Hardening components, hardened substances, and machinery

Abstract

To provide a curable composition that contains an ene compound and a thiol compound, has high storage stability, and gives a cured product having high flexibility even at low temperature.SOLUTION: A curable composition contains an ene compound (A1), a thiol compound (A2), a curing catalyst (B), a stabilizer (C), and an acrylic polymer (D) with a glass transition temperature of -30°C or lower.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a cured product, and equipment, and more particularly to a curable composition containing an ene compound and a thiol compound, a cured product obtained by curing this curable composition, and equipment manufactured using this curable composition. [Background technology]

[0002] One type of adhesive composition is one containing an ene compound and a thiol compound. Cured products of this type tend to be flexible. For example, Patent Document 1 discloses a resin composition containing an acrylic resin, a thiol compound, a latent curing agent, a radical polymerization inhibitor, and an anionic polymerization inhibitor (see Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 4976575 [Overview of the project] [Problems that the invention aims to solve]

[0004] According to the inventor's research, adhesives used in camera modules, particularly in smartphones, require increasing flexibility in their cured form, in addition to storage stability, to withstand drop impact tests.

[0005] However, as a result of the inventor's independent research and development of compositions used as adhesives, when a composition containing an ene compound and a thiol compound is cured to produce a cured product, the flexibility of the cured product tends to decrease at low temperatures.

[0006] An object of the present invention is to provide a curable composition that contains an ene compound and a thiol compound, has high storage stability, and allows a cured product thereof to easily exhibit high flexibility even at low temperatures, a cured product obtained by curing the curable composition, and an apparatus manufactured using the curable composition. Means for Solving the Problem

[0007] A curable composition according to one aspect of the present invention contains an ene compound (A1), a thiol compound (A2), a latent curing catalyst (B1), a stabilizer (C), and an acrylic polymer (D) having a glass transition temperature of -30°C or lower.

[0008] A cured product according to one aspect of the present invention is obtained by curing the curable composition.

[0009] An apparatus according to one aspect of the present invention includes a first component, a second component, and a cured product that is interposed between the first component and the second component and bonds the first component and the second component, wherein the cured product is obtained by curing the curable composition. Effects of the Invention

[0010] According to the present invention, there can be obtained a curable composition that contains an ene compound and a thiol compound, has high storage stability, and allows a cured product thereof to easily exhibit high flexibility even at low temperatures, a cured product obtained by curing the curable composition, and an apparatus manufactured using the curable composition. Mode for Carrying Out the Invention

[0011] Hereinafter, one embodiment of the present invention will be described. The following embodiment is merely one of various embodiments of the present invention. Various alterations can be made to the following embodiment according to design as long as the object of the present invention can be achieved.

[0012] The curable composition according to this embodiment is preferably used as an adhesive, and more preferably for bonding components in precision equipment such as camera modules. When used as an adhesive, the curable composition may be used to bond any material; in other words, the use of the curable composition is not limited to bonding components in precision equipment such as camera modules. Furthermore, the curable composition according to this embodiment may be applied to uses other than as an adhesive, for example, as a encapsulant for electronic components.

[0013] The curable composition according to this embodiment (hereinafter also referred to as composition (X)) contains an ene compound (A1), a thiol compound (A2), a latent curing catalyst (B1), a stabilizer (C), and an acrylic polymer (D) having a glass transition temperature of -30°C or lower.

[0014] Since composition (X) contains a latent curing catalyst (B1) and a stabilizer (C), the composition has high storage stability. Furthermore, since composition (X) contains an acrylic polymer (D) with a glass transition temperature of -30°C or lower, the cured product of composition (X) tends to have high flexibility even at low temperatures.

[0015] The glass transition temperature of the acrylic polymer (D) is determined using a differential scanning calorimeter (e.g., model DSC7000X from Hitachi High-Tech Science Co., Ltd.) under the conditions of a nitrogen gas flow of 30 ml / min, a temperature range of -70 to 200°C, and a heating rate of 10°C / min. The temperature at the peak of the DDSC curve (i.e., the differential curve of the DSC curve) is defined as the glass transition temperature. In cases where the acrylic polymer (D) is a block polymer, more than one glass transition temperature may be measured. In such cases, it is sufficient that at least one glass transition temperature is -30°C or lower.

[0016] The details of the components contained in composition (X) will be described below.

[0017] The ene compound (A1) and the thiol compound (A2) are reaction-curing components for curing composition (X).

[0018] The ene compound (A1) contains at least one of the following: a compound having at least one of an acryloyl group and a methacryloyl group (hereinafter referred to as an acrylic compound) and a compound having a vinyl group (hereinafter referred to as a vinyl compound).

[0019] The acrylic compound contains at least one selected from the group consisting of, for example, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, dimethylol-tricyclodecane diacrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, tris-(2-acryloxyethyl) isocyanurate, bis-(2-acryloxyethyl) isocyanurate, caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, isocyanurate EO-modified diacrylate, and isocyanurate EO-modified triacrylate.

[0020] The vinyl compound contains at least one selected from the group consisting of triallyl isocyanurate, allyl glycidyl ether, trimethylolpropanediallyl ether, and pentaerythritol triallyl ether.

[0021] The ene compound (A1) preferably contains a compound having an isocyanurate skeleton. In this case, the adhesive strength of the cured product of composition (X) is likely to be improved when composition (X) is applied to an adhesive. In this case, the ene compound (A1) preferably contains at least one selected from the group consisting of tris-(2-acryloxyethyl)isocyanurate, bis-(2-acryloxyethyl)isocyanurate, caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, isocyanurate EO-modified diacrylate, isocyanurate EO-modified triacrylate, and triallyl isocyanurate.

