JP7442992B2 - Laminate and method for manufacturing the laminate - Google Patents

Description

The present invention relates to a laminate and a method for manufacturing the laminate.

Cured products of epoxy resins are excellent in many respects such as dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, and chemical resistance. However, cured products of epoxy resins have low fracture toughness and may exhibit very brittle properties, and these properties often pose problems in a wide range of applications. Various techniques have been disclosed to address this problem.

Patent Documents 1 and 2 disclose curable resin compositions in which fine polymer particles are dispersed in a curable resin such as an epoxy resin.

JP2015-078280A International Publication No. WO2016/163491

However, the cured products of the curable resin compositions disclosed in the prior art described above have poor elongation properties, and from the viewpoint of use in joining (adhering) adherends with different linear expansion coefficients, further improvement is required. There was room.

An embodiment of the present invention has been made in view of the above-mentioned problems, and its purpose is to provide a laminate containing a cured product with excellent elongation properties and a high glass transition temperature, and a method for manufacturing the laminate. It is to provide.

The present inventor has completed the present invention as a result of intensive studies to solve such problems.

That is, one embodiment of the present invention includes the following configuration.
[1] It has at least two adherends with different coefficients of linear expansion and a cured product made of a curable resin composition, and the cured product is laminated between the at least two adherends, and the cured product has The elastic resin composition includes an epoxy resin (A) and a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, based on 100 parts by mass of the epoxy resin (A). Containing 1 part by mass to 100 parts by mass of polymer fine particles (B) containing coalescence, 5 parts by mass to 50 parts by mass of blocked urethane (C), and 9.0 parts by mass to 17.0 parts by mass of dicyandiamide (D), laminate.
[2] The laminate according to [1], wherein the cured product has a glass transition temperature of 110° C. or higher, and the cured product has a tensile failure strain of 23.0% or higher obtained by a method compliant with JIS K 7113. body.
[3] It has at least two adherends with different coefficients of linear expansion and a cured product made of a curable resin composition, the cured product is laminated between the at least two adherends, and the cured product has The elastic resin composition includes an epoxy resin (A), polymer fine particles (B) containing a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, and blocked urethane (C). , and dicyandiamide (D), the glass transition temperature of the cured product is 110° C. or higher, and the tensile fracture strain of the cured product obtained by a method according to JIS K 7113 is 23.0% or higher. laminate.
[4] The curable resin composition contains 1 to 100 parts by mass of polymer particles (B) and 5 to 50 parts by mass of blocked urethane (C) per 100 parts by mass of the epoxy resin (A). , and 9.0 parts by mass to 17.0 parts by mass of dicyandiamide (D), the laminate according to [3].
[5] The epoxy resin (A) contains a bisphenol F-type epoxy resin (A1), and the content of the bisphenol F-type epoxy resin (A1) in 100 mass% of the epoxy resin (A) is 1% by mass. The laminate according to any one of [1] to [4], which has a content of 100% by mass.
[6] Further contains an inorganic filler (E), and the content of the inorganic filler (E) in 100% by mass of the curable resin composition is 0.1% by mass to 15% by mass, [ The laminate according to any one of [1] to [5].
[7] The curable resin composition further contains 0.1 to 10 parts by mass of a curing accelerator (F) based on 100 parts by mass of the epoxy resin (A), [1] to [ 6]. The laminate according to any one of [6].
[8] The elastic body is any one of [1] to [7], including one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic body. The laminate described in .
[9] The laminate according to any one of [1] to [8], wherein the diene rubber is a butadiene rubber and/or a butadiene-styrene rubber.
[10] The graft portion is a polymer containing, as a constitutional unit, a constitutional unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. The laminate according to any one of [1] to [9].
[11] The laminate according to any one of [1] to [10], wherein the graft portion is a polymer having an epoxy group.
[12] The graft part is a polymer having an epoxy group, and the content of the epoxy group with respect to the mass of the graft part is 0.1 mmol/g to 5.0 mmol/g [1] to [11] The laminate according to any one of the above.
[13] A bonding step of applying a curable resin composition to a first adherend and bonding a second adherend to the first adherend, and curing the curable resin composition. a curing step, the first adherend and the second adherend have different coefficients of linear expansion, and the curable resin composition comprises an epoxy resin (A) and an epoxy resin ( A) 1 to 100 parts by mass of polymer fine particles (B) containing a rubber-containing graft copolymer having an elastic body and a graft part grafted to the elastic body, blocked A method for producing a laminate containing 5 to 50 parts by mass of urethane (C) and 9.0 to 17.0 parts by mass of dicyandiamide (D).
[14] A bonding step of applying a curable resin composition to a first adherend and bonding a second adherend to the first adherend, and curing the curable resin composition. a curing step, the first adherend and the second adherend have different linear expansion coefficients, and the curable resin composition comprises an epoxy resin (A), an elastic body, and the elastic body. The cured product contains polymer fine particles (B) containing a rubber-containing graft copolymer having a graft moiety grafted to A method for manufacturing a laminate, wherein the temperature is 110° C. or higher, and the cured product obtained by a method according to JIS K 7113 has a tensile failure strain of 23.0% or higher.
[15] The method for producing a laminate according to [13] or [14], wherein in the curing step, the curing temperature of the curable resin composition is 130°C or higher.

According to one embodiment of the present invention, it is possible to provide a laminate including a cured product having excellent elongation properties and a high glass transition temperature, and a method for manufacturing the laminate.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to each configuration described below, and various changes can be made within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. Note that all academic literature and patent literature described in this specification are incorporated as references in this specification. In addition, unless otherwise specified in this specification, the numerical range "A to B" is intended to be "above A (including A and greater than A) and less than or equal to B (including B and less than B)."

[1. Technical idea of one embodiment of the present invention]
It is preferable that the curable resin composition used for joining different members (adherends) having different coefficients of linear expansion have excellent elongation properties. The curable resin compositions disclosed in Patent Document 1 and Patent Document 2 have poor elongation properties. The present inventor first conducted extensive studies with the aim of providing a cured product with excellent elongation properties. As a result, it was found that by adding a large amount of blocked urethane, it was possible to provide a cured product with excellent elongation properties. However, the present inventor independently discovered that the obtained cured product had a low glass transition temperature (sometimes referred to as Tg).

The lower the Tg of the cured product, the lower the elastic modulus. A laminate containing a cured product with a low elastic modulus has poor rigidity. Rigidity is required in fields such as vehicles, aircraft, space, machinery, electricity, architecture, and civil engineering. Therefore, in order to be suitably used in these fields, it is necessary to provide a laminate with excellent rigidity, and it is necessary to provide a laminate containing a cured product with a high modulus of elasticity. It is necessary to provide a laminate containing.

Therefore, the present inventor conducted further intensive studies with the aim of providing a cured product that has excellent elongation properties and a high Tg. As a result, the present inventors have found that by using dichyadiamide and blocked urethane in combination with polymer fine particles in amounts that would not normally be used by those skilled in the art, it is possible to provide a cured product with excellent elongation properties and a high Tg. We obtained new knowledge. Based on this knowledge, the present invention was completed by providing a laminate containing a cured product with excellent elongation properties and a high glass transition temperature, and a method for producing the laminate.

[2. Laminate]
One embodiment of the invention provides a first laminate. The first laminate includes at least two adherends having different coefficients of linear expansion and a cured product made of a curable resin composition, and the cured product is laminated between the at least two adherends. . In the first laminate, the curable resin composition contains the epoxy resin (A) and 1 to 100 parts by mass of the polymer fine particles (B), blocked polymer particles, and 100 parts by mass of the epoxy resin (A). Contains 5 to 50 parts by weight of urethane (C) and 9.0 to 17.0 parts by weight of dicyandiamide (D). In the first laminate, the polymer fine particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.

"Epoxy resin (A)," "polymer fine particles (B)," "blocked urethane (C)," and "dicyandiamide (D)" are respectively "component (A)," "component (B)," and "component (B)." (C) component" and "(D) component" in some cases.

