Curing composition, cured product thereof, and curing improver

Abstract

A curable composition comprising: a polymerizable compound (A) having a condensed polycyclic hydrocarbon structure and 2 or more polymerizable functional groups bonded to the condensed polycyclic hydrocarbon structure, and a polymerizable compound (B) having a condensed polycyclic hydrocarbon structure and 2 or more maleimide groups bonded to the condensed polycyclic hydrocarbon structure, the polymerizable compound (A) and the polymerizable compound (B) comprising the same condensed polycyclic hydrocarbon structure.

Description

Technical Field

[0001] This invention relates to curable compositions, cured products thereof, and curability enhancers. Background Technology

[0002] Tricyclodecanediethanol diacrylate (hereinafter sometimes referred to as "TCD-DA") is liquid at room temperature, and its cured product exhibits a high glass transition temperature (Tg), low water absorption, and flexibility. Therefore, TCD-DA is used as a raw material for various resin materials such as coating materials, optical lenses, and dental materials. Several techniques for using TCD-DA have been proposed (for example, see Patent Documents 1 and 2 below).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2012-177877

[0006] Patent Document 2: International Publication No. WO2017 / 170252 Summary of the Invention

[0007] When using cured products made from TCD-DA for the aforementioned applications, it is generally preferable that the surface of the cured product is non-sticky (tacky). However, in order to fully cure (polymerize) TCD-DA using light, it is necessary to increase the cumulative light intensity, and there is room for improvement from the viewpoint of productivity or energy efficiency. In addition, TCD-DA is sometimes used in combination with other polymerizable compounds, but sometimes the following problems occur: the pot life of the curable resin composition decreases, the flexibility of the cured product decreases, and the transparency decreases due to residual crystals or phase separation in the cured product. Therefore, there is a need to develop a technology that can both leverage the advantages of TCD-DA and improve the ease of curing TCD-DA under atmospheric conditions (i.e., in an oxygen atmosphere) (hereinafter sometimes referred to as "curability").

[0008] The purpose of this invention is to solve the above-mentioned problems and provide a curable composition with excellent curability, the cured product thereof, and a curability improver.

[0009] The inventors conducted in-depth research to solve the aforementioned problems. As a result, they discovered that by using a polymeric compound (A) such as TCD-DA and a polymeric compound (B) having a basic skeleton shared with that compound and containing maleimide groups, the aforementioned problems can be achieved, thus completing the present invention.

[0010] <1>

[0011] A curable composition comprising:

[0012] Polymerizable compound (A) having a fused polycyclic hydrocarbon structure and two or more polymerizable functional groups bonded to the aforementioned fused polycyclic hydrocarbon structure, and

[0013] Polymerizable compound (B) having a fused polycyclic hydrocarbon structure and two or more maleimide groups bonded to the fused polycyclic hydrocarbon structure.

[0014] The polymeric compound (A) and the polymeric compound (B) described above contain the same fused polycyclic hydrocarbon structure.

[0015] <2>

[0016] According to the curable composition described in <1> above, the fused polycyclic hydrocarbon structure of the polymeric compound (A) and the fused polycyclic hydrocarbon structure of the polymeric compound (B) are aliphatic fused polycyclic hydrocarbon structures.

[0017] <3>

[0018] According to the curable composition described in <1> or <2> above, at least one of the two or more polymeric functional groups of the polymeric compound (A) is a group having an olefinic unsaturated double bond.

[0019] <4>

[0020] The curable composition according to any one of <1> to <3> above, wherein the polymeric compound (A) comprises a compound represented by the following formula (I).

[0021]

[0022] (In formula (I), R) 1 R 2 Each can independently represent H or CH3, and n and m can independently be integers from 1 to 3.

[0023] <5>

[0024] The curable composition according to any one of <1> to <4> above, wherein the polymeric compound (B) comprises a compound represented by the following formula (II).

[0025]

[0026] (In equation (II), o, p, q, and r are each an independent integer from 1 to 3.)

[0027] <6>

[0028] The curable composition according to any one of <1> to <5> above, wherein it comprises a filler.

[0029] <7>

[0030] A curing improver comprising a compound represented by the following formula (II).

[0031]

[0032] (In equation (II), o, p, q, and r are each an independent integer from 1 to 3.)

[0033] <8>

[0034] A cured product is formed by curing the curable composition described in any one of <1> to <6> above.

[0035] According to the present invention, curable compositions with excellent curability, cured products thereof, and curability improvers can be provided. Detailed Implementation

[0036] The present invention will be described below, but its scope is not limited to this description. Throughout this specification, when referring to "(meth)acrylate," it means "acrylate" or "methacrylate," and when referring to "(meth)acrylate alkyl," it means "alkyl acrylate" or "alkyl methacrylate," and "(meth)acryloyl" means "acryloyl" or "methacryloyl." Furthermore, unless otherwise specified, the term "alkyl" includes straight-chain, branched-chain, and alicyclic alkyl groups. Additionally, when using "~" to indicate a numerical range, the values ​​at both ends are included.

[0037] Curing Compositions

[0038] The curable composition of this embodiment includes:

[0039] Polymerizable compound (A) having a fused polycyclic hydrocarbon structure and two or more polymerizable functional groups bonded to the aforementioned fused polycyclic hydrocarbon structure, and

[0040] Polymerizable compound (B) having a fused polycyclic hydrocarbon structure and two or more maleimide groups bonded to the fused polycyclic hydrocarbon structure.

[0041] The polymeric compound (A) and the polymeric compound (B) described above contain the same fused polycyclic hydrocarbon structure.

[0042] The curable composition of this embodiment improves atmospheric curability by combining a polymeric compound (A) with a polymeric compound (B) having maleimide groups. Although the mechanism by which atmospheric curability is achieved by combining polymeric compounds (A) and (B) is not yet certain, it is speculated that maleimide groups are more likely to generate free radicals using ultraviolet light, so the polymerization reaction is more dominant than the effect of oxygen inhibition even in the atmosphere, thereby improving curability.

[0043] Thus, especially under an oxygen-rich atmosphere, the polymeric composition of this embodiment can form a cured product with less cumulative light compared to conventional methods using only TCD-DA. Therefore, the polymeric composition of this embodiment exhibits excellent productivity and energy efficiency during curing.

[0044] Furthermore, the polymerizable composition of this embodiment can suppress cracking in the resulting cured product and has excellent moldability (crack-free).