[0022] The compounds that ene compound (A1) can contain are not limited to those listed above, and ene compound (A1) can contain various compounds having an ethylenically unsaturated bond.

[0023] The molecular weight of the ene compound (A1) is, for example, between 80 and 1000.

[0024] The thiol compound (A2) preferably contains a compound having at least two thiol groups in one molecule. The thiol compound (A21) more preferably contains a compound having three to six thiol groups in one molecule.

[0025] Thiol compounds (A2) include, for example, esters of polyols and mercaptoorganic acids. These esters contain at least one of a partial ester and a complete ester.

[0026] The polyol includes at least one selected from the group consisting of, for example, ethylene glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0027] Mercapto-organic acids include at least one selected from the group consisting of mercaptoaliphatic monocarboxylic acids, esters containing thiol and carboxyl groups obtained by the esterification reaction of a hydroxy acid with a mercapto-organic acid, mercaptoaliphatic dicarboxylic acids, and mercapto-aromatic monocarboxylic acids. Mercaptoaliphatic monocarboxylic acids include at least one selected from the group consisting of, for example, mercaptoacetic acid; mercaptopropionic acid such as 3-mercaptopropionic acid; and mercaptobutyric acid such as 3-mercaptobutyric acid and 4-mercaptobutyric acid. The number of carbon atoms in mercaptoaliphatic monocarboxylic acids is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 3. Mercaptoaliphatic monocarboxylic acids with 2 to 8 carbon atoms include at least one selected from the group consisting of, for example, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 4-mercaptobutyric acid. Mercaptoaliphatic dicarboxylic acids include, for example, at least one selected from the group consisting of mercaptosuccinic acid and dimercaptosuccinic acid such as 2,3-dimercaptosuccinic acid. Mercaptoaromatic monocarboxylic acids include, for example, mercaptobenzoic acid such as 4-mercaptobenzoic acid.

[0028] Partial esters of polyols and mercapto-organic acids include, for example, trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), and pentaerythritol It contains at least one selected from the group consisting of Lutris (4-mercaptobutyrate), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), and dipentaerythritol tetrakis (4-mercaptobutyrate), etc.

[0029] Complete esters of polyols and mercapto-organic acids include, for example, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), and dipentaerythritol. Examples include hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), and dipentaerythritol hexakis (4-mercaptobutyrate). Preferably, it includes at least one selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), and trimethylolpropane tris (3-mercaptopropionate).

[0030] The thiol compound (A2) may contain, for example, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, etc.

[0031] The thiol compound (A2) may contain compounds other than those listed above. For example, the thiol compound (A2) may contain at least one selected from the group consisting of 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 3,6-dioxa-1,8-octanedithiol, and bis-2-mercaptoethyl sulfide. The thiol compound (A2) may also contain at least one selected from the group consisting of tris(3-mercaptopropyl) isocyanurate and 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl.

[0032] The thiol compound (A2) preferably contains a compound having a secondary thiol group. For example, the thiol compound (A2) preferably contains at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinan-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate). Compounds having a secondary thiol group tend to improve the storage stability of composition (X) compared to compounds having a primary thiol group.

[0033] The total percentage of ene compound (A1) and thiol compound (A2) is preferably 70% by mass or more with respect to the solid content of composition (X). However, if composition (X) contains filler (E) as described later, the total percentage of ene compound (A1) and thiol compound (A2) is preferably 70% by mass or more with respect to the portion of composition (X) excluding filler (E) from the solid content. In this case, composition (X) can have good reaction curability. This percentage is more preferably 80% by mass or more, and even more preferably 90% by mass or more. Also, this percentage is, for example, 97% by mass or less. The solid content refers to the components of composition (X) excluding volatile components. Volatile components are components that volatilize during the curing process of composition (X) and the formation of a cured product, and do not constitute the cured product; for example, solvents.

[0034] Furthermore, regarding the mixing ratio of ene compound (A1) and thiol compound (A2), it is preferable that the equivalent ratio of thiol compound (A2) to ene compound (A1) is 0.5 or more and 1.5 or less. This mixing ratio is more preferable if it is 0.7 or more and 1.3 or less, and even more preferable if it is 0.85 or more and 1.15 or less.

[0035] The reaction-curing components in composition (X) may consist only of ene compound (A1) and thiol compound (A2). Composition (X) may also contain reaction-curing components other than ene compound (A1) and thiol compound (A2) (hereinafter referred to as component (A3)), to the extent that they do not excessively impair the effects of this embodiment. When composition (X) contains component (A3), the percentage of component (A3) to ene compound (A1) is preferably greater than 0% by mass and 70% by mass or less. This percentage is more preferably 50% by mass or less, and even more preferably 30% by mass or less. Examples of compounds included in component (A3) include epoxy compounds, oxetane compounds, phenol compounds, and amine compounds.

[0036] Composition (X) contains a curing catalyst (B). Therefore, heating of composition (X) facilitates the curing reaction of composition (X).

[0037] The curing catalyst (B) contains at least one component selected from the group consisting of, for example, imidazoles, cycloamidines, tertiary amines, organophosphines, tetrasubstituted phosphonium / tetrasubstituted borates, quaternary phosphonium salts having counteranions other than borates, and tetraphenylboron salts.

