Adhesive set, structure, and method for manufacturing the structure

Abstract

To provide a two-liquid adhesive set capable of exhibiting high adhesive strength.SOLUTION: There is provided an adhesive set which comprises a first liquid containing a (meth)acryloyl compound having two or more (meth)acryloyl groups and an epoxy resin having two or more epoxy groups and a second liquid containing a curing agent containing a compound having a nucleophilic reaction group reactive with both an epoxy group and a (meth)acryloyl group, wherein at least one of the first liquid and the second liquid further contains silica particles having a dimethylsilyl group, a butylsilyl group, a hexylsilyl group, an octylsilyl group or a (meth)acryloyl silyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to adhesive sets, structures, and methods of manufacturing structures. [Background technology]

[0002] Conventionally, two-component adhesives using (meth)acrylic monomers have been known as one type of adhesive (see, for example, Patent Document 1). In the case of conventional two-component adhesives using (meth)acrylic monomers, polymerization of the (meth)acrylic monomers generally proceeds due to a redox catalyst system formed by a polymerization initiator and a reducing agent, resulting in hardening of the adhesive. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-117011 Summary of the Invention [Problem to be solved by the invention]

[0004] It is desirable for two-component adhesives to have improved adhesive strength. One aspect of the present invention provides a two-component adhesive set that can exhibit high adhesive strength. [Means for solving the problem]

[0005] One aspect of the present invention provides an adhesive set comprising: a first liquid containing a (meth)acryloyl compound having two or more (meth)acryloyl groups and an epoxy resin having two or more epoxy groups; and a second liquid containing a curing agent including a compound having a nucleophilic reactive group that reacts with both the epoxy group and the (meth)acryloyl group, wherein at least one of the first liquid or the second liquid further contains an inorganic filler having a substituent. [Effects of the Invention]

[0006] According to one aspect of the present invention, it is possible to provide a two-component adhesive set that can exhibit high adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In this specification, (meth)acryloyl means acryloyl or methacryloyl, and the same applies to other similar expressions.

[0008] [Adhesive set] An adhesive set according to one embodiment comprises a first liquid containing a (meth)acryloyl compound having two or more (meth)acryloyl groups and an epoxy resin having two or more epoxy groups, and a second liquid containing a curing agent including a compound having a nucleophilic reactive group that reacts with both the epoxy group and the (meth)acryloyl group, wherein at least one of the first liquid or the second liquid further contains an inorganic filler having a substituent.

[0009] The (meth)acryloyl compound according to this embodiment is a bifunctional or higher functional compound having an acryloyl group, a methacryloyl group, or both. The number of (meth)acryloyl groups in the (meth)acryloyl compound may be 2 to 4.

[0010] The (meth)acryloyl compound may be, for example, a poly(meth)acrylate of an aliphatic polyol. Examples of the poly(meth)acrylate of an aliphatic polyol include bifunctional (meth)acryloyl compounds such as diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene polypropylene glycol di(meth)acrylate; trifunctional (meth)acryloyl compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; and tetrafunctional (meth)acryloyl compounds such as ditrimethylolpropane tetra(meth)acrylate. Other examples of the (meth)acryloyl compound include tris(2-(meth)acryloyloxyethyl)isocyanurate, 2,2'-di(meth)acryloyloxydiethylphosphate, and ethylene oxide-modified di(meth)acrylate phosphate. The (meth)acryloyl compounds can be used singly or in combination of two or more.

[0011] The (meth)acryloyl compound may have two or more (meth)acryloyl groups and an epoxy group. In this specification, a compound having two or more (meth)acryloyl groups and one or more epoxy groups is classified as a (meth)acryloyl compound. The (meth)acryloyl compound may be a compound having two or more (meth)acryloyl groups and no epoxy group.

[0012] The epoxy resin according to this embodiment may be a bifunctional or higher functional epoxy resin, and may have 2 to 4 epoxy groups.

[0013] Examples of epoxy resins include diglycidyl ether epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, and hydrogenated bisphenol A epoxy resin; novolac epoxy resins such as phenol novolac epoxy resin and cresol novolac epoxy resin; biphenyl epoxy resins such as biphenyl epoxy resin and biphenyl aralkyl epoxy resin; glycidyl ester epoxy resins which are reaction products of polybasic acids (e.g., phthalic acid, dimer acid) with epichlorohydrin; glycidylamine epoxy resins which are reaction products of amine compounds (e.g., p-aminophenol, diaminodiphenylmethane, isocyanuric acid) with epichlorohydrin; and aliphatic epoxy resins.