[0045] Furthermore, compounds with maleimide groups are relatively rigid compared to compounds with (meth)acryloyl groups. Generally, the more rigid the molecular structure, the harder it is, thereby increasing the glass transition temperature (Tg) of the cured product. On the other hand, since the carbon chains from the fused polycyclic hydrocarbon structure to the two terminal functional groups are relatively long, they are highly mobile and can impart flexibility to the cured product. Thus, the polymerizable composition according to this embodiment provides a cured product that has both a high Tg and excellent flexural modulus (flexibility).

[0046] Furthermore, the curable composition of this embodiment can mitigate the effects of curing shrinkage.

[0047] For example, since the maleimide group has low reactivity to heat, by adding a polymeric compound (B) containing a maleimide group to the polymeric compound (A), the reaction of the polymeric composition can proceed more slowly compared to curing TCD-DA only by heat. Therefore, it is speculated that this can mitigate deformation caused by rapid curing shrinkage.

[0048] Furthermore, for example, by using a polymeric compound (B) with a larger molecular weight compared to polymeric compounds (A) such as TCD-DA, the mass per unit mass is reduced, thereby reducing the number of C-C bonds per unit mass generated by polymerization. It is therefore hypothesized that by suppressing the effect of curing shrinkage, the formation of cracks in the cured product can be suppressed.

[0049] In this embodiment, polymeric compound (A) and polymeric compound (B) contain the same fused polycyclic hydrocarbon structure. Therefore, the excellent compatibility (hereinafter, sometimes simply referred to as "compatibility") between polymeric compounds (A) and (B) allows for a reduction in the amount of solvent used in the curable composition of this embodiment, or even allows for mixing without the use of a solvent. Furthermore, if the excellent compatibility between polymeric compounds (A) and (B) suppresses crystal precipitation or phase separation in the cured product, it enables the curable product to have good transparency.

[0050] Furthermore, composite materials obtained from curable compositions containing polymeric compounds (A) and (B) having a tricyclic decane structure and fillers (C) such as inorganic particles can have good heat resistance (low coefficient of linear expansion) and moldability (no cracking).

[0051] <Polymer compound (A)>

[0052] Polymerizable compound (A) has a fused polycyclic hydrocarbon structure and two or more polymerizable functional groups bonded to the aforementioned fused polycyclic hydrocarbon structure. In other words, polymerizable compound (A) is a fused polycyclic hydrocarbon compound having two or more polymerizable functional groups. As described above, polymerizable compound (A) and polymerizable compound (B) contain the same fused polycyclic hydrocarbon structure. Here, "containing the same fused polycyclic hydrocarbon structure" means that polymerizable compounds (A) and (B) have a common fused polycyclic hydrocarbon structure. In each fused polycyclic hydrocarbon structure, the carbon atoms bonded to the polymerizable functional groups or maleimide groups may be the same or different.

[0053] Examples of fused polycyclic hydrocarbon structures include aliphatic and aromatic fused polycyclic hydrocarbon structures. It should be noted that the fused polycyclic hydrocarbon structure possessed by polymeric compound (A) and the aforementioned polymeric compound (B) are preferably aliphatic fused polycyclic hydrocarbon structures.

[0054] Examples of aliphatic fused polycyclic hydrocarbon structures include bicyclic pentane, bicyclic heptane, bicyclic octane, tricyclic [5.2.1.0(2,6)]decane, adamantane, tricyclic [4.3.1.1(3,8)]undecane, and tricyclic [6.2.1.0(1,6)]undecane, among other tricyclic aliphatic fused polycyclic hydrocarbon structures. From the perspective of the heat resistance (hereinafter referred to as heat resistance) and compatibility of the obtained cured product, the number of carbon atoms in the aliphatic fused polycyclic hydrocarbon structure is preferably 8 to 24, more preferably 10 to 20, and particularly preferably 12 to 16. From the perspective of the heat resistance and compatibility of the obtained cured product, the aliphatic fused polycyclic hydrocarbon structure is preferably a tricyclic aliphatic fused polycyclic hydrocarbon structure, more preferably a tricyclic decane structure, and particularly preferably a tricyclic [5.2.1.0(2,6)]decane structure.

[0055] Furthermore, examples of aromatic fused polycyclic aromatic hydrocarbon (APH) structures include bicyclic APH structures such as indene, naphthalene, and azurite; tricyclic APH structures such as anthracene and phenanthrene; and tetracyclic APH structures such as tetraphenyl, benzo[a]phenanthrene, pyrene, and β-phenanthrene. From the perspective of heat resistance and compatibility, the number of carbon atoms in the aromatic fused polycyclic aromatic hydrocarbon structure is preferably 8–32, more preferably 10–24, and particularly preferably 12–16. From the perspective of heat resistance and compatibility, the aromatic fused polycyclic aromatic hydrocarbon structure is preferably a bicyclic APH structure, more preferably a naphthalene structure.

[0056] The polymeric compound (A) has two or more polymeric functional groups. There is no particular limitation as long as the number of polymeric functional groups is two or more, but from the perspective of being able to reduce the linear expansion rate of the cured product to a certain extent and increase the flexural modulus to a certain extent, it is preferred to have 2 to 4, more preferably 2 to 3, and particularly preferably 2.

[0057] The "polymerizable functional group" of polymerizable compound (A) refers to a polymerizable functional group other than a functional group containing a maleimide group (including the maleimide group itself). Examples of polymerizable functional groups of polymerizable compound (A) include groups having an olefinic unsaturated double bond, epoxy groups, etc. At least one of the two or more polymerizable functional groups possessed by polymerizable compound (A) is preferably a group having an olefinic unsaturated double bond, and more preferably a group having an olefinic unsaturated double bond.

[0058] Examples of groups having olefinic unsaturated double bonds include (meth)acryloyl, vinyl, allyl, and groups containing them, with (meth)acryloyl, allyl, and groups containing them being more preferred, and (meth)acryloyl being particularly preferred.

[0059] Furthermore, the polymerizable compound (A) may contain groups other than the polymerizable functional groups described above in the fused polycyclic hydrocarbon structure. Examples of such other groups include alkyl groups and haloalkyl groups.

[0060] In polymeric compound (A), the fused polycyclic hydrocarbon structure can be directly bonded to the polymeric functional group, or it can be bonded through other atoms or groups of atoms.