[0038] The curing catalyst (B) contains a latent curing catalyst (B1). In this case, the reaction of composition (X) in an unheated state can be suppressed, and the storage stability of composition (X) can be improved. The latent curing catalyst (B1) may contain at least one of a liquid latent curing accelerator and a solid-disperse latent curing accelerator. For example, it is preferable that the latent curing catalyst (B1) contains a microencapsulated latent curing catalyst (B11). The microencapsulated latent curing catalyst (B11) comprises a core made of a catalytically active compound and a shell covering the core. The shell is made of at least one of, for example, an organic polymer and an inorganic compound. The microencapsulated latent curing catalyst (B11) contains, for example, a microencapsulated imidazole containing imidazoles as the catalytically active compound.

[0039] The percentage of curing catalyst (B) to the total of ene compound (A1) and thiol compound (A2) is preferably 0.1% by mass or more and 35% by mass or less. When this percentage is 0.1% by mass or more, the reactivity of composition (X) when it is reacted and cured tends to increase. When this percentage is 35% by mass or less, the storage stability of composition (X) tends to increase. This percentage is more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more. This percentage is more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0040] Composition (X) contains a stabilizer (C) as described above. Stabilizer (C) is a compound that makes it difficult for the reactive components of composition (X), namely the ene compound (A1) and the thiol compound (A2), to react. When composition (X) contains stabilizer (C), its storage stability tends to increase.

[0041] The stabilizer (C) preferably contains at least one of a radical polymerization inhibitor and an anionic polymerization inhibitor. In this case, the storage stability of composition (X) is more likely to be improved. This is presumed to be because, during storage of composition (X), the radical polymerization inhibitor makes it difficult for the radical polymerization reaction between the ene compound (A1) and the thiol compound (A2) and the radical polymerization reaction between molecules in the ene compound (A1) to proceed, and the anionic polymerization inhibitor makes it difficult for the anionic polymerization reaction between the ene compound (A1) and the thiol compound (A2) to proceed.

[0042] The radical polymerization inhibitor may contain, for example, at least one compound selected from the group consisting of 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, dibutylhydroxytoluene, 1,1-diphenyl-2-picrylhydrazyl free radical, hydroquinone, hydroquinone monomethyl ether, mequinol, phenothiazine, and N-nitroso-N-phenylhydroxylamine aluminum. However, the compounds that the radical polymerization inhibitor may contain are not limited to those mentioned above.

[0043] The anionic polymerization inhibitor contains, for example, at least one of an organoboric acid compound and a compound having a phenolic hydroxyl group. The organoboric acid compound contains at least one boric acid ester selected from the group consisting of, for example, triethyl borate, tributyl borate, and triisopropyl borate. The compound having a phenolic hydroxyl group contains at least one selected from the group consisting of, for example, 2,3-dihydroxynaphthalene, 4-methoxy-1-naphthol, pyrogallol, methylhydroquinone, and t-butylhydroquinone.

[0044] In this embodiment, if composition (X) contains an anionic polymerization inhibitor, it is preferable that the anionic polymerization inhibitor contains a compound having a phenolic hydroxyl group. In this case, the storage stability of composition (X) is more likely to be improved. The reason for this is not clear, but it is presumed that compounds having a phenolic hydroxyl group are generally weakly acidic and can release protons, and that the action of these protons stabilizes the curing catalyst (B). On the other hand, organoboric acid compounds generally do not release protons.

[0045] The percentage of stabilizer (C) relative to the total of the ene compound (A1), thiol compound (A2), latent curing catalyst (B1), stabilizer (C), and acrylic polymer (D) is preferably 0.01% by mass or more and 1.0% by mass or less. If this percentage is 0.01% by mass or more, the storage stability of composition (X) is likely to be further enhanced. If this percentage is 1.0% by mass or less, the curability of composition (X) is less likely to be impaired, and there is an advantage that high adhesive strength is easily maintained when composition (X) is cured under appropriate conditions. This percentage is more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. Furthermore, this percentage is more preferably 0.5% by mass or less, even more preferably 0.35% by mass or less, and particularly preferably 0.25% by mass or less.

[0046] When the stabilizer contains a radical polymerization inhibitor, the percentage of the radical polymerization inhibitor relative to the total of the ene compound (A1), thiol compound (A2), latent curing catalyst (B1), stabilizer (C), and acrylic polymer (D) is preferably 0.01% by mass or more and 1.0% by mass or less. If this percentage is 0.01% by mass or more, the storage stability of composition (X) is likely to be further enhanced. If this percentage is 1.0% by mass or less, the curability of composition (X) is less likely to be impaired, and there is an advantage that high adhesive strength is easily maintained when composition (X) is cured under appropriate conditions. This percentage is more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. Furthermore, this percentage is more preferably 0.5% by mass or less, even more preferably 0.35% by mass or less, and particularly preferably 0.25% by mass or less.

[0047] When the stabilizer contains an anionic polymerization inhibitor, the percentage of the anionic polymerization inhibitor relative to the total of the ene compound (A1), thiol compound (A2), latent curing catalyst (B1), stabilizer (C), and acrylic polymer (D) is preferably 0.01% by mass or more and 1.0% by mass or less. If this percentage is 0.01% by mass or more, the storage stability of composition (X) is likely to be further enhanced. If this percentage is 1.0% by mass or less, the curability of composition (X) is less likely to be impaired, and there is an advantage that high adhesive strength is easily maintained when cured under appropriate conditions. This percentage is more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. Furthermore, this percentage is more preferably 0.5% by mass or less, even more preferably 0.35% by mass or less, and particularly preferably 0.25% by mass.

