Propenyl resins, compositions, cured products, printed circuit boards, semiconductor encapsulation materials, and build-up films.

Abstract

To provide a propenyl-based resin, resin composition, and cured product thereof that can achieve a high degree of both excellent heat resistance and low modulus of elasticity during curing. [Solution] General formula (1) (where M 1 and M 2 Each of these independently represents a divalent organic group, where n is an integer from 0 to 9, m is an integer from 1 to 10, and n+m is an integer from 1 to 10, R 1 and R 2 Each of these is independently a predetermined aromatic hydrocarbon group having a propenyl group. A propenyl resin containing a propenyl compound represented by ). TIFF2026076048000028.tif40170

Description

Technical Field

[0001] The present invention relates to a propenyl resin, a composition, a cured product, a printed wiring board, a semiconductor encapsulation material, and a build-up film.

Background Art

[0002] With the recent demands for energy conservation and reduction of CO2 emissions, the adoption of power semiconductors is spreading in the fields of new energy power conversion and EVs.

[0003] Conventionally, Si-based devices have been used for power semiconductors. Recently, however, SiC-based devices have attracted attention because they have high conversion efficiency and can be miniaturized and lightened. Since SiC-based devices can operate at high temperatures, high heat resistance that can ensure operational reliability at high temperatures is required for next-generation power semiconductor encapsulation materials.

[0004] Conventional semiconductor encapsulation materials have used epoxy resins that are excellent in the balance of various physical properties such as heat resistance and moisture resistance. In order to achieve further high heat resistance, studies are underway on the combined use or replacement of resins with higher heat resistance (Tg), such as maleimide resins, benzoxazine resins, and cyanate resins.

[0005] Patent Document 1 proposes a composition containing a maleimide compound and a propenyl group-containing resin as a composition that gives a cured product excellent in heat resistance. However, although the resin composition of Patent Document 1 mentions that it is excellent in heat resistance during curing, it does not evaluate the elastic modulus at all.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Therefore, the technical problem that this disclosure aims to solve is to provide a propenyl-based resin, a resin composition, and a cured product thereof that can achieve a high degree of both excellent heat resistance and low modulus of elasticity during curing. [Means for solving the problem]

[0008] The propenyl resin according to the present invention is It contains a propenyl compound represented by the following general formula (1). [ka] (In general formula (1), M 1 Each of these independently represents a divalent organic group. M 2 This represents a divalent organic group, n is an integer from 0 to 9. m is an integer between 1 and 10. n+m is an integer between 1 and 10. R 1 and R 2 Each of these is an aromatic hydrocarbon group represented by the following general formula (2): [ka] In general formula (2), R 3 This represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. p is 0, 1, 2, 3, or 4. * represents a bond that connects to the oxygen atom in general formula (1). This allows for a high-level balance of excellent heat resistance and low modulus of elasticity during the curing process.

[0009] In one embodiment of the propenyl resin according to the present invention, M of general formula (1) 1 Or M 2However, it is one of the groups representing the following structures (i) to (iv). [ka]

[0010] In one embodiment of the propenyl resin according to the present invention, the softening point of the propenyl resin is 50°C or higher and 100°C or lower.

[0011] The resin composition according to the present invention comprises any of the above-mentioned propenyl resins and a maleimide resin.

[0012] In one embodiment of the resin composition according to the present invention, when measured with a differential scanning calorimetry (DSC), the exothermic peak of the resin composition is located at 175°C or below.

[0013] The cured product according to the present invention is a cured product of any of the above resin compositions.

[0014] The printed circuit board according to the present invention is made using any of the above resin compositions.

[0015] The semiconductor encapsulating material according to the present invention is made using any of the above resin compositions.

[0016] The build-up film according to the present invention is made using any of the above resin compositions. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a propenyl-based resin, a resin composition, and a cured product thereof that can achieve a high degree of both excellent heat resistance and low elastic modulus during curing. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 shows the MALDI-TOFMS spectrum of the propenyl resin (1) of Example 1. [Figure 2]Figure 2 is the GPC chart of the propenyl resin (1) of Example 1. [Figure 3] Figure 3 shows the 1H-NMR spectrum of the propenyl resin (1) of Example 1. [Figure 4] Figure 4 shows the 13C-NMR spectrum of the propenyl resin (1) of Example 1. [Figure 5] Figure 5 shows the MALDI-TOFMS spectrum of the propenyl resin (2) of Example 2. [Figure 6] Figure 6 is the GPC chart for the propenyl resin (2) of Example 2. [Figure 7] Figure 7 shows the 1H-NMR spectrum of the propenyl resin (2) of Example 2. [Figure 8] Figure 8 shows the 13C-NMR spectrum of the propenyl resin (2) of Example 2. [Figure 9] Figure 9 shows the MALDI-TOFMS spectrum of the propenyl resin (3) of Example 3. [Figure 10] Figure 10 is the GPC chart for the propenyl resin (3) of Example 3. [Figure 11] Figure 11 shows the 1H-NMR spectrum of the propenyl resin (3) of Example 3. [Figure 12] Figure 12 shows the 13C-NMR spectrum of the propenyl resin (3) of Example 3. [Figure 13] Figure 13 shows the FD-MS spectrum of the propenyl compound-containing mixture (1) of Comparative Example 1. [Figure 14] Figure 14 shows the 1H-NMR spectrum of the propenyl compound-containing mixture (1) of Comparative Example 1. [Figure 15] Figure 15 shows the 13C-NMR spectrum of the propenyl compound-containing mixture (1) of Comparative Example 1. [Modes for carrying out the invention]

[0019] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.

[0020] In the present invention, two or more embodiments can be arbitrarily combined.