Since the first laminate has the above-mentioned configuration, in particular, the curable resin composition contains specific amounts of each of component (A), component (B), component (C), and component (D). It has the advantage of having excellent physical properties and containing a cured product with a high glass transition temperature (Tg).

In this specification, the physical property of elongation of the cured product is evaluated by the tensile fracture strain (%) of the cured product. That is, the physical property of elongation refers to the value of tensile fracture strain (%). It means that the larger the tensile fracture strain (%) of the cured product is, the better the physical properties of elongation are. It can also be said that the first laminate includes a cured product with a large tensile fracture strain (%). A cured product with a high glass transition temperature (Tg) has excellent heat resistance and elastic modulus (rigidity). Therefore, it can be said that the first laminate includes a cured product having excellent heat resistance and elastic modulus (rigidity). The first laminate has both high elongation physical properties (tensile fracture strain (%)) and high Tg. Therefore, it can be said that the first laminate has an excellent balance between physical properties of elongation and Tg.

Another embodiment of the invention provides a second laminate. The second laminate includes at least two adherends having different coefficients of linear expansion and a cured product made of a curable resin composition, and the cured product is laminated between the at least two adherends. . In the second laminate, the curable resin composition contains an epoxy resin (A), polymer particles (B), blocked urethane (C), and dicyandiamide (D). In the second laminate, the polymer fine particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body. In the second laminate, the glass transition temperature (Tg) of the cured product is 110° C. or higher, and the tensile fracture strain of the cured product obtained by a method based on JIS K 7113 is 23.0% or higher.

Since the second laminate has the above structure, the curable resin composition contains the (A) component, the (B) component, the (C) component, and the (D) component, and the cured product has a specific Therefore, it has the advantage of having excellent physical properties of elongation and containing a cured product with a high glass transition temperature (Tg). In the second laminate, the content of each of component (A), component (B), component (C), and component (D) in the curable resin composition is particularly limited as long as the cured product has specific physical properties. However, it can be set as appropriate.

Both the first laminate and the second laminate are laminates according to one embodiment of the present invention. "The laminate according to an embodiment of the present invention" may also be referred to as "this laminate". The curable resin composition used in the first laminate and the curable resin composition used in the second laminate are both curable resins according to an embodiment of the present invention. It is a composition. "The curable resin composition according to one embodiment of the present invention" may be referred to as "the present curable resin composition". Both the cured product contained in the first laminate and the cured product contained in the second laminate are cured products according to an embodiment of the present invention. "The cured product according to one embodiment of the present invention" may be referred to as "main cured product".

(2-1. Curable resin composition)
(2-1-1. Epoxy resin (A))
This curable resin composition contains an epoxy resin (A) as a main component.

As the epoxy resin (A), various hard epoxy resins can be used, excluding the rubber-modified epoxy resin and urethane-modified epoxy resin described below. Examples of the epoxy resin (A) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, and novolac epoxy resin. , glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, flame-retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoin Acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanate nurate, divinylbenzene dioxide, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, glycidyl ether of dihydric or higher polyhydric aliphatic alcohol such as glycerin , chelate-modified epoxy resins, hydantoin-type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, aminoglycidyl ether resins, and the above-mentioned epoxy resins, bisphenol A (or F), polybasic acids, etc. Examples include epoxy compounds obtained by addition reaction of . The epoxy resin (A) is not limited to these, and commonly used epoxy resins may be used.

The above-mentioned "hard epoxy resin" is intended to be an epoxy resin having a specific glass transition temperature (Tg), and includes, for example, an epoxy resin having a Tg of 50° C. or higher.

More specifically, the polyalkylene glycol diglycidyl ether includes polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like. More specific examples of the glycol diglycidyl ether include neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and cyclohexanedimethanol diglycidyl ether. It will be done. More specifically, the diglycidyl ester of the aliphatic polybasic acid includes dimer acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, maleic acid diglycidyl ester, and the like. More specifically, the glycidyl ether of dihydric or higher polyhydric aliphatic alcohol includes trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil modified polyglycidyl ether, propoxylated glycerin triglycidyl ether, and sorbitol. Examples include polyglycidyl ether. Examples of epoxy compounds obtained by addition-reacting polybasic acids to epoxy resins include tall oil fatty acid dimer (dimer acid) and bisphenol A-type epoxy as described in WO2010-098950. Examples include addition reaction products with resins. These epoxy resins may be used alone or in combination of two or more.

The polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of an aliphatic polybasic acid, and the glycidyl ether of a dihydric or higher polyhydric aliphatic alcohol are epoxy resins having a relatively low viscosity. . In this specification, polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, and glycidyl ether of polyhydric aliphatic alcohol having two or more hydrides are referred to as low-viscosity epoxy resins. When the low viscosity epoxy resin is used in conjunction with an epoxy resin other than low viscosity epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, the low viscosity epoxy resin can function as a reactive diluent. As a result, the low-viscosity epoxy resin can improve the balance between the viscosity of the curable resin composition and the physical properties of the cured product obtained from the curable resin composition. The curable resin composition may include an epoxy resin (eg, a low viscosity epoxy resin) that can function as a reactive diluent. The content of the epoxy resin that functions as a reactive diluent is preferably 0.5% to 20% by mass, more preferably 1% to 10% by mass, and more preferably 2% by mass based on 100% by mass of the epoxy resin (A). % to 5% by mass is more preferred.

The chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound containing a chelate functional group (chelate ligand). When a chelate-modified epoxy resin is added to the present curable resin composition and used as an adhesive, adhesion to the surface of a metal substrate contaminated with an oily substance can be improved. A chelate functional group is a functional group of a compound that has multiple coordination sites in its molecule that can coordinate to metal ions, and includes, for example, a phosphorus-containing acid group (for example, -PO(OH) ₂ ), a carboxylic acid group (- CO ₂ H), sulfur-containing acid groups (eg -SO ₃ H), amino groups and hydroxyl groups (especially hydroxyl groups adjacent to each other in an aromatic ring). Examples of chelate ligands include ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether, and the like. Commercially available chelate-modified epoxy resins include ADEKA RESIN EP-49-10N manufactured by ADEKA.

The amount of the chelate-modified epoxy resin used in component (A) is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight.

In this specification, the "amount used" of a certain component can also be said to be the "amount added" of the component, and also the "content" of the component in the curable resin composition or cured product.

Among these epoxy resins, those having at least two epoxy groups in one molecule have high reactivity in curing the resulting curable resin composition, and the resulting cured product tends to form a three-dimensional network. Preferable from this point of view.

Since the curable resin composition can provide a cured product with a large tensile failure strain, the epoxy resin (A) preferably contains a bisphenol F-type epoxy resin (A1). On the other hand, the bisphenol F-type epoxy resin (A1) can lower the Tg of the cured product provided by the curable resin composition. Bisphenol F type epoxy resin (A1 ) is preferably 1% by mass to 100% by mass, more preferably 5% to 70% by mass, even more preferably 10% to 50% by mass, and even more preferably 15% by mass. It is particularly preferred that the amount is 30% by mass.

As the epoxy resin (A), bisphenol A type epoxy resin and bisphenol F type epoxy resin (A1) are used as the epoxy resin (A) because a cured product having a high elastic modulus and excellent heat resistance and adhesiveness can be obtained and is relatively inexpensive. is preferred, and bisphenol A type epoxy resin is more preferred.

Moreover, among the various epoxy resins mentioned above, epoxy resins having an epoxy equivalent of less than 220 are preferable because the obtained cured product has high elastic modulus and heat resistance, and has low temperature dependence of viscosity. Among the above-mentioned epoxy resins, epoxy resins with an epoxy equivalent of 90 or more and less than 210 are more preferable, and epoxy resins with an epoxy equivalent of 150 or more and less than 200 are still more preferable.