[0048] As described above, composition (X) contains an acrylic polymer (D) having a glass transition temperature of -30°C or lower. An acrylic polymer is a polymer of one or more monomers having at least one of an acryloyl group and a methacryloyl group. The glass transition temperature of the acrylic polymer (D) is more preferably -35°C or lower, and even more preferably -40°C or lower. This glass transition temperature is, for example, -100°C or higher. The number-average molecular weight of the acrylic polymer (D) is, for example, 2,000 to 80,000. This number-average molecular weight is measured by GPC (gel permeation chromatography) using an HLC-8329GPC manufactured by Tosoh Corporation, with a TSKgel SuperMultiprore HZ-M manufactured by Tosoh Corporation as the GPC column and tetrahydrofuran as the GPC solvent, using the standard polystyrene equivalent method.

[0049] The acrylic polymer (D) preferably contains a reactive polymer (D1) having radically polymerizable unsaturated bonds in its molecule. In this case, the adhesion of composition (X) is less likely to be inhibited by the acrylic polymer (D). However, the acrylic polymer (D) may also contain a polymer (D2) that does not have radically polymerizable unsaturated bonds.

[0050] The acrylic polymer (D) may be liquid or solid at room temperature. That is, the reactive polymer (D1) may be liquid or solid at room temperature, and the polymer (D2) may also be liquid or solid at room temperature.

[0051] The reactive polymer (D1) preferably contains a polymer (D11) having the structure shown in formula (1) below. In this case, the cured product of composition (X) tends to have higher flexibility over a wide temperature range.

[0052] [ka]

[0053] In formula (1), Fn is a crosslinkable functional group, R is H or an alkyl group having 1 to 10 carbon atoms, and n is a number between 8 and 9000.

[0054] The acrylic polymer (D) may contain compounds other than those listed above.

[0055] For example, among reactive polymers (D1), liquid compounds include XMAP RC100C, RC200C, MM110C manufactured by Kaneka Corporation, and compounds having acryloyl groups, methacryloyl groups, or allyl groups in their molecules, such as NISSO PB TE-2000 and TEAI-1000 manufactured by Nippon Soda Co., Ltd.

[0056] Furthermore, among the polymers (D2), examples of liquid compounds include compounds having a butyl polyacrylate structure in the molecule, such as Clarity LA-2114 manufactured by Kuraray Co., Ltd., and UP-1000 manufactured by Toagosei Co., Ltd.

[0057] Furthermore, among polymers (D2), examples of solid compounds include compounds having a butyl polyacrylate structure in their molecules, such as Clarity LA-2140 and LK-9243 manufactured by Kuraray Co., Ltd.

[0058] When the acrylic polymer (D) contains polymer (D2), it is preferable that polymer (D2) is in a solid state. In that case, the adhesion is less likely to be inhibited by polymer (D2).

[0059] The percentage of acrylic polymer (D) to the total of the ene compound (A1), thiol compound (A2), latent curing catalyst (B1), stabilizer (C), and acrylic polymer (D) is preferably 1% by mass or more and 16% by mass or less. If this percentage is 1% by mass or more, the cured product tends to have higher flexibility over a wide temperature range. If this percentage is 16% by mass or less, the good adhesion of composition (X) tends to be maintained. This percentage is more preferably 2% by mass or more, even more preferably 4% by mass or more, and particularly preferably 6% by mass or more. Furthermore, this percentage is more preferably 12% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

[0060] Composition (X) may contain a filler (E). The filler (E) can reduce curing shrinkage when composition (X) hardens.

[0061] The filler (E) preferably contains silicone powder (E1). In that case, the flexibility of the cured product tends to be further increased.

[0062] The silicone powder (E1) contains at least one selected from the group consisting of, for example, a powder made of silicone rubber (silicone rubber powder), a powder made of silicone resin (silicone resin powder), and a powder having a core made of silicone rubber and a shell made of silicone resin (silicone composite powder). Note that silicone resin is a silicone having a three-dimensional skeleton mainly composed of siloxane bonds, and silicone rubber is a silicone having a two-dimensional skeleton mainly composed of siloxane bonds.

[0063] The silicone powder (E1) preferably contains at least one of silicone resin powder and silicone composite powder. In this case, the cured product of composition (X) is more likely to have a lower elastic modulus over a wide temperature range.

[0064] The average particle size of the silicone powder (E1) is preferably 0.3 μm or more and 30 μm or less. An average particle size of 0.3 μm or more has the advantage of suppressing an excessive increase in the viscosity of composition (X). An average particle size of 30 μm or less has the advantage of maintaining high penetration into narrow spaces of composition (X). This average particle size is more preferably 0.5 μm or more, and even more preferably 0.7 μm or more. Furthermore, this average particle size is more preferably 20 μm or less, and even more preferably 10 μm or less. Note that the average particle size is the particle size with a cumulative frequency of 50% (d) calculated from the particle size distribution measured by laser diffraction. 50 )

[0065] The percentage of silicone powder (E1) to composition (X) is preferably 15% by mass or more and 50% by mass or less. If this percentage is 15% by mass or more, the flexibility of the cured product (X) tends to be particularly high and curing shrinkage tends to be reduced. Furthermore, if this percentage is 50% by mass or less, there is the advantage that an excessive increase in the viscosity of composition (X) can be suppressed. This percentage is more preferably 20% by mass or more, even more preferably 23% by mass or more, and particularly preferably 27% by mass or more. Furthermore, this percentage is more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less.

[0066] The filler (E) may contain only silicone powder (E1), or it may further contain fillers other than silicone powder (E1) (hereinafter also referred to as filler (E2)).

[0067] Filler (E2) may contain an inorganic filler. Filler (E2) may contain only an inorganic filler. When composition (X) contains an inorganic filler, curing shrinkage during the process of curing composition (X) and producing a cured product is less likely to occur. Therefore, composition (X) becomes even more suitable for bonding parts in precision equipment such as camera modules. The inorganic filler contains at least one selected from the group consisting of, for example, silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium dioxide, barium zirconate, and calcium zirconate.