[0021] [Terms] As used herein, the "reaction raw material" refers to a compound used to obtain a target compound through a chemical reaction such as combination or decomposition, and is a compound that partially constitutes the chemical structure of the target compound. Substances that play the role of chemical reaction aids such as solvents and catalysts are excluded. In particular, as used herein, the "reaction raw material" refers to a precursor for obtaining a target propenyl-based resin through a chemical reaction. As used herein, an "organic group" is a group whose chemical structure is constituted by an organic compound containing one or more carbon atoms in the form of a monovalent to tetravalent group. In other words, an "organic group" refers to an atomic group obtained by removing 1 to 4 hydrogen atoms from an organic compound containing one or more carbon atoms. Therefore, in addition to carbon atoms, the organic group may include one or more selected from the group consisting of hydrogen atoms, nitrogen atoms, oxygen atoms, halogen atoms, sulfur atoms, and phosphorus atoms. As used herein, the "linking group" represents a bond or atomic group for linking structural units, and examples include a divalent organic group, a single bond, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, or -N(R 0 )-. Here, the R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As used herein, an "aromatic hydrocarbon group" may be a hydrocarbon group having an n-valent (for example, monovalent to tetravalent) aromatic ring, and examples include an aryl group, an aralkyl group, or a group obtained by removing n - 1 arbitrary hydrogen atoms from the aryl group or the aralkyl group. The divalent or higher aromatic hydrocarbon group may preferably be a group obtained by removing 1 to 3 arbitrary hydrogen atoms from an aryl group or an aralkyl group. Examples of the aromatic rings include monocyclic aromatic rings, fused aromatic rings, and ring-aggregated aromatic rings. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of fused aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of ring-aggregated aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. In this specification, "aliphatic hydrocarbon group" refers to a group containing a hydrocarbon having one or more carbon atoms, and includes linear or branched hydrocarbon groups and monocyclic or polycyclic alicyclic hydrocarbon groups such as alkyl groups, alkenyl groups, alkylene groups, alkendiyl groups, and alkynediyl groups. Furthermore, one or more -CH2- groups in the alkyl group, alkenyl group, and alkynediyl group are -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, or -N(R 0 ) may be substituted with ). Therefore, “aliphatic hydrocarbon group” includes groups containing ether bonds, sulfide bonds, carbonyl groups, sulfinyl groups, sulfonyl groups, ester bonds, thioester bonds, amino groups, or amide bonds. In this specification, "alkyl group" may be linear, branched, or cyclic, and examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, or cyclononyl group. The aforementioned "alkyl group" includes a "cycloalkyl group," and examples of such "cycloalkyl groups" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, or an adamantyl group. In this specification, "alkenyl group" refers to a vinyl group, a 1-propenyl group (hereinafter also simply referred to as a propenyl group), a 2-propenyl group (hereinafter also simply referred to as an allyl group), an isopropenyl group, or a 2-methylpropenyl group (methallyl group), etc. In this specification, "alkoxy group" refers to, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group. In this specification, "aryl group" refers to a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, among others. In this specification, "halogen atom" refers to, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In this specification, "structural unit" refers to a (repeating) unit of chemical structure formed during a reaction or polymerization. In other words, in a compound formed by a reaction or polymerization, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization, and is commonly known as a residue.

[0022] Unless otherwise specified, the materials, components, compounds, catalysts, and solvents described herein may be used individually or in combination of two or more.

[0023] In this specification, unless otherwise specified, numerical ranges are intended to include the upper and lower limits of that range. For example, 50~100°C means the range of 50°C or more and 100°C or less.

[0024] (Propenyl resin) The propenyl resin according to the present invention is It contains a propenyl compound represented by the following general formula (1). [ka] In general formula (1), M 1 Each of these independently represents a divalent organic group. M 2 This represents a divalent organic group, n is an integer from 0 to 9. m is an integer between 1 and 10. n+m is an integer between 1 and 10. R 1 and R 2 Each of these is an aromatic hydrocarbon group represented by the following general formula (2): [ka] In general formula (2), R 3 This represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. p is 0, 1, 2, 3, or 4. * represents a bond that connects to the oxygen atom in general formula (1).

[0025] In the above general formula (1), M 1 Each of these independently represents a divalent organic group, M 2 This represents a divalent organic group. M1 and M 2 The organic group is preferably a hydrocarbon group, more preferably a cyclic hydrocarbon group, and even more preferably an aromatic hydrocarbon group. When the organic group is a cyclic hydrocarbon group, it tends to exhibit low dielectric properties and low hygroscopicity. Furthermore, when it is an aromatic cyclic hydrocarbon group, it tends to exhibit high heat resistance and high flame retardancy. The number of carbon atoms in the organic group is preferably 1 to 50, more preferably 6 to 40, even more preferably 10 to 30, and still more preferably 10 to 20. When the number of carbon atoms in the organic group is 10 or more, the distance between crosslinking points becomes longer, making it easier to suppress cracking that occurs during hardening. When the number of carbon atoms in the organic group is 20 or less, the viscosity becomes low, making it easier to fill the material with filler. Preferred M in general formula (1) 1 and M 2 Preferably, the chemical structure has a rigid portion (a so-called mesogenic structure, such as a cyclic group), more preferably a chemical structure having a cyclic group and a linear or branched linking group, and even more preferably a chemical structure having a cyclic group having 6 to 10 carbon atoms and a linear or branched aliphatic hydrocarbon group having 1 to 12 carbon atoms bonded to the carbon atoms in the cyclic group. M in general formula (1) 1 and M 2 As an example, it is preferable that the group is represented by the following formulas (I) to (IV). [ka] In the above equations (I) to (IV), * indicates a bond that connects to the oxygen atom in general formula (1). R e and R f Each of these independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. R 4 and R 5 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Each 'ne' independently represents an integer between 0 and 4, nf represents an integer between 0 and 6 (inclusive). In the groups represented by formulas (I) to (III) above, it is preferable that the linking group -* is bonded to the para (4th) carbon atom of each benzene ring. In the group represented by formula (IV) above, it is preferable that the linking group -* is bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of the naphthalene ring, respectively. In the chemical structure of the propenyl resin of this embodiment, M in general formula (1) 1 Or M 2 The presence of a cyclic group, particularly an aromatic ring, allows for the formation of a rigid mesogenic structure within the molecule, resulting in excellent heat resistance (especially at the glass transition temperature).