The epoxy resin (A) is preferably a bisphenol A epoxy resin and/or a bisphenol F epoxy resin having an epoxy equivalent of less than 220. Since bisphenol A type epoxy resin and bisphenol F type epoxy resin are liquid at room temperature, according to the above configuration, the temperature dependence of the viscosity of the resulting curable resin composition is reduced, resulting in good handling properties.

Epoxy resin (A) contains bisphenol A type epoxy resin and/or bisphenol F type epoxy resin having an epoxy equivalent of 220 or more and less than 5000, preferably 40% by mass or less, more preferably 40% by mass or less, in 100% by mass of component (A). It is preferable to add in an amount of 20% by mass or less. According to the above configuration, there is an advantage that the obtained cured product has excellent impact resistance.

(2-1-2. Polymer fine particles (B))
The curable resin composition according to one embodiment of the present invention can provide a cured product with excellent toughness and impact peel adhesion due to the toughness improving effect of component (B). In addition, the curable resin composition according to an embodiment of the present invention contains the component (B), so that the cured product has excellent physical properties of elongation, high Tg, and good heat resistance and elastic modulus (rigidity). can be provided. In other words, a cured product provided by a curable resin composition containing components (A), (C), and (D) without containing component (B) has a small tensile fracture strain, that is, a low elongation. It has poor physical properties, low Tg, and poor heat resistance and elastic modulus (rigidity).

The curable resin composition according to an embodiment of the present invention preferably contains 1 part by mass to 100 parts by mass of component (B), and preferably 3 parts by mass to 70 parts by mass, based on 100 parts by mass of component (A). It is more preferable to contain 1 part by weight, more preferably 5 parts by weight to 50 parts by weight, and particularly preferably 10 parts by weight to 40 parts by weight. According to this configuration, (a) the obtained curable resin composition has an excellent balance between the shear rate dependence of the viscosity and the ease of handling, and the toughness improvement effect of the obtained cured product, and (b) the obtained curable resin The composition has excellent elongation properties and can provide a cured product with a high Tg.

The volume average particle diameter (Mv) of the polymer fine particles (B) is not particularly limited, but in consideration of industrial productivity, it is preferably 10 nm to 2000 nm, more preferably 30 nm to 600 nm, even more preferably 50 nm to 400 nm, and even more preferably 100 nm to 200 nm. is particularly preferred. According to the above configuration, there is also an advantage that a highly stable curable resin composition having a desired viscosity can be obtained. In addition, in this specification, the "volume average particle diameter (Mv) of the polymer fine particles (B)" is intended to mean the volume average particle diameter of the primary particles of the polymer fine particles (B), unless otherwise specified. The volume average particle diameter (Mv) of the polymer fine particles (B) is measured using a dynamic light scattering particle size distribution measuring device (for example, Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.)) using an aqueous latex containing the polymer fine particles (B) as a sample. It can be measured using The method for measuring the body volume average particle diameter of the polymer fine particles (B) will be described in detail in the Examples below. In addition, the volume average particle diameter of the polymer fine particles (B) can be determined by cutting the cured product of the laminate, imaging the cut surface of the cured product using an electron microscope, etc., and then using the obtained imaging data (captured image). It can also be measured by

In the curable resin composition according to an embodiment of the present invention, component (B) has a half-value width of 0.5 times or more and 1 time or less of the volume average particle size in the number distribution of the volume average particle size. It is preferable to have the following because the resulting curable resin composition has a low viscosity and is easy to handle.

Since the above-mentioned specific particle size distribution can be easily realized, it is preferable that two or more maximum values exist in the number distribution of the volume average particle size of the component (B). It is more preferable that there are 2 to 3 maximum values in the number distribution of the volume average particle diameter of component (B), and it is preferable that there be 2 maximum values, because it requires less time and effort during production and the cost is low. is even more preferable. Component (B) particularly includes 10 to 90% by mass of polymer fine particles having a volume average particle size of 10 nm or more and less than 150 nm, and 90 to 10 mass% of polymer fine particles (B) having a volume average particle size of 150 nm or more and 2000 nm or less. It is preferable.

Component (B) is preferably dispersed in the form of primary particles in the curable resin composition or cured product. In one embodiment of the present invention, "the polymer fine particles (B) are dispersed in the state of primary particles in the curable resin composition or cured product" means that in the curable resin composition or cured product, This means that the polymer fine particles (B) are substantially independently dispersed (without contacting each other). The dispersion state of the polymer fine particles (B) in the curable resin composition or cured product can be expressed as, for example, the volume average particle diameter (Mv)/number average particle diameter (Mn) of the polymer fine particles (B) (hereinafter referred to as "Mv/Mn"). ) can be confirmed by measuring.

Mv/Mn of the polymer fine particles (B) is determined by measuring the volume average particle diameter (Mv ) and the number average particle diameter (Mn), respectively, and can be determined by dividing Mv by Mn. The Mv/Mn of the polymer fine particles (B) in the curable resin composition can be determined, for example, by dissolving a part of the curable resin composition in a solvent such as methyl ethyl ketone, and subjecting the resulting mixture (dissolved material) to dynamic light. It can be measured by using a scattering type particle size distribution measuring device. The Mv/Mn of the polymer fine particles (B) in the cured product can be determined by, for example, cutting the cured product of the laminate and imaging the cut surface of the cured product using an electron microscope or the like. ).

The value of volume average particle diameter (Mv)/number average particle diameter (Mn) of the polymer fine particles (B) is not particularly limited, but is preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less. It is preferably 1.5 or less, particularly preferably 1.5 or less. When the volume average particle diameter (Mv)/number average particle diameter (Mn) of the polymer fine particles (B) is 3 or less, the polymer fine particles (B) form well in the curable resin composition or cured product, that is, as primary particles. It is thought that they are dispersed in a state of . A curable resin composition in which the polymer fine particles (B) have Mv/Mn of 3 or less, that is, a curable resin composition in which the polymer fine particles (B) have good dispersibility, has physical properties such as impact resistance, adhesion, and elongation. It is possible to provide a cured product that has excellent properties, high Tg, and good heat resistance and elastic modulus (rigidity). A cured product in which the Mv/Mn of the polymer particles (B) is 3 or less, that is, a cured product in which the polymer particles (B) have good dispersibility, has excellent physical properties such as impact resistance, adhesion, and elongation, and has a high Tg. , heat resistance and elastic modulus (rigidity) are improved.

In addition, the state in which the polymer fine particles (B) are constantly dispersed over a long period of time under normal conditions without agglomerating, separating, or precipitating in the continuous layer can be confirmed. , may also be referred to as a "stable dispersion" of the polymer fine particles (B). Examples of the "continuous layer" include curable resin compositions and cured products. It is preferable that the distribution of the polymer fine particles (B) in the continuous layer does not change substantially. Furthermore, even if the continuous layer (for example, a curable resin composition) is heated within a non-hazardous range to lower the viscosity of the continuous layer and then stirred, the polymer fine particles (B) in the continuous layer may be "stabilized." Preferably, a "dispersion" is maintained.

Component (B) may be used alone or in combination of two or more.

(elastic body)
The elastic body preferably contains one or more selected from the group consisting of natural rubber, diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic body, and diene rubber, (meth)acrylate rubber and polysiloxane rubber-based elastomer. The elastic body can also be referred to as rubber particles. (Meth)acrylate as used herein means acrylate and/or methacrylate. Polysiloxane rubber-based elastic bodies are sometimes referred to as organosiloxane-based rubbers.

(a) The resulting cured product has a high toughness-improving effect and impact-resistant peel adhesion-improving effect, and (b) has low affinity with matrix resins (e.g., epoxy resin (A)), resulting in curable properties. The elastic body preferably contains a diene rubber, and more preferably a diene rubber, since the viscosity of the resin composition is unlikely to increase over time due to swelling of the elastic body. When the elastic body contains a diene rubber, the resulting curable resin composition can also provide a cured product with excellent toughness and impact resistance.