[0061] Examples of other atoms or atomic groups mentioned above include oxygen atoms, nitrogen atoms, and sulfur atoms; alkylene groups and arylene groups with substituents may also be included. From the perspective of heat resistance, alkylene groups with 1 to 5 carbon atoms are preferred as other atoms or atomic groups mentioned above, and alkylene groups with 1 to 3 carbon atoms are more preferred.

[0062] Polymerizable compound (A) may contain compounds represented by formula (I) below. There may be two or more compounds represented by formula (I) below; in other words, polymerizable compound (A) may contain two or more compounds represented by formula (I) below. Examples of combinations of two or more compounds represented by formula (I) below include compounds in which the n and m of each compound are the same (wherein, the n and m of a compound may be different), and compounds with fused polycyclic hydrocarbon structures (tricyclic [5.2.1.0(2,6)]decane structure) and different bonding sites of groups containing polymerizable functional groups ((meth)acryloyl)

[0063]

[0064] (In formula (I), R) 1 R 2 Each can independently represent H or CH3, and n and m can independently be integers from 1 to 3.

[0065] In equation (I), R 1 R 2 Each can be represented independently as H or CH3, and from the perspective of formability mentioned above, CH3 is preferred. Furthermore, in formula (I), n and m are each independently integers from 1 to 3, and from the perspective of heat resistance, 1 or 2 are preferred, and 1 is more preferred. Examples of compounds represented by formula (I) include tricyclodecanediethanol diacrylate (TCD-DA) and tricyclodecanediethanol dimethacrylate (TCD-DMA).

[0066] The polymerizable compound (A) can be a single compound or a combination of two or more compounds. When the polymerizable compound (A) contains two or more compounds, examples include combinations of polymerizable compounds (A) having the same fused polycyclic hydrocarbon structure, combinations of polymerizable compounds (A) having the same polymerizable functional groups, or combinations of polymerizable compounds (A) having the same fused polycyclic hydrocarbon structure and the same polymerizable functional groups, etc., wherein combinations of polymerizable compounds (A) having the same fused polycyclic hydrocarbon structure and the same polymerizable functional groups are preferred.

[0067] As an example of "a combination of polymeric compounds (A) having the same fused polycyclic hydrocarbon structure and the same polymerizable functional groups", examples include polymeric compounds (A) having the same fused polycyclic hydrocarbon structure and the same polymerizable functional groups, and cases where the bonding positions of the polymerizable functional groups on the fused polycyclic hydrocarbon structures in each identical fused polycyclic hydrocarbon structure are different. Furthermore, when polymeric compound (A) contains two or more compounds having the same polymerizable functional groups, compounds in which the polymerizable functional groups of each polymeric compound (A) are directly bonded to the fused polycyclic hydrocarbon structure, and compounds bonded through other atoms (or groups of atoms) can coexist.

[0068] When the polymeric compound (A) contains two or more compounds, as a preferred embodiment, a combination of polymeric compounds (A) having the same fused polycyclic hydrocarbon structure and the same polymeric functional groups, wherein the polymeric functional groups of each polymeric compound (A) have the same bonding with the fused polycyclic hydrocarbon structure, but the bonding positions of the polymeric functional groups on the fused polycyclic hydrocarbon structure in each fused polycyclic hydrocarbon structure are different.

[0069] The polymeric compound (A) is preferably in liquid form under atmospheric conditions and at room temperature.

[0070] Furthermore, from the viewpoint of the heat resistance of the cured product, the glass transition temperature (Tg) of the polymeric compound (A) is preferably 100°C or higher.

[0071] The glass transition temperature (Tg) of the polymerizable compound (A) can be determined as follows: The monomer and polymerization initiator are injected into a molding mold (a mold made by attaching release films to two glass plates, face to face, with a 4mm thick silicone spacer forming a 100mm x 100mm area between the release film surfaces, and the silicone spacer held between the two glass plates at intervals of approximately 2-4mm). The molding mold is then irradiated with ultraviolet light (wavelength: 365nm) for 1 hour using an LED exposure machine to obtain the polymer.

[0072] 10 mg of the obtained polymer was weighed and placed in a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.). The temperature was measured at a heating rate of 10 °C / min within a temperature range of -130 to 100 °C. The temperature of the endothermic peak from the polymer during the first heating process was defined as the glass transition temperature (Tg) of the polymer, and this temperature was taken as the Tg of the monomer (polymeric compound (A)). The Tg of polymeric compound (B) and the Tg of the cured product, described later, could also be measured in the same manner. Sure.

[0073] From the viewpoint of making the viscosity of the curable composition within an easily operable range, the content of the polymeric compound (A) in the curable composition relative to the total amount of the composition is preferably 40 to 93% by mass, more preferably 50 to 85% by mass, and particularly preferably 60 to 75% by mass.

[0074] There are no particular limitations on the synthesis method of the polymeric compound (A). For example, it can be synthesized by reacting a compound corresponding to a fused polycyclic hydrocarbon structure having two or more hydroxyl groups in one molecule with a carboxylic acid having polymeric functional groups.

[0075] <Polymerizing Compound (B)>

[0076] Polymerizable compound (B) has a fused polycyclic hydrocarbon structure and two or more maleimide groups bonded to the aforementioned fused polycyclic hydrocarbon structure. In other words, polymerizable compound (B) is a fused polycyclic hydrocarbon compound having two or more maleimide groups. As described above, the fused polycyclic hydrocarbon structure of polymerizable compound (B) and the fused polycyclic hydrocarbon structure of polymerizable compound (A) contain the same fused polycyclic hydrocarbon structure.

[0077] Examples of fused polycyclic hydrocarbon structures for polymerizable compound (B) include aliphatic and aromatic fused polycyclic hydrocarbon structures, with aliphatic fused polycyclic hydrocarbon structures being preferred. Examples and preferred ranges of fused polycyclic hydrocarbon structures are the same as those for polymerizable compound (A) described above.

[0078] The polymeric compound (B) has two or more maleimide groups. There is no particular limitation as long as the number of maleimide groups is two or more, but from the perspective of being able to reduce the linear expansion rate of the cured product to a certain extent and increase the flexural modulus to a certain extent, it is preferred to have 2 to 4, more preferably 2 to 3, and particularly preferably 2.

[0079] The polymerizable compound (B) may contain groups other than the polymerizable functional groups described above in its fused polycyclic hydrocarbon structure. Examples of such other groups include alkyl groups, haloalkyl groups, etc.