[0026] In the above general formula (1), M 1 Or M 2 It is particularly preferable that M is one of the groups representing the structure of the following formulas (i) to (iv), 1 and M 2 However, it is preferable that the group is one of the groups representing the structure of the following formulas (i) to (iv). [ka] In the above equations (i) to (iv), * indicates a bond that connects to the oxygen atom in general formula (1). In the groups represented by formulas (i) to (iii) above, it is preferable that the linking group -* is bonded to the para (4th) carbon atom of each benzene ring. In the group represented by formula (iv) above, it is preferable that the linking group -* is bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of the naphthalene ring, respectively. Note that M in general formula (1) 1 and M 2 This is included in the group (so-called residue) derived from the epoxy compound described later.

[0027] In the above general formula (1), R 1and R 2 Each of these is an aromatic hydrocarbon group represented by the following general formula (2): [ka] In general formula (2), R 3 This represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. p is 0, 1, 2, 3, or 4. * represents a bond that connects to the oxygen atom in general formula (1).

[0028] Preferred R in general formula (1) 3 For example, R 3 From the viewpoint of increasing the HOMO of the aromatic ring to which it is bonded, it is preferably an electron-donating group, and more preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Note that R in general formula (1) 1 and R 2 This is included in the group (so-called residue) derived from the alkenylphenol compound described later.

[0029] The propenyl resin of this embodiment more preferably contains one or more compounds selected from the group consisting of the following general formulas (1-i) to (1-iv). [ka] In general formulas (1-i) to (1-iv), n, m, R 1 and R 2 This is defined as in general formula (1).

[0030] (Properties of propenyl resins) <Double bond equivalent (g / mol) of propenyl resin> The double bond equivalent (g / mol) of the propenyl resin in this embodiment is preferably 100 g / mol or more and 1000 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less, and even more preferably 300 g / mol or more and 600 g / mol or less. In this specification, "double bond equivalent (g / mol)" is an indicator of the amount of double bonds contained in a molecule. For compounds of the same molecular weight, a smaller double bond equivalent value tends to indicate a greater amount of double bonds. The "double bond equivalent (g / mol)" is a calculated value obtained from the method described below and the method described in the Examples section. The preferred range for the double bond equivalent (g / mol) can be adjusted by appropriately rearranging the above upper and lower limits. -Method for calculating the double bond equivalent of propenyl resins- The double bond equivalent, which is the carbon-carbon double bond content in the propenyl resin of this embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0031] <Molecular weight of propenyl resins> The number-average molecular weight (Mn) of the propenyl resin in this embodiment is preferably in the range of 600 to 3000, more preferably in the range of 800 to 2500, and even more preferably in the range of 1000 to 2000. Furthermore, the weight-average molecular weight (Mw) of the propenyl resin is preferably in the range of 600 to 5000, more preferably in the range of 800 to 4000, and even more preferably in the range of 1000 to 3000. The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propenyl resin in this embodiment is preferably in the range of 1.0 to 2.5, and more preferably in the range of 1.0 to 2.0. -Method for measuring the molecular weight of propenyl resins- The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the propenyl resin in this embodiment are measured by gel permeation chromatography (hereinafter abbreviated as "GPC") as described in the examples below.

[0032] <Softening point of propenyl resins> The softening point (or melting point) of the propenyl resin in this embodiment is preferably in the range of 40°C to 120°C, more preferably in the range of 50°C to 110°C, and even more preferably in the range of 50°C to 100°C. -Method for measuring the softening point of propenyl resins- The softening point of the propenyl resin in this embodiment is measured using the ring-ball method in accordance with JIS K7234:1986, as described in the examples below. In one embodiment, the softening point of the propenyl resin is 50°C to 100°C.

[0033] (Another embodiment of propenyl resin) In this embodiment, the propenyl resin preferably uses an epoxy compound and an alkenylphenol compound as reaction raw materials.

[0034] As the epoxy compound, for example, a compound having a structure represented by the following general formula (3) is preferred. [ka] In the above general formula (3), M 6 This represents a divalent organic group, L 3 and L 4 Each of these is independently a single bond or one or more -CH2- groups, and -O-, -C(=O)-, or -N(R 0 This represents an alkylene group having 1 to 6 carbon atoms, which may be substituted with )-.

[0035] In the above general formula (3), M 6 This is M in the general formula (1) mentioned above. 1 and M 2 Since it is the same as, M in the general formula (1) above 1 and M 2 We will use the content of [this document] as a reference.

[0036] As the aforementioned alkenylphenol compound, for example, a compound having a structure represented by the following general formula (4) is preferred. [ka] In the above general formula (4), R 3 This represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. p is 0, 1, 2, 3, or 4.

[0037] In the above general formula (4), R 3 This is R in the general formula (2) mentioned above. 3 Since it is the same as, R in the general formula (2) above 3 We will use the content of [this document] as a reference.

[0038] <Epoxy compounds> In this embodiment, the propenyl resin preferably uses a divalent epoxy compound as a reaction raw material. The divalent epoxy compound is not particularly limited as long as it is a compound having two glycidyl groups in one molecule. Hereinafter, a compound having two glycidyl groups in one molecule will simply be referred to as an epoxy compound. Furthermore, it is preferable that the epoxy compound is a compound having a structure represented by general formula (3).