Hereinafter, a case where the elastic body contains a diene rubber (case A) will be described. The diene rubber is an elastic body containing, as a constitutional unit, a constitutional unit derived from a diene monomer. The diene monomer can also be referred to as a conjugated diene monomer. In case A, the diene rubber contains 50 to 100% by mass of structural units derived from diene monomers out of 100% by mass of structural units, and vinyl monomers other than diene monomers that can be copolymerized with diene monomers. It may contain 0 to 50% by mass of structural units derived from the above. In case A, the diene rubber may contain, as a structural unit, a structural unit derived from a (meth)acrylate monomer in a smaller amount than the structural unit derived from a diene monomer.

Examples of diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene monomers may be used alone or in combination of two or more.

Examples of vinyl monomers other than diene monomers (hereinafter also referred to as vinyl monomer A) that can be copolymerized with diene monomers include (i) styrene, α-methylstyrene, monochlorostyrene, dichlorostyrene, etc. (ii) Vinyl carboxylic acids such as acrylic acid and methacrylic acid; (iii) Vinyl cyanates such as acrylonitrile and methacrylonitrile; (iv) Vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene. (v) vinyl acetate; alkenes such as ethylene, propylene, butylene, and isobutylene; (vi) polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The above-mentioned vinyl monomer A may be used alone or in combination of two or more types. Among the vinyl monomers A mentioned above, styrene is particularly preferred.

The elastic body is preferably butadiene rubber and/or butadiene-styrene rubber, more preferably butadiene rubber. The butadiene rubber is a rubber composed of structural units derived from 1,3-butadiene, and is also called polybutadiene rubber. The butadiene-styrene rubber is a copolymer of 1,3-butadiene and styrene, and is also called polystyrene-butadiene. According to the above structure, (a) the obtained cured product has the advantage of having a higher toughness improving effect, and (b) the obtained curability is lower because the affinity with the matrix resin (for example, epoxy resin (A)) is lower. This has the advantage that viscosity increase over time due to swelling of the elastic body is less likely to occur in the resin composition. Further, butadiene-styrene rubber is more preferable in that the transparency of the obtained cured product can be improved by adjusting the refractive index.

Since a wide variety of polymer designs are possible by combining various monomers, the elastic body preferably contains (meth)acrylate rubber, and more preferably (meth)acrylate rubber. The case where the elastic body contains (meth)acrylate rubber (case B) will be described below.

The (meth)acrylate rubber is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate monomer. In case B, the (meth)acrylate rubber contains 50 to 100% by mass of structural units derived from the (meth)acrylate monomer out of 100% by mass of the structural units, and is copolymerizable with the (meth)acrylate monomer. It may contain 0 to 50% by mass of structural units derived from vinyl monomers other than (meth)acrylate monomers. In case B, the (meth)acrylate rubber may contain, as a structural unit, a structural unit derived from a diene monomer in a smaller amount than the structural unit derived from a (meth)acrylate monomer.

Examples of (meth)acrylate monomers include (i) methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate; Alkyl (meth)acrylates such as acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (ii) Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; (iii) ) hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (iv) glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; (v) alkoxyalkyl (meth)acrylates; (vi) allyl alkyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; (vii) monoethylene glycol di(meth)acrylate; Examples include polyfunctional (meth)acrylates such as triethylene glycol di(meth)acrylate and tetraethylene glycol di(meth)acrylate. These (meth)acrylate monomers may be used alone or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are particularly preferred.

The vinyl monomer other than the (meth)acrylate monomer that can be copolymerized with the (meth)acrylate monomer (hereinafter also referred to as vinyl monomer other than the (meth)acrylate monomer) is the vinyl monomer A. Examples include the monomers listed in . Vinyl monomers other than (meth)acrylate monomers may be used alone or in combination of two or more. Among vinyl monomers other than (meth)acrylate monomers, styrene is particularly preferred.

When attempting to improve the impact resistance of the cured product at low temperatures without reducing the heat resistance of the resulting cured product, it is preferable that the elastic body contains a polysiloxane rubber-based elastic body; More preferably, it is a body. Hereinafter, a case where the elastic body includes a polysiloxane rubber-based elastic body (case C) will be described.

The polysiloxane rubber elastomer is, for example, (a) composed of alkyl or aryl di-substituted silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, etc. and (b) a polysiloxane polymer composed of alkyl or aryl monosubstituted silyloxy units, such as organohydrogensilyloxy in which some of the alkyl side chains are substituted with hydrogen atoms. , can be mentioned. These polysiloxane polymers may be used alone or in combination of two or more. Among these polysiloxane-based polymers, (a) dimethylsilyloxy units, methylphenylsilyloxy units, and/or dimethyl Polymers composed of silyloxy-diphenylsilyloxy units are preferred, and (b) polymers composed of dimethylsilyloxy units are most preferred because they are readily available and economical.

In case C, the polymer fine particles (B) preferably contain 80% by mass or more of polysiloxane rubber-based elastic material, and preferably contain 90% by mass or more of the 100 mass% of elastic material contained in the polymer fine particles (B). It is more preferable that you do so. According to the configuration, the resulting curable resin composition can provide a cured product with excellent heat resistance.

The elastic body may further contain an elastic body other than diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic body. Examples of elastic bodies other than diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic bodies include natural rubber.

(Crosslinked structure of elastic body)
Since the dispersion stability of the polymer fine particles (B) in the curable resin composition can be maintained, it is preferable that a crosslinked structure is introduced into the elastic body. As a method for introducing a crosslinked structure into an elastic body, commonly used methods can be employed, and examples include the following method. That is, in the production of an elastic body, a method may be mentioned in which a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound is mixed with a monomer that can constitute the elastic body, and then polymerized. In this specification, producing a polymer such as an elastomer is also referred to as polymerizing the polymer.

In addition, as a method for introducing a crosslinked structure into a polysiloxane rubber-based elastomer, the following method may be mentioned: (a) When polymerizing a polysiloxane rubber-based elastomer, a polyfunctional alkoxysilane compound is added to the polysiloxane rubber-based elastomer. (b) A method in which a reactive group such as a vinyl-reactive group or a mercapto group is introduced into a polysiloxane rubber elastomer, and then a vinyl-polymerizable monomer or organic peroxide is added. or (c) when polymerizing the polysiloxane rubber-based elastomer, a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound is mixed with other materials, and then polymerized. how to do it, etc.

A polyfunctional monomer can also be said to be a monomer having two or more radically polymerizable reactive groups within the same molecule. The radically polymerizable reactive group is preferably a carbon-carbon double bond. Examples of polyfunctional monomers include allyl (meth)acrylates, allyl alkyl (meth)acrylates such as allyl alkyl (meth)acrylate, and ethylenically unsaturated double bonds such as allyloxyalkyl (meth)acrylates. Examples include (meth)acrylates having the following. Examples of monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. Examples include meth)acrylates. Examples of the polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, etc. is exemplified. In addition, monomers having three (meth)acrylate groups include alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-hydroxyethyl). Examples include isocyanurate tri(meth)acrylate. Examples of the alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, and the like. Furthermore, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, examples of the monomer having five (meth)acrylic groups include dipentaerythritol penta(meth)acrylate. Furthermore, examples of the monomer having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Polyfunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like. Among these, particularly preferred polyfunctional monomers are allyl methacrylate, triallylisocyanurate, butanediol di(meth)acrylate, and divinylbenzene.