[0068] If the filler (E) contains a filler (E2) other than silicone powder (E1), the percentage of filler (E2) to composition (X) is, for example, greater than 0% by mass and 30% by mass or less.

[0069] Composition (X) may contain a carbodiimide compound (F). In this case, the cured product of composition (X) is less likely to deteriorate even under high temperature and high humidity conditions, and the reliability of the cured product tends to be increased.

[0070] A carbodiimide compound (F) is a compound having a carbodiimide group (-N=C=N-) in its molecule. Carbodiimide compounds may include at least one selected from the group consisting of polycarbodiimides, monocarbodiimides, and cyclic carbodiimides. Polycarbodiimides may include at least one of aliphatic polycarbodiimides and aromatic polycarbodiimides. Aliphatic polycarbodiimides have a main chain composed of aliphatic hydrocarbons. Aromatic polycarbodiimides have a main chain composed of aromatic hydrocarbons. Monocarbodiimides may include at least one of aliphatic monocarbodiimides and aromatic monocarbodiimides.

[0071] Monocarbodiimide is, for example, N,N'-di-o-toluylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-bis(propylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-di-tert-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodi mid, and contains at least one selected from the group consisting of N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-di-p-toluylcarbodiimide, and the like.

[0072] Polycarbodiimide is, for example, a compound represented by the following formula.

[0073] R 2 -(-N=C=N-R 1 -) m -R 3 In the formula, m R 1 are each independently a divalent aromatic group or aliphatic group. When R 1 is an aromatic group, R 1 may be substituted with at least one selected from among an aliphatic substituent having at least one carbon atom, an alicyclic substituent, and an aromatic substituent. These substituents may have a heteroatom, and may be substituted at at least one ortho position of the aromatic group to which the carbodiimide group bonds. R 2 is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 18 carbon atoms, an aryl group, an aralkyl group having 7 to 18 carbon atoms, -R 4 -NH-COS-R 5 , -R 4 COOR 5 , -R 4 -OR 5 , -R 4 -N(R 5)2, -R 4 -SR 5 , -R 4 -OH, -R 4 -NH2, -R 4 -NHR 5 , -R 4 -Epoxy, -R 4 -NCO, -R 4 -NHCONHR 5 , -R 4 -NHCONR 5 R 6 or -R 4 -NHCOOR 7 That is. R 3 -N=C=N-aryl, -N=C=N-alkyl, -N=C=N-cycloalkyl, -N=C=N-aralkyl, -NCO, -NHCONHR 5 -NHCONHR 5 R 6 , -NHCOOR 7 7. -NHCOS-R 5 ,-COOR 5 , -OR 5 , epoxy, -N(R 5 )2, -SR 5 -OH, -NH2, or -NHR 5 That is. R 4 R is a divalent aromatic group or aliphatic group. 5 and R 6 Each of these is independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, an oligo / polyethylene glycol, or an oligo / polypropylene glycol. 7 R 5 It has one of the above definitions, or it is a polyester group or a polyamide group. m is an integer of 2 or more.

[0074] Polycarbodiimide includes at least one selected from the group consisting of, for example, poly(4,4'-dicyclohexylmethanecarbodiimide), poly(N,N'-di-2,6-diisopropylphenylcarbodiimide), and poly(1,3,5-triisopropylphenylene-2,4-carbodiimide). Examples of commercially available polycarbodiimides include at least one selected from the group consisting of aliphatic polycarbodiimide (Nisshinbo Chemical Co., Ltd., Elastostabb H-01) and carbodiimide-modified isocyanate (Nisshinbo Chemical Co., Ltd., Carbodilite V-05).

[0075] A cyclic carbodiimide comprises one carbodiimide group and a group (bonding group) bonded to either of the two nitrogen atoms (primary and secondary nitrogen) of the carbodiimide group in a single molecule. The bonding group is a divalent group selected from, for example, aliphatic groups, alicyclic groups, aromatic groups, and combinations thereof. The bonding group may also contain a heteroatom. Aromatic groups are selected from, for example, the group consisting of allylene groups having 5 to 15 carbon atoms, arenetriyl groups having 5 to 15 carbon atoms, and arenetetrayl groups having 5 to 15 carbon atoms. Aliphatic groups are selected from, for example, the group consisting of alkylene groups having 1 to 20 carbon atoms, alkanetriyl groups having 1 to 20 carbon atoms, and alkanetetrayl groups having 1 to 20 carbon atoms. Alicyclic groups are selected from, for example, the group consisting of cycloalkylene groups having 3 to 20 carbon atoms, cycloalkanetriyl groups having 3 to 20 carbon atoms, and cycloalkanetetrayl groups having 3 to 20 carbon atoms.

[0076] The carbodiimide compound (F) preferably contains a cyclic carbodiimide. In this case, the storage stability of composition (X) is less likely to be impaired, and the adhesive strength of the cured product is more likely to be increased.

[0077] The percentage of the carbodiimide compound (FE) to the total of the ene compound (A1) and the thiol compound (A2) is preferably 1% by mass or more and 20% by mass or less. When this percentage is 1% by mass or more, the reliability of the cured product tends to be particularly high. When this percentage is 20% by mass or less, the deep curability during curing of composition (X) tends to be maintained. This percentage is more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more. Furthermore, this percentage is more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less.

[0078] Composition (X) may further contain a photopolymerization initiator (G). The photopolymerization initiator (G) can impart photocurability to composition (X). In particular, when composition (X) is used as an adhesive, if composition (X) contains a photopolymerization initiator (G), composition (X) can be partially cured by irradiating it with light to perform temporary adhesion, and then composition (X) can be fully cured by heating to perform permanent adhesion.

