a good balance of practical properties and making it an excellent substrate material.
• the present curable resin which has an ⁇ -olefin structure and a specific iodine value and a specific Mw, has excellent adhesion to metal foil and good electrical properties and heat resistance. Furthermore, the present disclosure can provide electronic materials that have excellent electrical properties, heat resistance, etc., such as curable resin compositions, cured products, prepregs, and metal-clad laminates that use the present curable resin.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Reinforced Plastic Materials (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

Family

ID=95448741

Family Applications (1)

Country Status (3)

Citations (7)

• 2024
  • 2024-10-16 JP JP2025553210A patent/JPWO2025084301A1/ja active Pending
  • 2024-10-16 TW TW113139407A patent/TW202536022A/zh unknown
  • 2024-10-16 WO PCT/JP2024/036761 patent/WO2025084301A1/ja active Pending

Patent Citations (7)

Also Published As

Similar Documents

Legal Events