Examples of mercapto group-containing compounds include alkyl-substituted mercaptans, allyl-substituted mercaptans, aryl-substituted mercaptans, hydroxy-substituted mercaptans, alkoxy-substituted mercaptans, cyano-substituted mercaptans, amino-substituted mercaptans, silyl-substituted mercaptans, and acid-substituted mercaptans. Examples include mercaptan, halo group-substituted mercaptan, and acyl group-substituted mercaptan. The alkyl group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having 1 to 20 carbon atoms, more preferably an alkyl group-substituted mercaptan having 1 to 10 carbon atoms. As the aryl group-substituted mercaptan, phenyl group-substituted mercaptan is preferred. The alkoxy-substituted mercaptan is preferably an alkoxy-substituted mercaptan having 1 to 20 carbon atoms, more preferably an alkoxy-substituted mercaptan having 1 to 10 carbon atoms. The acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms, or a mercaptan having a carboxyl group and having an aryl group having 1 to 12 carbon atoms.

(gel content of elastic body)
The elastic body of the polymer fine particles (B) preferably has rubber properties in order to increase the toughness of the resulting cured product. The elastic body is preferably one that can swell in a suitable solvent but does not substantially dissolve in it. The elastic body is preferably insoluble in the epoxy resin (A) used.

The gel content of the elastic body is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, since the resulting cured product has excellent toughness. It is particularly preferable that the content is 95% by mass or more.

In this specification, the method for calculating gel content is as follows. First, an aqueous latex containing polymer fine particles (B) is obtained, and then a powder of polymer fine particles (B) is obtained from the aqueous latex. The method for obtaining the powder of polymer fine particles (B) from the aqueous latex is not particularly limited, but includes, for example, (i) agglomerating the polymer fine particles (B) in the aqueous latex, and (ii) dehydrating the resulting agglomerates. and (iii) further drying the aggregate to obtain a powder of polymer fine particles (B). Next, 0.5 g of powder of polymer fine particles (B) is immersed in 100 g of toluene. Next, the resulting mixture is allowed to stand at 23° C. for 24 hours. Thereafter, the obtained mixture is separated into a component soluble in toluene (toluene soluble component) and a component insoluble in toluene (toluene insoluble component). The masses of the obtained toluene-soluble and toluene-insoluble components are measured, and the gel content is calculated from the following formula.
Gel content (%) = (mass of toluene insoluble matter) / {(mass of toluene insoluble matter) + (mass of toluene soluble matter)} x 100
(Glass transition temperature of elastic body)
The glass transition temperature (Tg) of the elastic body is preferably 0°C or lower, more preferably -20°C or lower, even more preferably -40°C or lower, and -60°C or lower, in order to improve the toughness of the resulting cured product. The following is particularly preferable.

On the other hand, when it is desired to suppress a decrease in the elastic modulus (rigidity) of the obtained cured product, the Tg of the elastic body is preferably larger than 0°C, more preferably 20°C or higher, and more preferably 50°C or higher. The temperature is more preferably 80°C or higher, particularly preferably 120°C or higher, and most preferably 120°C or higher.

The Tg of the elastic body can be determined by the composition of the structural units contained in the elastic body. In other words, by changing the composition of the monomer used when producing (polymerizing) the elastic body, the Tg of the resulting elastic body can be adjusted.

Here, when a homopolymer is obtained by polymerizing only one type of monomer, a group of monomers that provides a homopolymer having a Tg greater than 0° C. is referred to as monomer group a. Further, when a homopolymer is obtained by polymerizing only one type of monomer, a group of monomers that provides a homopolymer having a Tg of less than 0° C. is referred to as monomer group b. Polymers that have a Tg greater than 0°C and can form an elastic body that can suppress a decrease in rigidity of the resulting cured product include:
50 to 100% by mass (more preferably 65 to 99% by mass) of structural units derived from at least one monomer selected from monomer group a, and derived from at least one monomer selected from monomer group b Examples include polymers containing 0 to 50% by mass (more preferably 1 to 35% by mass) of structural units.

Even when the Tg of the elastic body is greater than 0° C., it is preferable that a crosslinked structure is introduced into the elastic body. Examples of the method for introducing the crosslinked structure include the methods described above.

Examples of monomers that can be included in monomer group a include, but are not limited to, (i) unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; (ii) α-methylstyrene and the like; Vinyl-substituted aromatic compounds; (iii) 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc. (iv) Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; (v) Ring halogenation such as 2-chlorostyrene and 3-chlorostyrene. Vinyl aromatic compounds; (vi) Ring ester substituted vinyl aromatic compounds such as 4-acetoxystyrene; (vii) Ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; (viii) Vinyl benzoate, vinyl Vinyl esters such as cyclohexanoate; (ix) Vinyl halides such as vinyl chloride; (x) Aromatic monomers such as acenaphthalene and indene; (xi) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate. (xii) aromatic methacrylates such as phenyl methacrylate; (xiii) methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; (xiv) methacrylic monomers including methacrylic acid derivatives such as methacrylonitrile; (xv) isobornyl Acrylates, certain acrylic esters such as tert-butyl acrylate; (xvi) acrylic monomers including acrylic acid derivatives such as acrylonitrile; Further, monomers that can be included in monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl acrylate, and - Adamantyl methacrylate, etc., which when made into a homopolymer can provide a homopolymer having a Tg of 120° C. or more. Furthermore, examples of monomers that can be included in monomer group a include various compounds described in paragraph [0084] of the specification of WO2014-196607. The monomers selected from these monomer group a may be used alone or in combination of two or more.

Examples of the monomer group b include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. The monomers selected from these monomer group b may be used alone or in combination of two or more. Among monomer group b, particularly preferred are ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.

(Volume average particle diameter of elastic body)
The volume average particle diameter of the elastic body is preferably 0.03 to 2 μm, more preferably 0.05 to 1 μm, even more preferably 0.1 to 0.8 μm, and particularly preferably 0.1 to 0.5 μm. When the volume average particle size of the elastic body is (a) 0.03 μm or more, an elastic body having a desired volume average particle size can be stably obtained; (b) when it is 2 μm or less, the resulting hardening The heat resistance and impact resistance of the product are improved. The volume average particle diameter of the elastic body can be measured using a dynamic light scattering particle size distribution measuring device or the like using an aqueous latex containing the elastic body as a sample. The method for measuring the volume average particle diameter of the elastic body will be described in detail in the Examples below.

(Percentage (ratio) of elastic body)
The proportion of the elastic body in the polymer microparticles (B) is preferably 40 to 97% by mass, more preferably 60 to 95% by mass, and further preferably 70 to 93% by mass, based on the entire polymer microparticles (B) being 100% by mass. Preferably, 80 to 90% by weight is particularly preferable. When the proportion of the elastic body is (a) 40% by mass or more, there is no risk that the effect of improving the toughness of the cured product of the resulting curable resin composition will decrease, and (b) if it is 97% by mass or less, Since the polymer fine particles (B) are difficult to aggregate, the curable resin composition does not have high viscosity, and as a result, the resulting curable resin composition can be easily handled.

(Example of modification of elastic body)
In one embodiment of the present invention, the elastic body is one type selected from the group consisting of diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic body, and has constituent units of the same composition. It may be made of only one type of elastic body. In one embodiment of the present invention, the elastic body may be composed of a plurality of types of elastic bodies each having constituent units of different compositions.

In one embodiment of the present invention, a case will be described in which the elastic body is composed of a plurality of types of elastic bodies. In this case, the plurality of types of elastic bodies are respectively referred to as elastic body ₁ , elastic body ₂ , . . . , and elastic body _n . Here, n is an integer of 2 or more. The elastic body may include a mixture obtained by mixing separately polymerized elastic body ₁ , elastic body ₂ , . . . , and elastic body _n . The elastic body may include a polymer obtained by polymerizing each of elastic body ₁ , elastic body ₂ , . . . , and elastic body _n in order. The process of sequentially polymerizing a plurality of polymers (elastic bodies) in this manner is also referred to as multistage polymerization. A polymer obtained by multistage polymerization of multiple types of elastic bodies is also referred to as a multistage polymerized elastic body. The method for producing the multistage polymerized elastic body will be described in detail later.