[0080] In polymeric compound (B), the fused polycyclic hydrocarbon structure can be directly bonded to the polymeric functional group, or it can be bonded through other atoms or groups of atoms. Examples and preferred ranges of other atoms or groups of atoms in polymeric compound (B) are the same as those in polymeric compound (A) described above.

[0081] There are no particular limitations on the synthesis method of polymeric compound (B). For example, it can be synthesized by reacting a compound corresponding to a fused polycyclic hydrocarbon structure having two or more hydroxyl groups in one molecule with a carboxylic acid having a maleimide group.

[0082] Polymerizable compound (B) may contain compounds represented by formula (II) below. There may be two or more compounds represented by formula (II) below; in other words, polymerizable compound (B) may contain two or more compounds represented by formula (II) below. Examples of combinations of two or more compounds represented by formula (II) below include compounds in which the o, p, q, and r of each compound are the same (where the o, p, q, and r of a compound may be different), fused polycyclic hydrocarbon structures (tricyclic [5.2.1.0(2,6)]decane structure), and compounds with different bonding sites of groups containing maleimide groups.

[0083]

[0084] (In equation (II), o, p, q, and r are each an independent integer from 1 to 3.)

[0085] In formula (II), o, p, q, and r are each an integer from 1 to 3, and from the perspective of the heat resistance of the cured product, 1 or 2 is preferred, and 1 is more preferred. As a compound represented by formula (II), for example, tricyclodecanediethanol dimaleimide (hereinafter sometimes referred to as "TCD-DMI") can be cited.

[0086] Polymerizable compound (B) can be a single compound, just like polymerizable compound (A), or a combination of two or more compounds. When polymerizable compound (B) contains two or more compounds, examples include combinations of polymerizable compounds (B) having the same fused polycyclic hydrocarbon structure, combinations of polymerizable compounds (B) having the same "maleimide group", or combinations of polymerizable compounds (B) having the same fused polycyclic hydrocarbon structure and the same "maleimide group", etc., wherein combinations of polymerizable compounds (B) having the same fused polycyclic hydrocarbon structure and the same "maleimide group" are preferred.

[0087] As an example of "a combination of polymeric compounds (B) having the same fused polycyclic hydrocarbon structure and the same group containing a maleimide group", examples include polymeric compounds (B) having the same fused polycyclic hydrocarbon structure and the same group containing a maleimide group, and cases where the bonding positions of the maleimide-containing groups on the fused polycyclic hydrocarbon structures of each identical fused polycyclic hydrocarbon structure are different. Furthermore, when polymeric compound (B) contains two or more compounds and has the same group containing a maleimide group, compounds in which the maleimide-containing groups of each polymeric compound (B) are directly bonded to the fused polycyclic hydrocarbon structure and compounds bonded through other atoms (or groups of atoms) can coexist.

[0088] When the polymeric compound (B) contains two or more compounds, as a preferred embodiment, a combination of polymeric compounds (B) having the same fused polycyclic hydrocarbon structure and the same maleimide-containing group can be provided, wherein the bonding between the maleimide-containing group and the fused polycyclic hydrocarbon structure of each polymeric compound (B) is the same, and the bonding positions of the maleimide-containing group on the fused polycyclic hydrocarbon structure of each fused polycyclic hydrocarbon structure are different.

[0089] The polymeric compound (B) is preferably in a liquid state under atmospheric conditions and at room temperature.

[0090] Furthermore, from the viewpoint of heat resistance, the glass transition temperature (Tg) of the polymeric compound (B) is preferably 100°C or higher.

[0091] From the viewpoint of making the viscosity of the curable composition within an easily operable range, the content of the polymeric compound (B) in the curable composition is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 40 parts by mass or less, relative to 100 parts by mass of the total composition.

[0092] From the perspective of the transparency of the cured product, the polymeric compound (B) is preferably soluble in the polymeric compound (A). In the curable composition of this embodiment, when the polymeric compound (B) is soluble in the polymeric compound (A) (i.e., when the polymeric compound (A) and the polymeric compound (B) are miscible), the curable composition can be formed without using a solvent or with a reduced solvent content. While not particularly limiting, from the viewpoint of improving the transparency of the curable composition, the solubility of the polymeric compound (B) relative to 100g of the polymeric compound (A) (at 1 atmosphere, liquid temperature 25°C) is preferably 20% by mass or more, more preferably 50% by mass or more, more preferably 100% by mass or more, and particularly preferably 150% by mass or more. If the solubility of the polymeric compound (B) is 100% by mass or more, the amount of solvent in the composition can be less than 5% by mass. This solubility can be confirmed, for example, by adding 10g of the polymeric compound (A) dropwise to the polymeric compound (B), heating and mixing at 50°C, and observing the state after cooling. The polymeric compound (B) can be added dropwise, for example, in increments of 0.5 g. The upper limit of the concentration at which a homogeneous solution is formed after cooling and visual inspection reveals no insoluble matter is taken as the solubility of the polymer. For example, the solubility is 10% by mass if no insoluble matter is found when dissolving 1 g of polymeric compound (B), but can be found when dissolving 1.5 g of polymeric compound (B).

[0093] It should be noted that, from the viewpoint of curability, the total amount of polymeric compound (B) in the composition of this embodiment is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 70 parts by mass or more, relative to the total amount of 100 parts by mass of the composition.

[0094] <Polymerization Initiator>

[0095] When the compositions of this embodiment are polymerized using the polymerization method described below, for example, the manufacturing method described later, a polymerization initiator can be used. Examples of polymerization initiators include known photopolymerization initiators and thermal polymerization initiators.

[0096] -Photopolymerization initiator-

[0097] Examples of photopolymerization initiators include free radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators. These photopolymerization initiators can be used individually or in combination of two or more. For example, two or more free radical photopolymerization initiators can be used together.

[0098] Examples of compounds that can be cited as free radical photopolymerization initiators include the following compounds.