[0079] The photopolymerization initiator (G) contains, for example, at least one compound selected from the group consisting of aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds.

[0080] The percentage of the photopolymerization initiator (G) to the total of the ene compound (A1) and the thiol compound (A2) is preferably 0.05% by mass or more and 2.0% by mass or less. A percentage of 0.05% by mass or more provides composition (X) with sufficient photocurability for temporary adhesion. Furthermore, a percentage of 2.0% by mass or less makes it easier to cure composition (X) to a deep level when irradiated with light. A percentage of 0.1% by mass or more is more preferable, 0.2% by mass or more is even more preferable, and 0.4% by mass or more is particularly preferable. Furthermore, a percentage of 1.5% by mass or less is even more preferable, 1.0% by mass or less is even more preferable, and 0.8% by mass or less is particularly preferable.

[0081] Composition (X) may further contain additives other than those mentioned above, to the extent that the effects of this embodiment are not excessively impaired. The additives include, for example, at least one selected from the group consisting of radical scavengers, diluents, solvents, pigments, flexibility imparters, coupling agents, antioxidants, thixotropy imparters, and dispersants.

[0082] Composition (X) can be prepared by mixing the components of composition (X) described above.

[0083] As described above, composition (X) can be used as an adhesive. That is, a cured product can be obtained by curing composition (X), and this cured product can be used to bond, for example, two parts that make up a device (hereinafter also referred to as the first part and the second part).

[0084] The cured product according to this embodiment is obtained by curing composition (X). As described above, the first part and the second part can be bonded together with this cured product.

[0085] The device according to this embodiment comprises a first component, a second component, and a cured material interposed between the first and second components to bond them together. This cured material is obtained by curing composition (X). As described above, the device is a precision instrument such as a camera module, but is not limited to this. For example, the device can be an electronic component such as a semiconductor element, integrated circuit, large-scale integrated circuit, transistor, thyristor, diode, or capacitor. If the device is a camera module, bonding the first component to the second component means bonding the components of the camera module together. Examples of bonding the first component to the second component include joining a substrate to a camera housing and joining a lens unit to a camera housing. The first and second components are not limited to these examples.

[0086] The materials of the first and second components may be, but are not limited to, resins such as liquid crystal polymer, polycarbonate, polyester, metals such as nickel and copper, ceramics, polyimide, glass, or various other substrate materials.

[0087] A method for bonding a first part and a second part using composition (X), and a method for manufacturing an apparatus comprising the first part, the second part, and a cured product are described below.

[0088] A composition (X) is interposed between the first and second parts. In this state, the composition (X) is heated to harden it and produce a hardened product. The first and second parts are bonded together by this hardened product.

[0089] If composition (X) contains a photopolymerization initiator (G), the composition (X) is interposed between the first and second parts, and before heating the composition (X), it is irradiated with light to allow the curing of the composition (X) to progress to a certain extent. This allows the first and second parts to be temporarily bonded together. In this case, the wavelength of the light irradiated onto the composition (X) is appropriately selected depending on the type of photopolymerization initiator (G) in the composition (X). This light is, for example, ultraviolet light. By temporarily bonding the first and second parts in this way, the alignment accuracy can be easily improved by appropriately adjusting the relative positions of the first and second parts.

[0090] The heating conditions for composition (X) are set appropriately so that composition (X) hardens sufficiently. For example, the heating conditions are a heating temperature of 80°C to 120°C and a heating time of 30 minutes to 120 minutes.

[0091] (summary) The curable composition according to the first embodiment contains an ene compound (A1), a thiol compound (A2), a latent curing catalyst (B1), a stabilizer (C), and an acrylic polymer (D) having a glass transition temperature of -30°C or lower.

[0092] According to this embodiment, a curable composition containing an ene compound and a thiol compound can be provided, which has high storage stability and in which the cured product tends to have high flexibility even at low temperatures.

[0093] In a second embodiment, the acrylic polymer (D) contains a reactive polymer (D1) having radically polymerizable unsaturated bonds in its molecule.

[0094] In a third embodiment, in the second embodiment, the reactive polymer (D1) contains a polymer (D11) having the structure shown in the following formula (1). [ka] In formula (1), Fn is a crosslinkable functional group, R is H or an alkyl group having 1 to 10 carbon atoms, and n is a number between 8 and 9000.

[0095] In the fourth embodiment, in any one of the first to third embodiments, the total percentage of the ene compound (A1) and the thiol compound (A2) is 70% by mass or more with respect to the solid content of the curable composition, provided that if the curable composition contains a filler (E), it is 70% by mass or more with respect to the portion of the solid content excluding the filler (E).

[0096] In the fifth embodiment, in any one of the first to fourth embodiments, the stabilizer (C) contains at least one of a radical polymerization inhibitor and an anionic polymerization inhibitor.

[0097] In the sixth embodiment, as in the fifth embodiment, the stabilizer (C) contains an anionic polymerization inhibitor, and the anionic polymerization inhibitor contains a compound having a phenolic hydroxyl group.

[0098] In the seventh embodiment, in any one of the first to sixth embodiments, the curable composition further contains a filler (E), the filler (E) contains a silicone powder (E1).

[0099] In the eighth aspect, as in the seventh aspect, the silicone powder (E1) contains at least one of a silicone composite powder and a silicone resin powder.

[0100] In the ninth embodiment, in any one of the first to eighth embodiments, the curable composition further contains a carbodiimide compound (F).