A multistage polymerized elastic body consisting of elastic body ₁ , elastic body ₂ , . . . , and elastic body _n will be explained. In the multi-stage polymerized elastic body, the elastic body _n may cover at least a portion of the elastic body _n-1 , or may cover the entire elastic body _n-1 . In the multistage polymerized elastic body, a part of the elastic body _n may enter inside the elastic body _n-1 .

In the multistage polymerized elastic body, each of the plurality of elastic bodies may have a layered structure. For example, when a multistage polymerized elastic body consists of elastic body ₁ , elastic body ₂ , and elastic body ₃ , elastic body ₁ is the innermost layer, a layer of elastic body ₂ is present outside of elastic body ₁ , and An embodiment in which the layer of elastic body ₃ exists outside of layer ₂ as the outermost layer of the elastic body is also an embodiment of the present invention. In this way, a multistage polymerized elastic body in which each of the plurality of elastic bodies has a layered structure can also be called a multilayer elastic body. That is, in one embodiment of the present invention, the elastic body may include a mixture of multiple types of elastic bodies, a multistage polymerized elastic body, and/or a multilayer elastic body.

(graft part)
In this specification, a polymer grafted to an elastic body is referred to as a graft portion. The graft can serve a variety of roles. "Various roles" include, for example, (a) improving the compatibility between components (B) and (A), and (b) improving the dispersibility of polymer particles (B) in the epoxy resin (A). and (c) enabling the polymer fine particles (B) to be dispersed in the state of primary particles in the present curable resin composition or its cured product.

The graft portion of component (B) preferably contains a hydroxy group. With this configuration, the resulting curable resin composition has a high dependence of viscosity on shear rate, and as a result, it is possible to provide a method for producing a laminate with excellent workability. Furthermore, by containing a combination of component (B) containing a hydroxy group in the graft portion and fumed silica (C) described below, the resulting curable resin composition has a higher shear rate dependence of viscosity, As a result, it is possible to provide a method for manufacturing a laminate with better workability. Since the graft portion of component (B) contains a hydroxy group, the resulting curable resin composition also has the advantage of being able to provide a cured product with excellent impact-resistant peel adhesion.

The content of hydroxy groups contained in the graft portion of component (B) is not particularly limited. The content of hydroxy groups in the graft part of component (B) is preferably 0.01 mmol/g or more, more preferably 0.1 mmol/g or more, and 0.01 mmol/g or more, more preferably 0.1 mmol/g or more, based on the total mass of the graft part. It is more preferably 2 mmol/g or more, particularly preferably 0.4 mmol/g or more. The greater the content of hydroxyl groups contained in the grafted part of component (B), the higher the shear rate dependence of the viscosity in the resulting curable resin composition, and the higher the shear rate dependence of the viscosity in the resulting curable resin composition. Impact resistance and peel adhesion properties are good. The graft portion of component (B) is preferably 5.0 mmol/g or less, more preferably 4.0 mmol/g or less, and 2.5 mmol/g or less based on the total mass of the graft portion. More preferably, it is 1.5 mmol/g or less. The lower the content of hydroxy groups contained in the graft portion of component (B), the smaller the viscosity change during storage of the resulting curable resin composition, and the easier the handling of the curable resin composition.

It can also be said that the graft portion of component (B) preferably contains a structural unit derived from a hydroxy group-containing monomer as a structural unit.

Specific examples of monomers having hydroxy groups include (i) hydroxy linear alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (especially hydroxy linear C1-6 alkyl (meth)acrylate); (ii) caprolactone-modified hydroxy (meth)acrylate; (iii) methyl α-(hydroxymethyl)acrylate, ethyl α-(hydroxymethyl)acrylate, etc. hydroxy-branched alkyl (meth)acrylates; (iv) mono(meth)acrylates of polyester diols (especially saturated polyester diols) obtained from divalent carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol); Examples include hydroxyl group-containing (meth)acrylates.

The graft part preferably contains 0.2% to 70.0% by mass, and preferably 2.0% to 50.0% by mass of structural units derived from a hydroxy group-containing monomer based on 100% by mass of the grafted part. It is more preferable to contain 4.0% by mass to 40.0% by mass, and particularly preferably to contain 10.0% by mass to 30.0% by mass. When 0.2% by mass or more of a structural unit derived from a hydroxy group-containing monomer is contained in 100% by mass of the graft portion, the dependence of the viscosity on the shear rate in the resulting curable resin composition (a) becomes high, and the resulting cured resin composition increases. The cured product provided by the curable resin composition has good impact resistance and peel adhesion, and (b) the resulting curable resin composition can provide a cured product having sufficient impact resistance. When the 100% by mass of the graft portion contains 70.0% by mass or less of a structural unit derived from a hydroxy group-containing monomer, the resulting curable resin composition cannot provide a cured product with sufficient impact resistance. , and has the advantage that the curable resin composition has good storage stability.

The structural unit derived from the hydroxy group or the hydroxy group-containing monomer is preferably contained in the graft portion, and more preferably contained only in the graft portion.

The hydroxy group can also be said to be a reactive group, which will be described later, and the hydroxy group-containing monomer can also be said to be a reactive group-containing monomer, which will be described later.

Since component (B) has good compatibility and dispersibility in the curable resin composition, the graft portion is a group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer as a structural unit. A polymer containing a structural unit derived from one or more selected monomers is preferable, and a polymer containing a structural unit derived from a (meth)acrylate monomer is more preferable.

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, and vinylbenzenes such as divinylbenzene.

The content of cyano groups relative to the total mass of the grafted portion of component (B) is not particularly limited, but the temperature dependence of the viscosity of the resulting curable resin composition and the impact strength of the resulting cured product are good. Therefore, 0.5 mmol/g to 15.0 mmol/g is preferable, 1.0 mmol/g to 13.0 mmol/g is more preferable, 1.5 mmol/g to 11.0 mmol/g is more preferable, and 2 .0 mmol/g to 11.0 mmol/g is more preferable, 2.0 mmol/g to 10.0 mmol/g is more preferable, 2.5 mmol/g to 9.0 mmol/g is more preferable, 3.0 mmol/g to 9.0 mmol/g is more preferable, 5.0 mmol/g to 10.0 mmol/g is even more preferable, 5.5 mmol/g to 9.5 mmol/g is even more preferable, and 7.0 mmol/g to 9.0 mmol/g. g is particularly preferred. When the content of cyano groups relative to the total mass of the grafted portion of component (B) is (a) 0.5 mmol/g or more, there is an advantage that the temperature dependence of the viscosity of the resulting curable resin composition is reduced. and (b) is 15.0 mmol/g or less, there is no possibility that the amount of the cyano group-containing monomer remaining in the polymer fine particles (B) will increase, and as a result, there is an advantage that safety is high.

Specific examples of vinyl cyan monomers include acrylonitrile and methacrylonitrile.

Specific examples of (meth)acrylate monomers include (a) (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; and (b) hydroxyethyl (meth)acrylate. Acrylate, (meth)acrylic acid hydroxyalkyl esters such as hydroxybutyl (meth)acrylate, and the like.

The above-mentioned one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone or in combination of two or more. Good too.

The graft part contains, as structural units, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyan monomer, and a structural unit derived from a (meth)acrylate monomer in 100% by mass of the total structural units. It is preferable to contain 10 to 95% by mass, more preferably to contain 30 to 92% by mass, even more preferably to contain 50 to 90% by mass, particularly preferably to contain 60 to 87% by mass, and preferably to contain 70 to 85% by mass. is most preferred.

It is preferable that the graft portion contains a structural unit derived from a reactive group-containing monomer as a structural unit. The reactive group-containing monomer is selected from the group consisting of an epoxy group, an oxetane group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. The monomer is preferably a monomer containing one or more reactive groups selected from the group consisting of an epoxy group and a carboxylic acid group, and more preferably a monomer containing one or more reactive groups selected from the group consisting of an epoxy group and a carboxylic acid group. More preferably, it is a monomer containing a group. According to the above configuration, the graft portion of the polymer fine particles (B) and the epoxy resin (A) can be chemically bonded in the curable resin composition and cured product. Thereby, a good dispersion state of the polymer particles (B) can be maintained in the curable resin composition and the cured product without causing the polymer particles (B) to aggregate. That is, the graft portion is preferably a polymer having an epoxy group.