[0039] Specific examples of epoxy compounds include glycidyl ether type epoxy resins obtained by the condensation of epichlorohydrin with divalent phenols such as bisphenols or divalent alcohols, such as bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenylaralkyl type, biphenylaralkyl type, and dicyclopentadienephenol type. Other examples include glycidyl ester type epoxy resins obtained by the condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids, glycidylamine type epoxy resins obtained by the reaction of epichlorohydrin with amines and hydantoins, and epoxy resins modified by various methods, but are not limited to these. In this embodiment, the molecular weight of the epoxy compound is preferably 100 to 600, preferably 150 to 500, and preferably 200 to 400.

[0040] The epoxy compound of this embodiment is more preferably represented by the following general formula (5). [ka] In the above general formula (5), M 7 This represents a divalent organic group. This represents a group selected from the group consisting of the above formulas (I) to (IV).

[0041] In the above general formula (5), M 7 This is M in the general formula (1) mentioned above. 1 and M 2 Since it is the same as, M in the general formula (1) above 1 and M 2 We will use the content of [this document] as a reference.

[0042] <Alkenylphenol compounds> In this embodiment, the propenyl resin preferably uses an alkenylphenol compound as a reaction raw material. The alkenylphenol compound refers to an aromatic compound in which an alkenyl group (which may be substituted), a phenolic hydroxyl group, and the alkenyl group and the hydroxyl group are bonded, and it is preferable that the alkenylphenol compound is a compound having a structure represented by general formula (4). Examples of alkenylphenol compounds include 2-allylphenol, 4-allylphenol, 2-(1-propenyl)phenol, 4-(1-propenyl)phenol, 4-(1-propenyl)-2,6-xylenol, eugenol, isoeugenol, hydroxycavicol, and propenylguaetol. Of these alkenylphenol compounds, 4-(1-propenyl)-2,6-xylenol, eugenol, and isoeugenol are preferred, eugenol and isoeugenol are more preferred, and isoeugenol is even more preferred. Eugenol is a component found in spices such as cloves and bay leaves, and is a biomass compound derived from natural products that is classified as a monophenylpropanoid. Therefore, by using eugenol, or isoeugenol obtained by the isomerization reaction of eugenol, as a reaction raw material, the environmental burden can be reduced. When the alkenylphenol compound in this embodiment is isoeugenol, plant-derived isoeugenol can be incorporated into the chemical structure of the target propenyl resin, thereby providing a compound that reduces environmental impact.

[0043] (Propenyl resin) This disclosure relates to a propenyl resin containing a propenyl compound represented by general formula (1). The content of the propenyl compound represented by general formula (1) in this embodiment can be calculated in area % of GPC by the method described later, and is preferably 20 area % or more, more preferably 40 area % or more and 100 area % or less, and even more preferably 60 area % or more and 100 area % or less, relative to the total amount of the propenyl resin (100 area %). The resin can exert its effect if it contains 20 area percent or more of the propenyl compound represented by general formula (1). Components other than the propenyl compound represented by general formula (1) contained in the propenyl resin may be compounds in which n and m are 0 in general formula (1), by-products and polymers generated in the manufacturing process of the reaction raw materials.

[0044] (Method for manufacturing propenyl resins) The following describes the method for producing the propenyl resin of this disclosure. The method for producing the propenyl resin of this embodiment is not particularly limited as long as it is a method that can produce a resin containing the compound represented by general formula (1). For example, as a method for producing the propenyl resin of this disclosure, the epoxy compound represented by general formula (3) and the alkenylphenol compound represented by general formula (4) can be used as reaction raw materials. Furthermore, the method for producing the propenyl resin can take into consideration known synthesis conditions and synthesis methods.

[0045] An example of a reaction scheme for producing the propenyl resin of this disclosure is shown below. In Scheme 1 below, an example is shown in which a bisphenol A type epoxy resin and isoeugenol are used as the epoxy compound and alkenylphenol compound, respectively. [ka] In the first step of Scheme 1, a bisphenol A type epoxy resin is reacted with isoeugenol to obtain intermediate 1. A compound (mono-epoxy compound) is also prepared by reacting one of the glycidyl groups of the bisphenol A type epoxy resin with the hydroxyl group of isoeugenol. Then, in the second step of Scheme 1, intermediate 1 is reacted with the mono-epoxy compound to obtain propenyl compound (1-ia), which is one of the propenyl compounds of this embodiment.

[0046] An example of a reaction scheme for producing another propenyl compound of this disclosure is shown below. Scheme 2 below shows an example in which the propenyl compound (1-ia) obtained in Scheme 1 is further reacted with a monoepoxy compound. [ka] In Scheme 2, the propenyl compound (1-ia) is reacted with the monoepoxy compound of Scheme 1. By repeating this reaction, one of the propenyl compounds of this embodiment, which has repeating m and n units of general formula (1), is obtained.

[0047] In the propenyl compound of this embodiment, the number of n+m (i.e., R of general formula (1)) 2 If we define the compound with 1 double bond as n1, and similarly, the compound with 2 n+m is the n2, the compound with 3 n+m is the n3, and so on, then structural isomers of the propenyl compound exist for n2 and above. For example, the propenyl compound (1-ia) shown in Scheme 1 has hydroxyl groups in three locations: on the right side of the molecule, in the center of the molecule, and on the left side. When the glycidyl group of the monoepoxy compound shown in Scheme 1 reacts with the hydroxyl groups on the right side, in the center, and on the left side of the propenyl compound (1-ia), the following propenyl compounds (1-i-1), (1-i-2), and (1-i-3) are produced, respectively. The amount produced is similar for propenyl compound (1-i-1) and propenyl compound (1-i-2), while the amount produced for propenyl compound (1-i-3) tends to be less than that of propenyl compound (1-i-1) and propenyl compound (1-i-2). [ka]

[0048] An example of a method for producing the propenyl resin of this disclosure is a manufacturing method comprising, for example, the following steps (1) and (2) which may be provided as needed. Step (1): A step of reacting an epoxy compound with an alkenylphenol compound as reaction raw materials; Step (2): A step of purifying the reaction product from a mixture containing the reaction product of the epoxy compound and the alkenylphenol compound. Specifically, the method for producing the propenyl resin of this embodiment preferably comprises the steps of (1-1) reacting an epoxy compound with an alkenylphenol compound in the presence of a basic compound, and (2-1) purifying the reaction product produced in step (1-1) using an acidic aqueous solution and an organic solvent. The following describes each step of the method for producing the propenyl resin of this disclosure.