[0014] The epoxy resin may further have a (meth)acryloyl group. In this specification, a compound having two or more epoxy groups and one (meth)acryloyl group is classified as an epoxy resin. The epoxy resin may also be a compound having two or more epoxy groups and no (meth)acryloyl group.

[0015] The first liquid may further contain a monofunctional (meth)acryloyl compound having one (meth)acryloyl group, a monofunctional epoxy resin having one epoxy group, or both of these.

[0016] The content of the (meth)acryloyl compound in the first liquid may be 10 to 90 mass %, 20 to 80 mass %, 30 to 70 mass %, or 40 to 60 mass % relative to the total amount of the (meth)acryloyl compound and the epoxy resin.

[0017] The curing agent contained in the second liquid is a component that reacts with the epoxy resin, the (meth)acryloyl compound, or both to cure the mixture (adhesive) of the first and second liquids. The curing agent contains at least a compound having a nucleophilic reactive group that reacts with both the epoxy group and the (meth)acryloyl group. This compound may have 2 to 4 or 2 to 3 nucleophilic reactive groups.

[0018] The nucleophilic reactive group may be, for example, an aliphatic amino group or a thiol group. From the viewpoint of reactivity with the (meth)acryloyl group, the nucleophilic reactive group may be an aliphatic amino group. Examples of compounds having an aliphatic amino group include aliphatic amine compounds having two or more primary aliphatic amino groups, such as 1,3-bisaminomethylcyclohexane and 1,6-hexanediamine. An example of a commercially available compound having an aliphatic amino group is jER Cure 3080 (trade name, manufactured by Mitsubishi Chemical Corporation).

[0019] The curing agent contained in the second liquid may further contain a compound that reacts substantially only with the epoxy resin, such as an aromatic amine compound.

[0020] The content of the compound having a nucleophilic reactive group in the second liquid may be 80% by mass or more, 85% by mass or more, or 90% by mass or more, relative to the amount of the second liquid, or 100% by mass or less, 99% by mass or less, or 98% by mass or less.

[0021] The inorganic filler according to this embodiment has a substituent. By incorporating an inorganic filler having a substituent, the coatability of the mixture of the first liquid and the second liquid can be improved, and the adhesive strength with the adherend can be increased. The inorganic filler having a substituent may be contained in the first liquid, the second liquid, or both. When the first liquid contains an inorganic filler, the effects of the present invention are more easily achieved.

[0022] Examples of inorganic fillers include silica particles, calcium carbonate particles, zirconia particles, and alumina particles. The substituent may have an alkyl group or a (meth)acryloyl group. The alkyl group may have 1 to 10, 1 to 9, 2 to 8, 2 to 6, or 2 to 4 carbon atoms.

[0023] When the inorganic filler is a silica particle, it may have a substituent substituted on the hydroxy group on the surface of the silica particle.In this case, the silicon atom derived from the silica particle and the substituent may form a silyl group having a substituent.Examples of such a silyl group having a substituent include a dimethylsilyl group, a trimethylsilyl group, a butylsilyl group, a hexylsilyl group, an octylsilyl group, and a (meth)acryloylsilyl group.The silyl group having a substituent is preferably a dimethylsilyl group, a trimethylsilyl group, a butylsilyl group, a hexylsilyl group, or an octylsilyl group, and more preferably a dimethylsilyl group or a trimethylsilyl group.

[0024] The specific surface area of the inorganic filler according to this embodiment is 60 to 250 m 2 / g, 70-200m 2 / g, or 80-180m 2 / g.

[0025] From the viewpoint of further improving adhesive strength, the content of the inorganic filler may be 1 to 15 parts by mass, 2 to 10 parts by mass, 4 to 9 parts by mass, or 5 to 8 parts by mass relative to 100 parts by mass of the epoxy resin. The content of the inorganic filler in the first liquid may be 1 to 10% by mass, 1 to 8% by mass, or 2 to 5% by mass relative to the amount of the first liquid. The content of the inorganic filler in the second liquid may be 0 to 10% by mass, 0 to 8% by mass, or 0 to 5% by mass relative to the amount of the second liquid.