The graft portion is preferably a polymer having an epoxy group. The content of epoxy groups relative to the total mass of the graft part is preferably 0.1 mmol/g to 5.0 mmol/g, more preferably 0.2 to 4.0 mmol/g, and more preferably 0.3 to 3.0 mmol/g. Preferably, 0.4 to 2.0 mmol/g, more preferably 0.4 to 1.5 mmol/g, even more preferably 0.4 to 1.2 mmol/g, and even more preferably 0.4 to 1.0 mmol/g. g is particularly preferred. According to this configuration, the resulting curable resin composition has the advantage that it can provide a cured product with excellent physical properties such as toughness and elongation. When the content of epoxy groups relative to the total mass of the grafted portion of component (B) is (a) 0.1 mmol/g or more, there is an advantage that the toughness of the cured product of the resulting curable resin composition is increased. However, when (b) it is 5.0 mmol/g or less, the resulting cured product of the curable resin composition has the advantage of having excellent physical properties such as elongation.

Specific examples of monomers having epoxy groups include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.

Specific examples of monomers having carboxylic acid groups include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. As the monomer having a carboxylic acid group, the monocarboxylic acid mentioned above is preferably used.

The above-mentioned reactive group-containing monomers may be used alone or in combination of two or more.

The graft part preferably contains 0.5 to 90 mass %, more preferably 1 to 50 mass %, and 2 to 35 mass % of structural units derived from the reactive group-containing monomer based on 100 mass % of the graft part. %, and particularly preferably 3 to 20% by mass. When the graft part contains (a) 0.5% by mass or more of a structural unit derived from a reactive group-containing monomer based on 100% by mass of the graft part, the resulting curable resin composition has sufficient resistance. (b) When the content is 90% by mass or less, the resulting curable resin composition cannot provide a cured product with sufficient impact resistance. , and has the advantage that the curable resin composition has good storage stability.

The structural unit derived from the reactive group-containing monomer is preferably contained in the graft portion, and more preferably contained only in the graft portion.

The graft portion may contain, as a structural unit, a structural unit derived from a polyfunctional monomer. When the graft portion contains a structural unit derived from a polyfunctional monomer, (a) it is possible to prevent swelling of the polymer fine particles (B) in the curable resin composition, and (b) it is possible to prevent the swelling of the polymer particles (B) in the curable resin composition. Since the viscosity is lower, the curable resin composition tends to be easier to handle, and (c) the dispersibility of the polymer fine particles (B) in the epoxy resin (A) is improved.

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the resulting curable resin composition has the advantage of being able to provide a cured product that is excellent in improving toughness and impact-resistant peel adhesion.

The polyfunctional monomers that can be used in the polymerization of the graft portion include the same monomers as the polyfunctional monomers described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used for polymerization of the graft portion include allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and hexanediol di(meth)acrylate. , cyclohexanedimethanol di(meth)acrylate, triallyl isocyanurate and polyethylene glycol di(meth)acrylates, with allyl methacrylate and triallyl isocyanurate being more preferred. These polyfunctional monomers may be used alone or in combination of two or more.

The graft part may contain 0% to 20% by mass, preferably 1% to 20% by mass, and preferably 5% by mass of structural units derived from polyfunctional monomers based on 100% by mass of the grafted part. It is more preferable to contain up to 15% by mass.

The graft portion preferably contains structural units derived from an aromatic vinyl monomer (especially styrene) from 0% to 50% by weight (more preferably from 1% to 50% by weight) out of 100% by weight of all structural units. , more preferably 2% to 48% by mass), 0% to 50% by mass (more preferably 0% to 30% by mass, even more preferably 10% by mass) of structural units derived from vinyl cyan monomers (especially acrylonitrile) 25% by mass), structural units derived from (meth)acrylate monomers (especially methyl methacrylate) 0% by mass to 90% by mass (more preferably 5% to 85% by mass, still more preferably 20% to 80% by mass) ), and 5% to 90% by mass (more preferably 10% to 50% by mass, even more preferably 15% to 30% by mass) of structural units derived from monomers having epoxy groups (especially glycidyl methacrylate), Contains a total of 100% by mass. According to this configuration, a curable resin composition whose viscosity is less dependent on temperature can be obtained.

In the polymerization of the graft portion, the above-mentioned monomers may be used alone or in combination of two or more.

The graft portion may contain, as a structural unit, a structural unit derived from another monomer in addition to the structural unit derived from the above-mentioned monomer.

(Graft rate of graft part)
In one embodiment of the present invention, the polymer fine particles (B) are a polymer having the same structure as the graft portion, and may include a polymer that is not grafted to the elastic body. In this specification, a polymer having the same structure as the graft portion and not grafted to the elastic body is also referred to as a non-grafted polymer. The non-grafted polymer also constitutes a part of the polymer fine particles (B) according to one embodiment of the present invention. The non-grafted polymer can also be said to be one of the polymers produced in the polymerization of the graft portion that is not graft-bonded to the elastic body.

In this specification, the ratio of the polymer graft-bonded to the elastic body, that is, the proportion of the graft portion among the polymers produced in the polymerization of the graft portion, is referred to as the graft ratio. The graft ratio can also be said to be a value expressed by (mass of grafted part)/{(mass of grafted part)+(mass of non-grafted polymer)}×100.

The graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the graft ratio is 70% or more, there is an advantage that the viscosity of the curable resin composition does not become too high.

In this specification, the method for calculating the graft ratio is as follows. First, an aqueous latex containing polymer fine particles (B) is obtained, and then a powder of polymer fine particles (B) is obtained from the aqueous latex. The method described in the section (Gel content of elastic body) can be used to obtain the powder of polymer particles (B) from the aqueous latex. Next, 2 g of powder of polymer fine particles (B) is immersed in 100 g of methyl ethyl ketone (hereinafter sometimes referred to as MEK). Next, the resulting mixture is allowed to stand at 23° C. for 24 hours. Thereafter, the obtained mixture is separated into a component soluble in MEK (MEK soluble component) and a component insoluble in MEK (MEK insoluble component). Furthermore, by mixing the MEK soluble content with methanol, etc., the methanol insoluble content is separated from the MEK soluble content. Then, the mass of the obtained MEK-insoluble matter and methanol-insoluble matter is measured, and the grafting ratio is calculated by determining the ratio of the MEK-insoluble matter to the total amount of the MEK-insoluble matter and the methanol-insoluble matter. Specifically, the grafting rate is calculated using the following formula.
Grafting rate (%) = (mass of MEK insoluble matter) / {(mass of MEK insoluble matter) + (mass of methanol insoluble matter)} x 100
(Modified example of graft part)
In one embodiment of the invention, the graft portion may consist of only one type of graft portion having constitutional units of the same composition. In one embodiment of the present invention, the graft portion may be composed of multiple types of graft portions each having a different composition of structural units.

In one embodiment of the present invention, a case will be described in which the graft portion is composed of multiple types of graft portions. In this case, each of the plurality of types of graft parts is referred to as graft part ₁ , graft part ₂ , . . . , graft part _n (n is an integer of 2 or more). The graft portion may include a mixture obtained by mixing graft portion ₁ , graft portion ₂ , . . . , and graft portion _n , which are respectively polymerized separately. The graft portion may include a polymer obtained by performing multistage polymerization of graft portion ₁ , graft portion ₂ , . . . , and graft portion _n . A polymer obtained by multistage polymerization of multiple types of graft parts is also referred to as a multistage polymerization graft part. The method for producing the multistage polymerization graft portion will be described in detail later.