[0049] <Process (1)> Regarding the blending ratio of the epoxy compound and the alkenylphenol compound, considering the balance of the moldability and curability properties of the resulting propenyl resin, it is preferable that the molar ratio of hydroxyl groups of the alkenylphenol compound to 1 mole of glycidyl groups of the epoxy compound is 0.50 to 1.00 moles, more preferably 0.60 to 0.95 moles, and even more preferably 0.70 to 0.90 moles. Furthermore, the specific methods for carrying out the above reaction generally involve either charging all the raw materials together and allowing them to react at a predetermined temperature, or charging the alkenylphenol compound and the basic compound, and allowing the epoxy compound to react dropwise while maintaining the predetermined temperature. In this case, the dropwise addition time is usually 0.5 to 24 hours, with 0.5 to 4 hours being preferable.

[0050] The basic compound used in step (1) of this embodiment can be an inorganic basic compound, an organic basic compound, or the like. Examples of inorganic basic compounds include alkali metal hydroxides such as potassium and sodium; alkali metal carbonates such as potassium and sodium; alkaline earth metal hydroxides such as calcium and barium; and carbonates of calcium and barium. Examples of organic basic compounds include phosphines such as triphenylphosphine. From the viewpoint of ease of purification by washing with water, alkali metal hydroxides (e.g., potassium hydroxide, sodium hydroxide, lithium hydroxide, etc.) are preferred as the basic compound in this embodiment, and potassium hydroxide and sodium hydroxide are more preferred. The basic compound is preferably used in an amount ranging from 0.01 to 10 parts by mass, and more preferably in an amount ranging from 1 to 5% by mass, based on 100 parts by mass of the total of the epoxy compound and the alkenylphenol compound.

[0051] The phase transfer catalyst used in step (1) of this embodiment may specifically include quaternary ammonium salts, quaternary phosphonium salts, or crown ethers. Quaternary ammonium salts and quaternary phosphonium salts are particularly preferred due to their excellent catalytic activity, and specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and tetrabutylphosphonium bromide. When used, these basic catalysts may be used in the form of an aqueous solution of about 10% to 55% by mass, or in solid form. The amount of the phase transfer catalyst is blended in the range of 0 to 15 parts by mass per 100 parts by mass of the total amount of raw materials to be charged (= total amount of epoxy compound and alkenylphenol compound). In step (1) of this embodiment, it is preferable to react the epoxy compound with the alkenylphenol compound using an organic solvent. Examples of such organic solvents include ketones such as methyl isobutyl ketone, acetone, methyl ethyl ketone (MEK), cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; and aromatic solvents such as benzene, toluene, and xylene. These may be used individually or in combination.

[0052] In step (1) of this embodiment, the reaction temperature between the epoxy compound and the alkenylphenol compound can normally be in the range of 50 to 170°C, but 100 to 140°C is preferred in order to avoid side reactions such as the formation of polymers and hydrolysis of the glycidyl group. In step (1) of this embodiment, the reaction time between the epoxy compound and the alkenylphenol compound is usually in the range of 0.5 to 24 hours, but preferably in the range of 1 to 6 hours, because if the reaction is too short, the reaction will not proceed completely, and if it is too long, side reactions such as thermal decomposition of the product will occur. Therefore, in step (1) of this embodiment, it is more preferable to carry out the reaction while stirring at a temperature range of 100 to 140°C for a period of 1 to 6 hours. Furthermore, it is preferable to carry out the reaction in step (1) under an inert gas atmosphere such as nitrogen, helium, or argon.

[0053] <Process (2)> Step (2) in this embodiment is performed as needed and is a step to recover the reaction product obtained in step (1). An acidic aqueous solution is added to the solution obtained in step (1) which contains the reaction product and an organic solvent, and after removing the salt of the basic compound and impurities by neutralization, washing with water, etc. using the acidic aqueous solution, dehydration is performed by azeotropy, and after microfiltration, the solvent and unreacted compounds are removed by distillation under reduced pressure to obtain the reaction product. A dehydrating agent may also be used during dehydration if necessary.

[0054] The stability of the resulting compound can be improved by washing the reaction product with an acidic aqueous solution. Specific examples of acids used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid, as well as their salts (e.g., alkali metal or alkaline earth metal salts). These acids may be used individually or in combination of two or more types. Examples of dehydrating agents used in step (2) of this embodiment include inorganic salts such as sodium sulfate and magnesium sulfate, and porous ceramics such as molecular sieves.

[0055] [Resin composition] The propenyl resin of this disclosure can be used to prepare resin compositions. That is, the resin composition of this disclosure preferably contains the above-described propenyl resin and a maleimide resin. Because the propenyl resin of this embodiment has excellent solvent solubility, compatibility with maleimide resins, fluidity when heated and melted, and handling properties, the resin composition containing the propenyl resin has excellent moldability and curability.

[0056] In the resin composition of this embodiment, the content of the propenyl resin containing the propenyl compound represented by general formula (1) is preferably 20 to 90% by mass, and more preferably 40 to 60% by mass, based on the total amount (100% by mass) of the resin composition.

[0057] The method for producing the resin composition of this embodiment is not particularly limited. For example, melt kneading is preferred as a method for producing the resin composition. Examples of equipment used in melt kneading include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batch or continuously. Generally, when manufacturing a resin composition, the resin composition is heated above its melting point and thoroughly melted and mixed using an extruder, kneader, rolls, etc., until it becomes uniform. On the other hand, because the propenyl resin of this embodiment has a low softening point (or melting point), it can be mixed with maleimide resins, etc., at conventional mixing temperatures (for example, 110°C (preferably 100°C)), and a uniform composition can be produced. As a result, by curing the resin composition of this embodiment, a cured product with excellent appearance and heat resistance can be produced.