[0101] In the tenth embodiment, in any one of the first to ninth embodiments, the curable composition further contains a photopolymerization initiator (G).

[0102] In the eleventh embodiment, in any one of the first to tenth embodiments, the curable composition is an adhesive.

[0103] The cured product according to the twelfth embodiment is obtained by curing a curable composition according to any one of the first to eleventh embodiments.

[0104] The apparatus according to the thirteenth embodiment comprises a first component, a second component, and a cured material interposed between the first component and the second component to bond them together. The cured material is obtained by curing a curable composition according to any one of the first to eleventh embodiments. [Examples]

[0105] More specific embodiments of this model are presented below. However, this model is not limited to the embodiments described below.

[0106] 1. Preparation of the composition The composition was prepared by mixing the raw materials shown in Tables 1 and 2. Details of the raw materials shown in Tables 1 and 2 are as follows. -En compounds: Isocyanuric acid EO modified di and triacrylate. Manufactured by Toagosei Co., Ltd. Aronics M-313. - Thiol compound: Pentaerythritol tetrakis(3-mercaptobutyrate). Manufactured by Showa Denko Corporation. Product name: Karens MTPE1 (registered trademark). -Epoxy compound: Liquid bisphenol A type epoxy resin. Manufactured by Nippon Steel Chemical & Materials Co., Ltd. Product name: YD-8125. - Latent curing catalyst #1: Amine adduct-type latent curing catalyst. Manufactured by Ajinomoto Fine Techno Co., Ltd. Amicure PN-40J. - Latent curing catalyst #2: A modified amine compound that is solid at room temperature. Manufactured by T&K TOKA Corporation. Product name: Fujicure FXR-1121. - Non-latent curing catalyst: 2-phenyl-1-benzyl-1H-imidazole. - Photopolymerization initiator #1: 1-hydroxycyclohexyl-phenyl ketone, manufactured by IGM Resins BV, product name Omnirad 184. - Photopolymerization initiator #2: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by IGM Resins BV, product name Omnirad TPO G. -Stabilizer #1: Radical polymerization inhibitor. N-nitroso-N-phenylhydroxylamine aluminum. Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Q-1301 -Stabilizer #2: Anionic polymerization inhibitor. 2,3-Dihydroxynaphthalene. -Acrylic polymer #1: A terminal-reacting liquid acrylic resin having the structure shown in formula (1). Manufactured by Kaneka Corporation. Product name: KANEKA XMAP RC100C. Glass transition temperature: -48°C and 84°C. Number average molecular weight: 5000 to 40000. -Acrylic polymer #2: A terminal-reacting liquid acrylic resin having the structure shown in formula (1). Manufactured by Kaneka Corporation. Product name: KANEKA XMAP RC200C. Glass transition temperature: -31°C and 48°C. Number average molecular weight: 5000 to 40000. -Acrylic Polymer #3: A solid acrylic block copolymer without unsaturated bonds. Manufactured by Kuraray Co., Ltd. Product name: Clarity LA2140. Glass transition temperature: -43°C. Number average molecular weight: 30,000 to 70,000. -Acrylic Polymer #4: A solid acrylic block copolymer without unsaturated bonds. Manufactured by Kuraray Co., Ltd. Product name: Clarity LK9243. Glass transition temperature: -52°C. Number average molecular weight: 30,000 to 70,000. - Acrylic Polymer #5: A solid acrylic copolymer containing epoxy groups. Manufactured by Toagosei Co., Ltd. Product name: ARUFON UG-4035. Glass transition temperature: 52°C. Number average molecular weight: 5000-15000. -Carbodiimide compound #1: Cyclic carbodiimide, manufactured by Teijin Limited, catalog number TCC-FP20M. -Carbodiimide compound #2: Manufactured by Nisshinbo Inc. Catalog number 10M-SP. -Silicone Powder #1: Silicone resin powder. Manufactured by Shin-Etsu Chemical Co., Ltd. Product name: KMP-706. Average particle size: 2 μm. -Silicone Powder #2: Silicone rubber powder. Manufactured by Shin-Etsu Chemical Co., Ltd. Product name KMP-597. Average particle size 5 μm.

[0107] 2. Evaluation Test (1) Storage stability The composition was placed in a light-shielding container, and its viscosity at 25°C was measured using a Type B viscometer at a rotation speed of 20 rpm. Viscosity measurements were performed continuously, and the time required for the viscosity at 25°C to become 2.0 times the initial value was used as an indicator of storage stability.

[0108] (2) Adhesive strength #1 A coating film with a diameter of 5 mm and a thickness of 0.5 mm was prepared by applying the composition to a substrate made of liquid crystal polymer (product name E463i, manufactured by Polyplastics Co., Ltd.). This coating film was exposed to ultraviolet light with a peak wavelength of 365 nm at an integrated illuminance of 500 mJ / cm². 2 The irradiation was performed under the specified conditions. Subsequently, the shear adhesion strength of the composition to the adherend was measured using a shear tester.

[0109] If the adhesive strength measured by this method is 0.3 MPa or higher, the composition can be determined to be suitable for temporary bonding of two components.

[0110] (3) Adhesive strength #2 A coating film with a diameter of 5 mm and a thickness of 0.5 mm was prepared by applying the composition to a substrate made of liquid crystal polymer (product name E463i, manufactured by Polyplastics Co., Ltd.). This coating film was exposed to ultraviolet light with a peak wavelength of 365 nm at an integrated illuminance of 500 mJ / cm². 2 After irradiation under these conditions, the coating film was heat-cured by heating at 80°C for 1 hour to obtain a cured product. The shear adhesion strength of the cured product to the substrate was measured using a shear tester.