[0099] Acylphosphine oxide compounds: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (product name: Irgacure TPO, manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name: Irgacure 819, manufactured by BASF; product name: Irgacure 819DW, manufactured by BASF)

[0100] α-Hydroxyketone compounds: 1-Hydroxy-cyclohexyl-phenyl-one (product name: Irgacure 184, manufactured by BASF), 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (product name: Irgacure 1173, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (Irgacure 2959, manufactured by BASF), 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one (product name: Irgacure 127, manufactured by BASF)

[0101] Intramolecular hydrogen abstraction compound: Methyl phenylglyoxylate (product name: Irgacure MBF, manufactured by BASF)

[0102] Dioctene compounds: 1-[4-(phenylthio)-2-(O-benzoyl oxime)], bis(η5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyltitanium] (product name: Irgacure 784, manufactured by BASF)

[0103] Benzoyl ketal compounds: 2,2-dimethoxy-1,2-diphenylethane-1-one (product name: Irgacure 651, manufactured by BASF)

[0104] α-Aminoketone compounds: 2-methyl-4'-methylthio-2-morpholinophenylacetone (product name: Irgacure 907, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (product name: Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (product name: Irgacure 379EG, manufactured by BASF)

[0105] Oxime ester compounds: 1-[4-(phenylthio)-2-(O-benzoyl oxime)] (product name: IrgacureOXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (e.g., product name: Irgacure OXE-02, manufactured by BASF; product name: Irgacure OXE-03, manufactured by BASF; product name: IrgacureOXE-04, manufactured by BASF; product name: N-1919, manufactured by ADEKA; product name: N-1414, manufactured by ADEKA), etc.

[0106] Other examples of free radical photopolymerization initiators include quinones (e.g., 2-ethylanthraquinone, 2-tert-butylanthraquinone); aromatic ketones (e.g., benzophenone, benzoin); benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether); acridine compounds (e.g., 9-phenyl acridine (product name: N-1717, manufactured by ADEKA)); and triazine compounds (e.g., 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine, 2,4-trichloromethyl-(piperyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one), etc.

[0107] Examples of cationic photopolymerization initiators include the following compounds.

[0108] iodine Salt compounds: diphenyliodine Tetrafluoroborate, diphenyliodide Hexafluorophosphate, 4,4'-di-tert-butyldiphenyliodide Tetrafluoroborate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodine Hexafluorophosphate (product name: Irgacure 250: manufactured by BASF)

[0109] Diazo Salt compounds: 4-Diethylaminophenylbenzenediazo hexafluorophosphate,

[0110] Sulfonium salt compounds: diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, triarylsulfonium tetra(pentafluorophenyl)borate (product name: Irgacure 290: manufactured by BASF), triarylsulfonium hexafluorophosphate (e.g., product name: Irgacure 270, manufactured by BASF; product name: CPI300, manufactured by Sanyo Chemical Industry; product name: CPI400, manufactured by Sanyo Chemical Industry)

[0111] Diceroxide Salt compounds

[0112] Examples of anionic photopolymerization initiators include 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-(9-oxoxazanthracene-2-yl)propionic acid.

[0113] In addition, photosensitizers can be used in conjunction with photopolymerization initiators. For example, as amines, ethyl 4-dimethylaminobenzoate (Darocur EDB: manufactured by BASF) and 2-ethylhexyl 4-dimethylaminobenzoate (Darocur EHA: manufactured by BASF) can be used; as ketones, benzophenones, thioxanthones, ketocumarins, and anthraquinones (Anthracure UVS-581: manufactured by Kawasaki Chemical Industry) can be used.

[0114] -Thermal polymerization initiator-

[0115] Examples of thermal polymerization initiators include, for instance, dialkyl peroxides, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobisisobutyronitrile, and azobisdimethylvalerate, as well as peroxide-based polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. However, this embodiment is not limited to the examples described above. These polymerization initiators can be used individually or in combination of two or more.

[0116] In this embodiment, from the viewpoint of operability in atmospheric and low-temperature regions (e.g., -20 to 40°C), it is preferable to use a polymerization initiator that can be refrigerated, such as dialkyl peroxides like PERBUTYL O and PERBUTYL P sold by Nippon Oil Co., Ltd. One type of polymerization initiator can be used alone or in combination of two or more appropriately.

[0117] From the viewpoint of moldability, the content of polymerization initiator in the curable composition of this embodiment is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of polymeric compound components (the total amount of polymeric compounds (A) and (B)), more preferably 0.3 to 6 parts by mass, and particularly preferably 0.5 to 2 parts by mass.

[0118] <Packaging (C)>

[0119] When the curable composition of this embodiment is used for applications such as encapsulation materials, it may contain a filler (C). As the filler (C), known fillers may be used, for example, materials selected from silica powder such as fused silica, synthetic silica, and crystalline silica; oxides such as alumina and titanium dioxide; silicates such as talc, calcined clay, uncalcined clay, mica, and glass; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride.

[0120] As filler (C), there are no particular limitations; for example, silica powder such as fused silica can be used. Fused silica can be either fused spherical silica or fused pulverized silica. Alternatively, fused silica with a surface modified with functional groups such as (meth)acryloyl groups can be used as fused silica.

[0121] The shape of the filler (C) can be pulverized, needle-like, flake-like, spherical, etc., without particular limitation, but from the viewpoint of improving the dispersibility of the filler (C) or controlling the viscosity of the curable composition, spherical is preferred.

[0122] From the viewpoint of increasing the filling density or controlling the viscosity of the curable composition, the average particle size of the filler (C) is preferably 0.1 μm to 20 μm, and more preferably 0.2 μm to 5 μm. It should be noted that the average particle size in this embodiment is the median particle size calculated based on the results of particle size distribution measurement using laser diffraction. Furthermore, from the viewpoint of high-density filling of the curable composition, two or more fillers (C) with different volume average particle sizes may be included.

[0123] When using filler (C), the mass ratio of the polymeric component (total amount of polymeric compounds (A) and (B)) to the total amount of filler (C) in the curable composition of this embodiment is not particularly limited, but from the viewpoint of being able to improve the heat resistance and flexural modulus of the obtained cured product, it is preferably 1:99 to 50:50, and more preferably 5:95 to 30:70.

[0124] Furthermore, when two or more fillers (C) with different volume average particle sizes are included, from the viewpoint of making the curable composition of this embodiment contain a large amount of filler (C), the mass ratio (A / B) of the filler with a large volume average particle size (A) to the filler with a small volume average particle size (B) is preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 80 / 20.

[0125] <Other>

[0126] In addition to the components described above, the curable composition of this embodiment may also contain dispersants and plasticizers as needed.

[0127] -Dispersant-

[0128] In order to improve the dispersibility of fillers (C) in each polymerizable compound, the curable composition of this embodiment may contain a dispersant.