[0058] (Maleimide resin) The maleimide resin in this embodiment is not particularly limited as long as it has a maleimide group. Examples of the maleimide resin include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimoidphenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 2,2'-bis[4-(4-maleimoidphenoxy)phenyl]propane. Other maleimide resins include the maleimide described in International Publication No. 2020 / 217679, the maleimide resin described in Japanese Patent No. 7140307, ​​the maleimide resin (A) described in Japanese Patent Application Publication No. 2023-146886, the acid-modified maleimide resin (A) described in International Publication No. 2020 / 166212, the first maleimide compound (A1) and / or the second maleimide compound (A2) described in Japanese Patent Application Publication No. 2023-152757, and the polymaleimide compound (A) described in Japanese Patent Application Publication No. 2023-152755. In the resin composition of this embodiment, the maleimide resin content is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, even more preferably 20 to 70% by mass, and particularly preferably 25 to 65% by mass, based on the total amount (100% by mass) of the resin composition. When the maleimide resin content is within the above range, excellent moldability, heat resistance, and mechanical strength are achieved. The upper and lower limits of the maleimide resin content can be adjusted as appropriate.

[0059] (Optional additives) The resin compositions of this disclosure may contain a curing agent other than a propenyl resin or a maleimide resin, and may further contain various compounding agents such as a curing accelerator, a silane coupling agent, a mold release agent, a pigment, an emulsifier, a non-halogenated flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus flame retardant, an organophosphorus flame retardant, a halogenated flame retardant), and a solvent, as needed. Furthermore, insofar as it does not impair the purpose of this disclosure, other known resin components may be included in addition to the propenyl resin and the maleimide resin. Such known resin components may include epoxy resins, phenolic resins, activated ester resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene-maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, and the like, as appropriate.

[0060] In one embodiment of the resin composition, when measured by differential scanning calorimeter (DSC), the exothermic peak of the resin composition is located at 175°C or below. In another embodiment of the resin composition, when measured by DSC, the exothermic peak of the resin composition is located at 175°C or below, and also exists in the portion above 175°C.

[0061] (Preferred properties and composition of the resin composition) When manufacturing semiconductor encapsulating materials using the resin composition of this embodiment, transfer molding is commonly used. This transfer molding method involves heating and softening the resin composition in a plunger, then allowing the softened resin composition to flow through internal mold channels such as gates, sprues, and runners, and finally pushing it into a heated mold cavity to harden. Therefore, the fluidity of the resin composition is crucial in transfer molding. If the fluidity is not appropriately adjusted for the desired shape of the semiconductor encapsulant, problems such as unfilled areas in the mold cavity or molding defects such as voids and cracks in the molded product are likely to occur. As described above, the resin composition of this embodiment contains a propenyl resin that can be cured at low temperatures and has a relatively low softening point (or melting point), so transfer molding can be performed at a relatively low temperature (for example, 175°C or below). Furthermore, as described above, the propenyl resin of this embodiment can undergo a synergistic reaction with the maleimide resin via a highly reactive Diels-Alder reaction, so the resin composition of this embodiment can be cured in a relatively short time (for example, within 180 seconds (more preferably within 120 seconds, even more preferably within 100 seconds, and particularly preferably within 50 seconds)). In the resin composition of this embodiment, if the resin composition contains a propenyl resin and a maleimide resin, and the maleimide resin content is 10 to 80% by mass and the propenyl resin content is 90 to 20% by mass relative to the total amount (100% by mass) of the resin composition, the gel time of the resin composition is preferably within 100 seconds, and more preferably within 50 seconds. In the resin composition of this embodiment, if the resin composition contains a propenyl resin and a maleimide resin, and the maleimide resin content is 10 to 80% by mass and the propenyl resin content is 90 to 20% by mass relative to the total amount (100% by mass) of the resin composition, the DSC exothermic peak of the resin composition is preferably 175°C or lower, and more preferably 165°C or lower. In the resin composition of this embodiment, the total content of propenyl resin and maleimide resin is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass, based on the total amount (100% by mass) of the resin composition. In the resin composition of this embodiment, the total content of the propenyl resin, maleimide resin, and any additive components is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass, based on the total amount (100% by mass) of the resin composition.

[0062] [Cured product] The cured product of this disclosure is a cured product of the resin composition. The cured product can be obtained by curing the resin composition. The resin composition can be obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent) and can be easily cured in the same manner as conventionally known methods. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.

[0063] The resin compositions of this disclosure can be used in various applications, such as semiconductor encapsulation materials, semiconductor devices, prepregs, printed circuit boards, build-up films, build-up substrates, adhesives, resist materials, matrix resins for fiber-reinforced resins, heat-resistant materials, and electronic materials. For printed circuit boards, semiconductor encapsulation materials, and build-up films, see, for example, Japanese Patent Application Publication No. 2024-010251. For heat-resistant materials and electronic materials, see, for example, Japanese Patent Application Publication No. 2024-004392. [Examples]

[0064] The present invention will be described in more detail below with reference to examples, but these examples are for illustrative purposes only and do not limit the present invention in any way.

[0065] (1) Measurement of softening point The softening points of the propenyl resins obtained in the examples were measured in accordance with JIS K7234:1986.

[0066] (2) Measurement of double bond equivalent (iodine value) The double bond equivalents of the propenyl resins obtained in the examples were calculated in accordance with JIS K 0070.