[0026] The first liquid, the second liquid, or both may further contain a silane coupling agent. The silane coupling agent may be, for example, a compound having a hydrolyzable silyl group and a functional group reactive with at least one of a (meth)acryloyl compound, an epoxy resin, or a curing agent. The hydrolyzable silyl group is, for example, a group having a silicon atom and 1 to 3 alkoxy groups bonded to the silicon atom. The alkoxy group bonded to the silicon atom may have, for example, 1 to 4 carbon atoms. Examples of functional groups reactive with at least one of a (meth)acryloyl compound or an epoxy resin include amino groups such as primary amino groups and secondary amino groups, epoxy groups, mercapto groups, and (meth)acryloyl groups. In this specification, compounds having a hydrolyzable silyl group and a (meth)acryloyl group are classified as silane coupling agents.

[0027] Specific examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.

[0028] Commercially available silane coupling agents include, for example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-5803, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-802, and KBM-803 (all of which are trade names manufactured by Shin-Etsu Chemical Co., Ltd.).

[0029] The content of the silane coupling agent in the first liquid may be 0 to 5 mass % or 0 to 3 mass % relative to the amount of the first liquid.The content of the silane coupling agent in the second liquid may be 0 to 5 mass % or 0 to 3 mass % relative to the amount of the second liquid.

[0030] The first liquid, the second liquid, or both may further contain other components as necessary, such as pigments (e.g., carbon black and titanium oxide particles) and elastomers.

[0031] [Structure] The adhesive sets exemplified above are used to bond adherends together with an adhesive that is a mixture of a first liquid and a second liquid, to obtain a desired structure having two or more adherends and an adhesive layer that bonds them together. The method for producing a structure according to this embodiment includes a step of bonding two or more adherends together using the above-mentioned adhesive set (adhesion step).

[0032] The adherend may be, for example, a molded article made of metal such as steel, iron, copper, tinplate, aluminum, or stainless steel, a resin, or carbon fiber reinforced plastic (CFRP). Two or more adherends may be molded articles made of the same or different materials.

[0033] In the bonding process, a mixture of a first liquid and a second liquid is placed between two or more adherends, and the mixture is cured. Specifically, for example, one adherend is placed with a predetermined gap between it and another adherend, and the first liquid and the second liquid are injected into the gap using a device such as a mixing nozzle, causing the mixture of the first liquid and the second liquid (adhesive) to cure and bond the adherends together. In this case, the first liquid and the second liquid may be mixed approximately simultaneously with the injection between the adherends, or the first liquid and the second liquid may be mixed just before the injection between the adherends.

[0034] The mixing ratio of the first liquid to the second liquid is adjusted so that the adhesive cures appropriately, taking into consideration the stoichiometric ratio of the reaction between the (meth)acryloyl compound and epoxy resin contained in the first liquid and the curing agent contained in the second liquid, etc. For example, the volume ratio of the first liquid to the second liquid may be 0.5 to 5.0.

[0035] The curing conditions are adjusted so that the adhesive is properly cured. For example, the adhesive may be cured in an environment of 10 to 40°C. The curing time may be, for example, 10 minutes or more and 1 week or less. The adhesive may be heated, and in this case, the heating temperature may be, for example, 40 to 120°C.

[0036] The above-described method for manufacturing a structure provides a structure including two or more adherends and an adhesive layer that bonds the two or more adherends together. The adhesive layer is a layer formed by the adhesive set described above. In other words, the adhesive layer is a cured product of a mixture containing the first liquid and the second liquid described above. [Example]

[0037] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to the following examples.

[0038] [Preparation of adhesive set] The following raw materials were used to prepare first and second liquids having the compositions shown in Table 1. (A) (Meth)acryloyl compound 1,6-Hexanediol diacrylate (Viscoat 230, Shin-Nakamura Chemical Co., Ltd.) Both-end acrylate polymer (XMAP RC110C, Kaneka Corporation, Mw: 10000) (B) Epoxy resin Bisfer F type epoxy resin (EPICLON830, DIC Corporation) (C) Hardener 1,3-bisaminomethylcyclohexane (1,3-BAC, Mitsubishi Gas Chemical Company, Inc.) Aliphatic amine curing agent (jER Cure 3080, Mitsubishi Chemical Corporation) (D) Inorganic filler Silica particles with dimethylsilyl groups (Aerosil R972CF, Nippon Aerosil Co., Ltd., specific surface area: 110 ± 20 m 2 / g) Silica particles with octylsilyl groups (Aerosil R805, Nippon Aerosil Co., Ltd., specific surface area: 150 ± 25 m2 / g) Silica particles with methacrylsilyl groups (Aerosil R711, Nippon Aerosil Co., Ltd., specific surface area: 150 ± 25 m 2 / g) Unmodified silica particles (Aerosil 200V, Nippon Aerosil Co., Ltd., specific surface area: 200 ± 25 m 2 / g) (E) Silane coupling agent 3-Glycidyloxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) 3-Aminopropyltrimethoxysilane (KBM-903, Shin-Etsu Chemical Co., Ltd.)