[0129] As a dispersant, known dispersants can be used without particular restriction. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polymeric surfactants, alcohols, compounds with carboxyl groups such as fatty acids, metal soaps, fatty acid oligomers, fluorinated surfactants, boron-based surfactants, etc., can be used. There can be one type of dispersant or two or more types used in combination.

[0130] When using a dispersant, from the viewpoint of easily adjusting the viscosity of the curable composition to an easily operable range, the content of the dispersant in the curable composition of this embodiment is preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total amount of filler (C), more preferably 0.5 to 3 parts by mass, and particularly preferably 1 to 2 parts by mass.

[0131] -Plasticizer-

[0132] For purposes such as adjusting the flexibility of the cured product, the curable composition of this embodiment may contain a plasticizer. There are no particular limitations on the plasticizer; for example, in addition to polymers that are commonly used as plasticizers, fatty acid ester compounds having unsaturated hydrocarbon groups, and aromatic carboxylic acid ester compounds, oils containing fatty acids having unsaturated hydrocarbon groups and aromatic carboxylic acids may also be mentioned.

[0133] When using a plasticizer, from the viewpoint of the softness of the resulting cured product, the content of the plasticizer in the curable composition of this embodiment is preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total amount of filler (C), more preferably 0.5 to 3 parts by mass, and particularly preferably 1 to 2 parts by mass.

[0134] -Polymerization inhibitor-

[0135] The curable composition of this embodiment may contain a polymerization inhibitor. The polymerization inhibitor can be any commonly used polymerization inhibitor and is not particularly limited. Examples include 2,2,6,6-tetramethylpiperidine-1-oxy radical derivatives such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (BTOX), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, and 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxy radical (AMX); aromatic amine compounds such as phenothiazine; and alkylphenols such as 4-methoxyphenol and 2,6-di-tert-butyl-p-cresol (BHT).

[0136] When using a polymerization inhibitor, from the perspective of preventing unintended reactions (polymerization) in the curable composition without hindering the polymerization reaction during the manufacture of the cured product, the content of the polymerization inhibitor in the curable composition of this embodiment is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and particularly preferably 0.7 to 1.5 parts by mass, relative to 100 parts by mass of the total amount of the polymeric compound components (the total amount of polymeric compounds (A) and (B). When the curable composition contains polymeric compounds other than polymeric compounds (A) and (B), it is their total amount).

[0137] -solvent-

[0138] The curable composition of this embodiment may contain a solvent. When the curable composition of this embodiment contains a solvent, the solvent content is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably solvent-free. It should be noted that, as described above, polymeric compound (A) and polymeric compound (B) sometimes have compatibility, but each polymeric compound is not considered a solvent in this embodiment.

[0139] As a solvent that can be used in the curable composition of this embodiment, there are no particular limitations as long as it can dissolve the polymeric compound (B) and polymeric compound (A) in this embodiment. Examples include benzene-based solvents (e.g., toluene, xylene, etc.), ketone-based solvents (e.g., cyclopentanone, methyl ethyl ketone (MEK), acetone, cyclohexanone, etc.), and ester-based solvents (e.g., ethyl acetate, hexyl acetate, butyl acetate, carbolic acid ester, etc.).

[0140] In addition to the components described above, the curable composition of this embodiment may, without impairing the effects of the present invention, incorporate other polymeric compounds, resin (polymer) crosslinking agents, curing catalysts, reducing agents, surfactants, chain transfer agents, photosensitizers, preservatives, rust inhibitors, etc., as needed. There are no particular limitations on the polymeric compounds other than polymeric compounds (A) and polymeric compounds (B). Examples of other polymeric compounds include styrene, acrylonitrile, divinyl ether, diallyl ether, etc.

[0141] [Method for manufacturing curable composition]

[0142] The method for manufacturing the curable composition according to this embodiment is not particularly limited. A curable composition can be obtained by adding polymeric compound (A) and polymeric compound (B), along with a polymerization initiator, filler (C), dispersant, and other additives as needed, to a mixing vessel and stirring and mixing them. It should be noted that a known mixer or similar device can be used for stirring and mixing. When adding other additives in the method for manufacturing the curable composition, the stirring time is sufficient to dissolve or disperse the additive. The additives can be added to the mixing vessel together with polymeric compound (A) and polymeric compound (B), or they can be added later. Furthermore, as described above, polymeric compound (B) can be used as a solvent to manufacture polymeric compound (A), and filler (C) and other components can be added to the mixture of polymeric compound (A) and polymeric compound (B).

[0143] Furthermore, the curable composition of this embodiment has an excellent pot life, so it can be manufactured into a single-liquid composition, resulting in excellent work efficiency and operability.

[0144] It should be noted that, in addition to the single-liquid composition, the curable composition of this embodiment can also be made into a two-liquid composition in which the polymeric compound (A) and the polymeric compound (B) are separate individual compositions. When making a two-liquid type, the content of polymeric compounds (A) and (B) can be adjusted in such a way that the content of each component in the two-liquid mixture is within the range described above.

[0145] "Solid Object"

[0146] The cured product of this embodiment can be obtained by curing the curable composition of this embodiment. There are no particular limitations on the method for curing the curable composition, and any commonly used method can be appropriately selected. Examples of curing methods include irradiation with active energy rays and heating.

[0147] When curing a curable composition by irradiation with active energy rays, the irradiation conditions are not particularly limited. For example, a high-pressure mercury lamp can be used under atmospheric conditions with a cumulative light intensity of 1200 mJ / cm². 2 Allow it to solidify completely.

[0148] When the curable composition is cured by heating, the heating temperature is preferably 70 to 250°C, more preferably 90 to 170°C. Furthermore, the heating time is preferably 90 minutes or less.

[0149] It should be noted that when using the curable composition of this embodiment as a two-component composition, it is preferable to mix the two components only before the curing process. Other curing conditions can be appropriately adopted according to the conditions described above.

[0150] Furthermore, as described above, the curing composition of the cured product of this embodiment exhibits excellent curing properties and pot life. Therefore, the cured product of this embodiment is advantageous from the viewpoint of productivity and energy efficiency during curing, and possesses excellent flexibility and cured state. Even when manufactured as a composite material containing filler, it exhibits good heat resistance (low coefficient of linear expansion) and moldability (no cracking). Therefore, the cured product of this embodiment can be used for various applications, such as coating agents, encapsulation materials (underfill), resin films with carriers, prepregs, and resin portions of metal-coated laminates. It should be noted that the filler (C) can be used depending on the application of the cured product of this embodiment. Examples of applications using the filler (C) include encapsulation materials and heat dissipation materials.