[0067] (3) MALDI-TOFMS measurement The MALDI-TOFMS spectra of the propenyl resins obtained in the examples were measured using the following measuring equipment and conditions. "Measuring device" JEOL's "JMS-S3000" "Measurement conditions" Measurement range: m / z = 500.00~5000.00 Matrix: 2,5-dihydroxybenzoic acid (DHB) Cationic agent: Sodium trifluoroacetate (TFANa)

[0068] (4) GPC measurement The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the propenyl resins obtained in the examples were calculated using the following measuring equipment and conditions. "Measuring device" Tosoh Corporation's "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation Guard Column "HXL-L" + Tosoh Corporation's "TSK-GEL G4000HXL" + Tosoh Corporation's "TSK-GEL G3000HXL" + Tosoh Corporation's "TSK-GEL G2000HXL" + Tosoh Corporation's "TSK-GEL G2000HXL" Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 1.0ml / min Sample: A tetrahydrofuran solution containing 1.0% by mass of the propenyl resin obtained in the examples, filtered through a microfilter (50 μl).

[0069] (5)NMR measurement The propenyl resin obtained in the example 1 H-NMR spectrum and 13 The 1C-NMR spectrum was measured using the following measuring instrument and conditions. "Measuring device" Manufactured by JEOL “JNM-ECA500” "Measurement conditions" 1 H-NMR spectrum Resonance frequency: 500MHz Total number of times: 16 Solvent: Chloroform-d Sample concentration: 4% by mass 13 C-NMR spectrum Resonance frequency: 125MHz Total number of times: 2000 Solvent: Chloroform-d Sample concentration: 30% by mass

[0070] (6) FD-MS measurement The FD-MS spectra of the propenyl compound-containing mixtures obtained in the comparative example were measured using the following measuring equipment and conditions. "Measuring device" JEOL Ltd. "JMS-T100GC AccuTOF" "Measurement conditions" Measurement range: m / z = 4.00~2000.00 Rate of change: 51.2 mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 sec

[0071] The raw materials used in the example are as follows: (Epoxy compound) • Epoxy compound 1: Manufactured by DIC Corporation, product name "Epiclon® EXA-850CRP", mainly composed of the following compound 1 (molecular weight: 340) • Epoxy compound 2: Manufactured by DIC Corporation, product name "Epiclon® EXA-830CRP", mainly composed of the following compound 2 (a mixture of ortho and para compounds, molecular weight: 312) • Epoxy compound 3: Manufactured by DIC Corporation, product name "Epiclon (registered trademark) HP-4032D", mainly composed of the following compound 3 (molecular weight: 272) [ka] (Alkenylphenol compounds) • Isoeugenol: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Isoeugenol" (Maleimide resin) • Maleimide resin: Polyphenylmethane-type maleimide resin, manufactured by Yamato Chemical Industries, Ltd., product name "BMI-2300"

[0072] <Comparative Example 1: Synthesis of Propenyl Compound (1)> In a flask equipped with a thermometer, fractionation column, and stirrer, 300 g (1.83 mol) of isoeugenol as an alkenylphenol compound, 15 g (0.18 mol) of 49% sodium hydroxide, 285 g of epoxy compound 1 (moles of glycidyl groups: 1.65 mol), 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone were added. The system was heated to 120°C while purging with nitrogen gas, and stirring was continued for 3 hours. After the reaction was complete, the system was cooled to 80°C. Next, 300 g of 12% monosodium phosphate aqueous solution was added to the flask. The mixture was then stirred for 15 minutes, allowed to stand, and the aqueous layer was removed by liquid-liquid extraction. Water was then added to the methyl isobutyl ketone layer in which the reaction products were dissolved. The mixture was stirred for 15 minutes, allowed to stand, and the aqueous layer was removed by liquid-liquid extraction. Dehydration was performed by azeotropic distillation. Next, the reaction product was microfiltered. Then, the solvent was removed under reduced pressure to obtain a propenyl compound-containing mixture (1). The propenyl compound-containing mixture (1) contained 89 area % of the propenyl compound (1) having the following structure. FD-MS spectrum of the propenyl compound-containing mixture (1), 1 H-NMR spectrum and 13 The 1C-NMR spectra are shown in Figures 13, 14, and 15, respectively. The physical properties of the propenyl compound-containing mixture (1) are as follows. Softening point: 60℃ Double bond equivalent: 341 g / mol [ka]

[0073] <Comparative Example 2: Synthesis of Propenyl Compound (2)> In Comparative Example 1, the reaction and processing were carried out in the same manner as in Comparative Example 1, except that epoxy compound 1 was changed to epoxy compound 2, to obtain a propenyl compound-containing mixture (2). The propenyl compound-containing mixture (2) contained 85 area % of propenyl compound (2) having the following structure. The chemical structure and molecular weight of propenyl compound (2) were determined by FD-MS spectroscopy, as in Comparative Example 1. 1 H-NMR spectrum and 13 This was confirmed by 13C-NMR spectroscopy. The physical properties of the propenyl compound-containing mixture (2) are as follows: Softening point: 58℃ Double bond equivalent: 328 g / mol [ka]

[0074] <Comparative Example 3: Synthesis of Propenyl Compound (3)> In Comparative Example 1, the reaction and treatment were carried out in the same manner as in Comparative Example 1, except that epoxy compound 1 was changed to epoxy compound 3, to obtain a propenyl compound-containing mixture (3). The propenyl compound-containing mixture (3) contained 88 area % of propenyl compound (3) having the following structure. The chemical structure and molecular weight of propenyl compound (3) were confirmed in the same manner as in Comparative Example 1. The physical properties of the propenyl compound-containing mixture (3) are as follows. Softening point: 71℃ Double bond equivalent: 310 g / mol [ka]