[0039] [Evaluation of adhesive strength] A two-liquid mixing dispenser equipped with a manual gun (Tomita Engineering Co., Ltd., model number: DMA51-1×1 / 2×1), a cartridge (Tomita Engineering Co., Ltd., volume ratio: 2:1, filling amount: 50 mL, model number: CD050-02-PP), and a mixing nozzle (Tomita Engineering Co., Ltd., total length: 124 mm, element: 5.4 mm x 21 pieces, cylinder outer diameter: 7.6 mm, discharge outlet inner diameter: 1.5 mm, model number: MA5.4-21-S) was used to dispense the first and second liquids.

[0040] Two steel plates (size: 25 mm × 100 mm, thickness: 2.0 mm) were prepared as adherends, and two silicone rubber sheets (size: 10 mm × 30 mm, thickness: 0.5 mm) were prepared as spacers. The two silicone rubber sheets were placed between the steel plates so that the adhesive layer was 25 mm × 12.5 mm in size and 0.5 mm in thickness. In this state, the first and second liquids, filled in a cartridge of a two-liquid mixing dispenser at a volume ratio of 2:1, were mixed with the mixing nozzle and dispensed with a manual gun, and the mixture of the first and second liquids was injected between the two steel plates. Next, the specimen was cured at room temperature for 30 minutes and then heated at 100°C for 1 hour. The silicone rubber sheets were then removed, and an evaluation sample was obtained.

[0041] A tensile shear test was performed using the above evaluation samples. For the tensile shear test, an autograph (50 kN, manufactured by Shimadzu Corporation) was used to measure the shear adhesive strength at a tensile speed of 1 mm / min. The maximum stress in the obtained stress-strain curve was taken as the shear adhesive strength. The stress was calculated from the measured load and adhesive area (25 mm x 12.5 mm). In addition, the fracture surface of the sample after the test was visually observed to evaluate the failure mode.

[0042] [Table 1]

Claims

1. a first liquid containing a (meth)acryloyl compound having two or more (meth)acryloyl groups and an epoxy resin having two or more epoxy groups; a second liquid containing a curing agent including a compound having a nucleophilic reactive group that reacts with both an epoxy group and a (meth)acryloyl group, The adhesive set, wherein the first liquid further contains silica particles having a dimethylsilyl group, a butylsilyl group, a hexylsilyl group, an octylsilyl group, or a (meth)acryloylsilyl group.

2. The adhesive set according to claim 1 , wherein the silica particles have a butylsilyl group, a hexylsilyl group, an octylsilyl group, or a (meth)acryloylsilyl group.

3. The specific surface area of the silica particles is 60 to 180 m ２ The adhesive set according to claim 1 or 2, wherein the viscosity is 1 / g.

4. 4. The adhesive set according to claim 1, wherein the (meth)acryloyl compound comprises a bifunctional (meth)acryloyl compound, and the content of the compound having a nucleophilic reactive group in the second liquid is 80 mass % or more relative to the amount of the second liquid.

5. An adhesive set according to any one of claims 1 to 4, wherein the first liquid, the second liquid, or both of them further contain a silane coupling agent.

6. The adhesive set according to any one of claims 1 to 5, wherein the content of the silica particles is 1 to 15 parts by mass per 100 parts by mass of the epoxy resin.

7. The adhesive set according to any one of claims 1 to 6, wherein the nucleophilic reactive group is an aliphatic amino group.

8. The adhesive tape has two or more adherends and an adhesive layer that adheres the two or more adherends, A structure, wherein the adhesive layer is a layer formed from the adhesive set according to any one of claims 1 to 7.

9. A method for producing a ... In the step, a mixture of the first liquid and the second liquid is placed between the two or more adherends, and the mixture is cured.

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