[0151] From the viewpoint of heat resistance, the glass transition temperature (Tg) of the cured product of this embodiment is preferably 50 to 300°C, more preferably 100 to 250°C, and particularly preferably 120 to 200°C.

[0152] From the viewpoint of heat resistance, the coefficient of linear expansion of the cured product of this embodiment is preferably 40 ppm / ℃ or less at 80℃, more preferably 30 ppm / ℃ or less, and particularly preferably 20 ppm / ℃ or less.

[0153] From the viewpoint of heat resistance, the coefficient of linear expansion of the cured product of this embodiment is preferably 45 ppm / ℃ or less at 140℃, more preferably 35 ppm / ℃ or less, and particularly preferably 25 ppm / ℃ or less.

[0154] From the viewpoint of giving the cured material a certain degree of flexibility and impact resistance, the flexural modulus of the cured material in this embodiment is preferably 8000 to 14000 MPa, more preferably 9000 to 13000 MPa, and particularly preferably 10000 to 12000 MPa.

[0155] Unless otherwise specified, the above numerical ranges can be obtained by the same method as described in the embodiments.

[0156] Curing property improver

[0157] As described above, the polymeric compound (B) can improve the curability of a curable composition in which the polymeric compound (A) is used alone. From this viewpoint, compounds represented by formula (II) belonging to polymeric compound (B) can be used as curability improvers for other polymeric compounds. As compounds that improve curability, polymeric compound (A) is preferred, and compounds represented by formula (I) are even more preferred.

[0158] The curability enhancer of this embodiment may be composed of one or more compounds represented by formula (II) below. As a combination of two or more compounds represented by formula (II) below, examples include combinations of compounds in which each compound has the same o, p, q, and r (wherein, o, p, q, and r in one compound may be different), fused polycyclic hydrocarbon structures (tricyclic [5.2.1.0(2,6)]decane structure), and compounds with different bonding sites of groups containing maleimide groups.

[0159]

[0160] (In equation (II), o, p, q, and r are each an independent integer from 1 to 3.)

[0161] The compound represented by formula (II) in the curing improver is preferably liquid at room temperature. In addition to the compound represented by formula (II), the curing improver may, as needed, contain solvents, surfactants, preservatives, rust inhibitors, etc., without impairing the effects of the present invention.

[0162] The embodiments of the present invention have been described above, but the present invention is not limited to the above description.

[0163] Example

[0164] The present invention will be specifically described below using examples. However, the present invention is not limited to the following examples.

[0165] [Manufacturing Example 1]

[0166] (Synthesis of TCD-DMI)

[0167] In a reaction vessel equipped with a distillation apparatus featuring a stirrer, thermometer, fractionation column, and cooler, 72.4 g (0.43 mol) of 3-maleimide propionic acid, 40.0 g (0.20 mol) of tricyclodecanediethanol, 50 g of n-hexane, 250 g of toluene, 3.9 g of p-toluenesulfonic acid monohydrate (catalyst), and 0.01 g of 4-methoxyphenol (polymerization inhibitor) were added. Air was blown into the added solution at a rate of 10 ml / min, and the reaction solution was heated to 90°C using an oil bath. A dehydration condensation reaction to remove water generated during the reaction was carried out at atmospheric pressure for 15 hours. Next, the reaction solution was added to a separatory funnel, and the organic layer was washed with a 10% sodium hydroxide aqueous solution to remove unreacted 3-maleimide propionic acid and catalyst. Subsequently, the organic layer was washed with water until the pH of the aqueous layer became below 7. The organic layer was concentrated at 60°C under reduced pressure to obtain the target tricyclodecanediethanol dimaleimide (TCD-DMI).

[0168] [Example 1-1 to Comparative Example 1-6]

[0169] (Preparation of polymeric compounds)

[0170] In a reaction vessel equipped with a stirrer, thermometer and reflux cooling pipe, the amounts of polymeric compounds (A) and (B) (polymeric compound (B')) and a photopolymerization initiator shown in Table 1 below were added under light-shielding conditions, and stirred at room temperature (about 23°C) to obtain the polymeric compositions of each example and comparative example.

[0171] (Curing property: the cumulative amount of light that becomes non-sticky)

[0172] The polymeric composition, coated to a final film thickness of 150 μm (size: 10 cm × 10 cm), was exposed to a high-pressure mercury lamp under the following conditions. The minimum cumulative light intensity (mJ / cm²) required to achieve a non-sticky state was determined. 2 It should be noted that the presence or absence of stickiness can be determined by touching the surface of the cured film with a finger and observing whether fingerprints are left.

[0173] -Exposure Conditions-

[0174] NV (%): 100%

[0175] Exposure lamp: High-pressure mercury lamp

[0176] Illuminance: 480mW / cm 2

[0177] Atmosphere: Under the atmosphere

[0178] GAP coating size: 300μm

[0179] Final film thickness: 150 μm

[0180] (Compatibility)

[0181] Polymer compounds (A) and (B) were mixed in the ratios shown in Table 1 below and stirred at room temperature. The compatibility of polymer compounds (A) and (B) was evaluated based on the following criteria.

[0182] -Benchmark-

[0183] A: No insoluble matter that could be visually observed was identified.

[0184] C: Insoluble matter that can be visually observed can be identified.

[0185] (Applicable period)

[0186] The pot life of the polymeric composition obtained by placing it in the dark at room temperature is evaluated according to the following criteria.

[0187] -Benchmark-

[0188] A: When placed at room temperature, it did not gel even after 30 days.

[0189] B: When left at room temperature, it did not gel even after 3 hours, but gelled before 30 days.

[0190] C: When placed at room temperature, it gels within 3 hours.

[0191] (Transparency)

[0192] The polymeric composition was coated to a final film thickness of 150 μm (size: 10 cm × 10 cm), and exposed to the above conditions until it became non-sticky to obtain a sample. The sample was visually observed, and its transparency was evaluated according to the following criteria.

[0193] [Benchmark]

[0194] A: Colorless and transparent.

[0195] B: Accompanied by yellow or brown.

[0196] C: Leukorrhea.