[0075] <Example 1: Synthesis of propenyl resin (1)> In Comparative Example 1, the reaction and processing were carried out in the same manner as in Comparative Example 1, except that the amount of isoeugenol was changed to 190 g (1.16 mol), to obtain a propenyl resin (1) containing a propenyl compound (1) having the following structure. The MALDI-TOFMS spectrum and GPC chart of the obtained propenyl resin (1) are shown below. 1 H-NMR spectrum and13 The 1C-NMR spectra are shown in Figures 1, 2, 3, and 4, respectively. The physical properties of the propenyl resin (1) are as follows. Softening point: 75℃ Double bond equivalent: 423 g / mol Mn=1438 Mw=2158 Mw / Mn = 1.501 [ka]

[0076] <Example 2: Synthesis of propenyl resin (2)> In Comparative Example 2, the reaction and processing were carried out in the same manner as in Comparative Example 2, except that the amount of isoeugenol was changed to 216 g (1.32 mol), to obtain a propenyl resin (2) containing a propenyl compound (2) having the following structure. The MALDI-TOFMS spectrum and GPC chart of the obtained propenyl resin (2) are shown below. 1 H-NMR spectrum and 13 The 1C-NMR spectra are shown in Figures 5, 6, 7, and 8, respectively. The physical properties of the propenyl resin (2) are as follows. Softening point: 67℃ Double bond equivalent: 368 g / mol Mn=1137 Mw=1580 Mw / Mn = 1.390 [ka]

[0077] <Example 3: Synthesis of propenyl resin (3)> In Comparative Example 3, the reaction and processing were carried out in the same manner as in Comparative Example 3, except that the amount of isoeugenol was changed to 243 g (1.49 mol), to obtain a propenyl resin (3) containing a propenyl compound (3) having the following structure. The MALDI-TOFMS spectrum and GPC chart of the obtained propenyl resin (3) are shown below. 1 H-NMR spectrum and 13The 1C-NMR spectra are shown in Figures 9, 10, 11, and 12, respectively. The physical properties of the propenyl resin (3) are as follows. Softening point: 75℃ Double bond equivalent: 321 g / mol Mn=915 Mw=1115 Mw / Mn = 1.218 [ka]

[0078] <Preparation of resin composition> Each component was blended according to the composition shown in Table 1, and the mixture was melt-kneaded at 90°C for 5 minutes using two rollers to prepare the resin compositions of Examples 4-6 and Comparative Examples 4-6. [Table 1]

[0079] The flexural modulus, flexural strength, and glass transition temperature of each prepared resin composition were measured as follows. The measurement results are shown in Table 1.

[0080] (Measurement of DSC fever peak) The DSC exothermic peaks of each resin composition were measured using the following measuring equipment and conditions. "Measuring device" Mettler-Toledo "DSC3" "Measurement conditions" Measurement range: 30~300℃ Heating rate: 10K / min Nitrogen flow rate: 40 mL / min Sample amount: approximately 5 mg

[0081] (Preparation of hardened material 1) Each resin composition was poured into a mold measuring 11 cm × 9 cm × 4.0 mm and molded using a press at a temperature of 175°C for 10 minutes. The molded product was removed from the mold. Then, it was cured at a temperature of 175°C for 5 hours to obtain cured resin composition 1 (thickness 4.0 mm).

[0082] (Measurement of flexural modulus and flexural strength) The prepared cured material 1 was cut to a size of 10 mm in width and 80 mm in length to form test specimen 1. The flexural modulus (MPa) and flexural strength (MPa) of test specimen 1 were then measured according to JIS K7171. A lower flexural modulus indicates superior low modulus properties. A higher flexural strength indicates superior mechanical properties.

[0083] (Preparation of hardened material 2) In preparing cured product 1, the procedure was carried out similarly except that the mold was changed to a mold measuring 11 cm × 9 cm × 2.4 mm, and cured product 2 (thickness 2.4 mm) of the resin composition was obtained.

[0084] (Measurement of glass transition temperature (°C)) The cured material 2 was cut into pieces measuring 5 mm in width and 54 mm in length, and these were designated as test specimens 2. Test specimens 2 were then measured using a viscoelasticity analyzer (DMA: Rheometric RSAII solid viscoelasticity analyzer, rectangular tension method, frequency 1 Hz, heating rate 3 °C / min) to determine the glass transition temperature (°C) at which the change in elastic modulus was maximum (the tanδ change rate was greatest). A higher glass transition temperature (°C) indicates superior heat resistance.

[0085] According to the present invention, we have been able to provide a propenyl-based resin, a resin composition, and a cured product thereof that can achieve a high degree of both excellent heat resistance and low elastic modulus during curing. [Industrial applicability]

[0086] According to the present invention, it is possible to provide a propenyl-based resin, a resin composition, and a cured product thereof that can achieve a high degree of both excellent heat resistance and low elastic modulus during curing.

Claims

1. A propenyl resin containing a propenyl compound represented by the following general formula (1). 【Chemistry 1】 (In general formula (1), M １ Each of these independently represents a divalent organic group. M ２ This represents a divalent organic group, n is an integer from 0 to 9. m is an integer between 1 and 10. n+m is an integer from 1 to 10. R １ and R ２ Each of these is an aromatic hydrocarbon group represented by the following general formula (2): 【Chemistry 2】 In general formula (2), R ３ This represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. p is 0, 1, 2, 3, or 4. * represents the bond that connects to the oxygen atom in general formula (1).

2. M １ or M ２ The propenyl resin according to claim 1, wherein the group is one of the following structures represented by (i) to (iv). 【Transformation 3】

3. The propenyl resin according to claim 1, wherein the softening point of the propenyl resin is 50°C or higher and 100°C or lower.

4. A resin composition comprising a propenyl resin according to any one of claims 1 to 3 and a maleimide resin.

5. The resin composition according to claim 4, wherein, when measured with a differential scanning calorimeter (DSC), the exothermic peak of the resin composition is located at 175°C or below.

6. A cured product of the resin composition according to claim 4.

7. A printed circuit board comprising the resin composition described in claim 4.

8. A semiconductor encapsulation material comprising the resin composition described in claim 4.

9. A build-up film made using the resin composition described in claim 4.

Images