[0111] (4) Contraction rate A release film made of polyethylene terephthalate was placed on a glass plate, and a silicone spacer with a plan view of 5 mm x 150 mm and a thickness of 0.5 mm, with open spaces at the top and bottom, was placed on the release film. After filling the space inside the spacer with the composition, a release film made of polyethylene terephthalate was placed on the top surface of the spacer, and the glass plate was placed on this release film. Ultraviolet light with a peak wavelength of 365 nm was directed from above the upper glass plate towards the composition in the space, with an integrated illuminance of 500 mJ / cm². 2 The composition was irradiated under the following conditions. Subsequently, the composition was heated at 80°C. The cured material was prepared by heat curing it by heating for one hour. The shrinkage rate was calculated from the specific gravity of the composition and the specific gravity of the cured material, in accordance with JIS K5600.

[0112] (5) Elastic modulus A cured material was prepared using the same method as described in "(4) Shrinkage Rate" above. A dynamic viscoelasticity test (DMA) using the tensile method was performed on this cured material in accordance with JIS K7244-4. The dynamic viscoelasticity test (DMA) was conducted using a Hitachi High-Tech Science Corporation model DMA7100 as the measuring device, under conditions of a frequency of 1.0 Hz and a heating rate of 10 °C / min. From the results, the maximum value of the elastic modulus (storage modulus) of the cured material within the range of -40 °C to 260 °C was calculated.

[0113] The results are shown in Tables 1 and 2 below.

[0114] [Table 1]

[0115] [Table 2]

[0116] As is clear from the results above, in Example 1, a composition was prepared containing an ene compound, a thiol compound, a curing catalyst, a stabilizer, and an acrylic polymer having a glass transition temperature of -30°C or lower. 12 In this case, the composition exhibited high storage stability, and the elastic modulus of the cured product was reduced over a wide temperature range. Among these, Examples 5, 6, and 11- 12 In this case, there was a tendency for the evaluation of adhesive strength after heating to be higher.

[0117] On the other hand, in Comparative Example 1, which did not contain a latent curing catalyst in the composition, and in Comparative Example 2, which did not contain a stabilizer in the composition, the storage stability of the composition decreased, and in Comparative Example 3, which did not contain an acrylic polymer with a glass transition temperature of -30°C or lower in the composition, the elastic modulus of the cured product increased. Furthermore, in Comparative Example 4, which contained an acrylic polymer with a glass transition temperature exceeding -30°C, the elastic modulus of the cured product could not be reduced.

Claims

1. Ene compound (A1) and, Thiol compound (A2) and, Curing catalyst (B), Stabilizer (C), It contains an acrylic polymer (D) having a glass transition temperature of -30°C or lower. The curing catalyst (B) is a latent curing catalyst (B1), The aforementioned ene compound (A1) does not contain the aforementioned acrylic polymer (D). The percentage of the latent curing catalyst (B1) relative to the sum of the ene compound (A1) and the thiol compound (A2) is 0.1% by mass or more and 35% by mass or less. The percentage of the stabilizer (C) relative to the total of the ene compound (A1), the thiol compound (A2), the latent curing catalyst (B1), the stabilizer (C), and the acrylic polymer (D) is 0.01% by mass or more and 1.0% by mass or less. The percentage of the acrylic polymer (D) relative to the sum of the ene compound (A1), the thiol compound (A2), the latent curing catalyst (B1), the stabilizer (C), and the acrylic polymer (D) is 1% by mass or more and 16% by mass or less. The aforementioned ene compound (A1) contains at least one of a compound having at least one of an acryloyl group and a methacryloyl group and an isocyanurate skeleton, and a compound having a vinyl group and an isocyanurate skeleton. The thiol compound (A2) contains an ester of a polyol and a mercapto organic acid, having at least two thiol groups in one molecule. The stabilizer (C) contains at least one of a radical polymerization inhibitor and an anionic polymerization inhibitor. Curable composition.

2. The acrylic polymer (D) contains a reactive polymer (D1) having a radically polymerizable unsaturated bond in its molecule. The curable composition according to claim 1.

3. The reactive polymer (D1) contains a polymer (D11) having the structure shown in the following formula (1), 【Chemistry 1】 In formula (1), Fn is a crosslinkable functional group, R is H or an alkyl group having 1 to 10 carbon atoms, and n is a number between 8 and 9000. The curable composition according to claim 2.

4. The total percentage of the ene compound (A1) and the thiol compound (A2) is 70% by mass or more with respect to the solid content of the curable composition; however, if the curable composition contains filler (E), it is 70% by mass or more with respect to the portion of the solid content excluding filler (E). A curable composition according to any one of claims 1 to 3.

5. The stabilizer (C) contains the anionic polymerization inhibitor, The anionic polymerization inhibitor contains a compound having a phenolic hydroxyl group. A curable composition according to any one of claims 1 to 3.

6. Further containing filler (E), The filler (E) contains silicone powder (E1), A curable composition according to any one of claims 1 to 3.

7. The silicone powder (E1) contains at least one of a silicone composite powder and a silicone resin powder. The curable composition according to claim 6.

8. Further comprising a carbodiimide compound (F), A curable composition according to any one of claims 1 to 3.

9. Further comprising a photopolymerization initiator (G), A curable composition according to any one of claims 1 to 3.

10. An adhesive, A curable composition according to any one of claims 1 to 3.

11. A curable composition obtained by curing any one of claims 1 to 3, cured product.

12. A first component, a second component, and a cured material interposed between the first component and the second component to bond the first component and the second component together, The cured product is obtained by curing the curable composition described in any one of claims 1 to 3. device.

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