[0197] [Table 1]

[0198]

[0199] Light Acrylate DCP-A: Manufactured by Kyoeisha Chemical Co., Ltd.; Dimethyloltricyclodecane diacrylate (tricyclodecanediethanol diacrylate)

[0200] TCD-DMI: Tricyclodecanedimethyl dimaleimide manufactured in Example 1

[0201] Viscoat#295: Manufactured by Osaka Organic Chemical Industry Co., Ltd.; Trimethylolpropane triacrylate

[0202] Karenz MT (registered trademark) PE1: Manufactured by Resonac Co., Ltd.; Pentaerythritol tetra(3-mercaptobutyrate)

[0203] 4,4'-Bismaleimide diphenylmethane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0204] Bis(ethylmethylmaleimidephenyl)methane: Manufactured by Tokyo Chemical Industry Co., Ltd.; Bis(3-ethyl-5-methyl-4-maleimidephenyl)methane

[0205] IPBM: Manufactured by Kawaguchi Chemical Industry Co., Ltd.; 1-maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane

[0206] TPO: Manufactured by BASF; 2,4,6-Trimethylbenzoyldiphenylphosphine oxide (trade name: IrgacureTPO)

[0207] As shown in Table 1, the examples using polymeric compounds (A) and (B) exhibited good curability through atmospheric light curing. In particular, Example 1-1 showed a significantly better result with approximately four times the non-stickiness compared to Comparative Example 1-1.

[0208] In Comparative Examples 1-2, TMP-3A, a multifunctional acrylate, was added to increase sensitivity, but the non-stickiness was only increased by about 2 times compared to Comparative Example 1-1.

[0209] Comparative Examples 1-3 added polyfunctional thiols, and as a result, the non-stickiness was increased by 4 times compared with Comparative Example 1-1, but the stability (pot life) of the polymerizable composition deteriorated, and gelation occurred within 3 hours.

[0210] Comparative Examples 1-4, 1-5, and 1-6 used common bismaleimide, but it is insoluble in DCP-A, and all results were worse than those of the Examples.

[0211] [Example 2-1 to Comparative Example 3-1]

[0212] (Preparation of polymeric compounds)

[0213] Add the amounts of polymeric compounds (A) and (B), filler, thermal polymerization initiator, and silane coupling agent shown in Table 2 below to a mixing container, and stir for 60 seconds at an orbital speed of 2000 rpm under atmospheric pressure using a rotary mixer (THINKY Corporation, name: Defoaming Rentaro ARV-310P) to obtain the polymeric compositions of each example and comparative example.

[0214] Next, the obtained polymeric composition is poured onto a 100mm × 100mm × 5mm soda-lime glass sheet. A 2mm thick silicone spacer is fixed to the periphery of the glass sheet, and the sheet is calendered to sandwich it between another soda-lime glass sheet. The two soda-lime glass sheets are clamped with long-tail clips at two equal positions on each side, and cured according to the curing conditions to obtain a sample with a final film thickness of 2mm (size: 5cm × 5cm).

[0215] (Coefficient of linear expansion)

[0216] The cured material was cut to a thickness of 2 mm to obtain a 5 mm × 5 mm × 2 mm test piece. Thermal expansion was measured using a thermomechanical analysis (TMA) machine (NETZCH JAPAN, TMA 4000SA) at a heating rate of 5 °C / min, a load of 5.0 g, and a nitrogen atmosphere until the temperature of the cured material exceeded 200 °C. The coefficient of linear expansion (80 °C, 140 °C) was calculated from the thermal expansion of the obtained sample.

[0217] (Flexural modulus)

[0218] The cured material was cut to a thickness of 0.5 mm to obtain a test piece of 50 mm × 10 mm × 0.5 mm. The displacement and stress were measured using a bending tester at a speed of 1 mm / min until the test piece broke. The flexural modulus of the sample was calculated from the obtained stress-strain curve.

[0219] (Cure state)

[0220] The surface of the sample obtained by visual inspection is evaluated for its curing state according to the following criteria.

[0221] [Benchmark]

[0222] A: No cracks were found.

[0223] B: The crack was discovered.

[0224] C: Poor curing (not completely uncured, but with residual liquid components or softened areas at the ends of the cured material)

[0225] [Table 2]

[0226]

[0227] NK Ester DCP: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; Tricyclodecanediethanol dimethacrylate

[0228] Silica: Manufactured by Denka Corporation; FB-3SDC (methacryl modified)

[0229] PERBUTYL O: Manufactured by Nippon Oil Co., Ltd.; tert-butyl peroxide (2-ethylhexanoate)

[0230] PERBUTYL P: Manufactured by Nippon Oil Co., Ltd.: α,α'-Di(tert-butylperoxide)diisopropylbenzene

[0231] As shown in Table 2, and in the examples using polymeric compounds (A) and (B), no cracks were generated on the surface of the cured product. Furthermore, it was observed that the increase in the coefficient of linear expansion was suppressed, resulting in excellent heat resistance.

[0232] The entire disclosure of Japanese Patent Application No. 2024-030040, filed on February 29, 2024, is incorporated herein by reference. Furthermore, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard were specifically and independently described and incorporated herein by reference.

Claims

1. A curable composition comprising: Polymer compound A having a fused polycyclic hydrocarbon structure and two or more polymerizable functional groups bonded to the fused polycyclic hydrocarbon structure. Polymerizable compound B having a fused polycyclic hydrocarbon structure and two or more maleimide groups bonded to the fused polycyclic hydrocarbon structure. The polymeric compound A and the polymeric compound B contain the same fused polycyclic hydrocarbon structure.

2. The curable composition according to claim 1, wherein, The fused polycyclic hydrocarbon structure of polymeric compound A and the fused polycyclic hydrocarbon structure of polymeric compound B are aliphatic fused polycyclic hydrocarbon structures.

3. The curable composition according to claim 1, wherein, At least one of the two or more polymerizable functional groups in the polymeric compound A is a group having an olefinic unsaturated double bond.

4. The curable composition according to claim 1, wherein, The polymeric compound A comprises a compound represented by the following formula (I), In equation (I), R 1 R 2 Each can independently represent H or CH3, and n and m can independently be integers from 1 to 3.

5. The curable composition according to claim 1, wherein, The polymeric compound B comprises a compound represented by the following formula (II), In equation (II), o, p, q, and r are each an integer from 1 to 3.

6. The curable composition according to claim 1, wherein, It contains filler.

7. A curing improver comprising a compound represented by formula (II) below, In equation (II), o, p, q, and r are each an integer from 1 to 3.

8. A cured product, which is formed by curing the curable composition according to any one of claims 1 to 6.

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