When the graft portion is composed of a plurality of types of graft portions, all of the plurality of types of graft portions do not need to be graft-bonded to the elastic body. It is sufficient that at least a part of at least one type of graft part is grafted to the elastic body, and the other types of graft parts (other types) are graft parts grafted to the elastic body. may be grafted to. In addition, when the graft part is composed of multiple types of graft parts, it is a polymer having the same structure as the multiple types of graft parts, and is not grafted to the elastic body (non-grafted polymer). ).

A multistage polymerization graft section consisting of graft section ₁ , graft section ₂ , . . . , and graft section _n will be explained. In the multi-stage polymerization graft section, the graft section _n may cover at least a portion of the graft section _n-1 or may cover the entire graft section _n-1 . In the multistage polymerization graft section, a part of the graft section _n may enter inside the graft section _n-1 .

In the multistage polymerization graft section, each of the plurality of graft sections may have a layered structure. For example, when the multistage polymerization graft section consists of graft section ₁ , graft section ₂ , and graft section ₃ , graft section ₁ is the innermost layer in the graft section, and the layer of graft section ₂ is present outside of graft section ₁ , Further, an embodiment in which the layer of graft section ₃ is present as the outermost layer outside the layer of graft section ₂ is also one embodiment of the present invention. In this way, a multistage polymerization graft section in which each of the plurality of graft sections has a layered structure can also be called a multilayer graft section. That is, in one embodiment of the present invention, the graft portion may include a mixture of multiple types of graft portions, a multistage polymerization graft portion, and/or a multilayer graft portion.

When the elastic body and the graft portion are polymerized in this order in the production of the polymer fine particles (B), at least a portion of the graft portion may cover at least a portion of the elastic body in the obtained polymer fine particles (B). In other words, when the elastic body and the graft portion are polymerized in this order, it can be said that the elastic body and the graft portion are polymerized in multiple stages. The polymer particles (B) obtained by multistage polymerization of an elastic body and a graft portion can also be said to be a multistage polymer.

When the polymer fine particles (B) are a multistage polymer, the graft portion may cover at least a portion of the elastic body or may cover the entire elastic body. When the polymer fine particles (B) are a multistage polymer, a part of the graft portion may enter inside the elastic body.

When the polymer fine particles (B) are a multistage polymer, the elastic body and the graft portion may have a layered structure. For example, an embodiment in which the elastic body is the innermost layer (also referred to as a core layer) and a graft portion layer is present outside the elastic body as the outermost layer (also referred to as a shell layer) is also an aspect of the present invention. A structure in which the elastic body is the core layer and the graft portion is the shell layer can also be called a core-shell structure. Thus, the polymer fine particles (B) in which the elastic body and the graft portion have a layered structure (core-shell structure) can also be said to be a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (B) may be a multistage polymer, and/or a multilayer polymer or a core-shell polymer. However, as long as the graft portion is graft-bonded to the elastic body, the polymer fine particles (B) are not limited to the above configuration.

Preferably, at least a portion of the graft portion covers at least a portion of the elastic body. In other words, at least a portion of the graft portion is preferably present on the outermost side of the polymer fine particles (B).

(Surface crosslinked polymer)
It is preferable that the polymer fine particles (B) have a surface crosslinked polymer in addition to the elastic body and the graft portion grafted to the elastic body. According to the above configuration, (a) the blocking resistance can be improved in the production of the polymer fine particles (B), and (b) the dispersibility of the polymer fine particles (B) in the epoxy resin (A) becomes better. . These reasons are not particularly limited, but can be assumed to be as follows: By covering at least a portion of the elastic body with the surface crosslinked polymer, the exposure of the elastic body portion of the polymer fine particles (B) is reduced; As a result, the elastic bodies become less likely to stick to each other, thereby improving the dispersibility of the polymer fine particles (B).

When the polymer fine particles (B) have a surface crosslinked polymer, they may also have the following effects: (a) an effect of lowering the viscosity of the present curable resin composition, (b) an effect of increasing the crosslinking density in the elastic body. , and (c) the effect of increasing the grafting efficiency (grafting rate) of the grafting part. The crosslinking density in an elastic body means the number of crosslinked structures in the entire elastic body.

Since the resulting cured product has excellent toughness and impact-resistant peel adhesion, it is preferable that the polymer fine particles (B) do not contain a surface crosslinked polymer.

The surface-crosslinked polymer is a polymer containing, as structural units, 30 to 100% by mass of structural units derived from polyfunctional monomers and 0 to 70% by mass of structural units derived from other vinyl monomers, for a total of 100% by mass. Consisting of

The polyfunctional monomers that can be used in the polymerization of the surface-crosslinked polymer include the same monomers as the polyfunctional monomers described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used in the polymerization of surface-crosslinked polymers include allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and hexanediol di(meth)acrylate. ) acrylate, cyclohexanedimethanol di(meth)acrylate, triallyl isocyanurate and polyethylene glycol di(meth)acrylates, with allyl methacrylate and triallyl isocyanurate being more preferred. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

The polymer microparticles (B) may contain a surface crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or a surface crosslinked polymer polymerized together with the rubber-containing graft copolymer. May contain. The polymer fine particles (B) may be a multistage polymer obtained by performing multistage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order. In any of these embodiments, the surface crosslinked polymer may cover at least a portion of the elastic body.

The surface crosslinked polymer can also be considered as part of the elastic body. When the polymer fine particles (B) contain a surface-crosslinked polymer, the graft portion may be (a) graft-bonded to an elastic body other than the surface-crosslinked polymer, and (b) graft-bonded to the surface-crosslinked polymer. It may be graft-bonded, or it may be graft-bonded to both the elastic body other than (c) the surface-crosslinked polymer and the surface-crosslinked polymer. When the polymer fine particles (B) contain a surface crosslinked polymer, the volume average particle diameter of the elastic body mentioned above is intended to be the volume average particle diameter of the elastic body containing the surface crosslinked polymer.

A case (case D) in which the polymer fine particles (B) are a multistage polymer obtained by performing multistage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order will be described. In case D, the surface crosslinked polymer may cover a portion of the elastic body or may cover the entire elastic body. In case D, a part of the surface crosslinked polymer may have entered the inside of the elastic body. In case D, the graft portion may cover a portion of the surface-crosslinked polymer or may cover the entire surface-crosslinked polymer. In case D, a part of the graft portion may be inside the surface crosslinked polymer. In case D, the elastic body, surface crosslinked polymer, and graft portion may have a layered structure. For example, the elastic body is the innermost layer (core layer), the surface crosslinked polymer layer is present as an intermediate layer on the outside of the elastic body, and the graft portion layer is the outermost layer (shell layer) outside the surface crosslinked polymer. The present embodiment is also an embodiment of the present invention.

(Method for producing polymer fine particles (B))
The polymer fine particles (B) can be produced by polymerizing an elastic body and then graft-polymerizing a polymer constituting the graft portion to the elastic body in the presence of the elastic body. The polymer constituting the graft portion is also referred to as a graft polymer.

The polymer fine particles (B) can be produced by a known method, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like. Specifically, the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer in the polymer fine particles (B) can be carried out by known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, etc. It can be manufactured by the following method. Among these, the composition design of the polymer fine particles (B) is easy, the industrial production is easy, and the aqueous latex of the polymer fine particles (B) that can be suitably used for manufacturing the present curable resin composition is easy. Emulsion polymerization is preferred as the method for producing polymer fine particles (B). Hereinafter, a method for producing an elastic body, a graft portion, and a surface-crosslinked polymer having an arbitrary structure that may be included in the polymer fine particles (B) will be described.

(Method for manufacturing elastic body)
Consider a case where the elastic body contains at least one selected from the group consisting of diene rubber and (meth)acrylate rubber. In this case, the elastic body can be manufactured, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in WO2005/028546 can be used as the manufacturing method. .

Consider a case where the elastic body includes a polysiloxane rubber-based elastic body. In this case, the elastic body can be manufactured by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in WO2006/070664 can be used as the manufacturing method. .

A method of manufacturing an elastic body will be described when the elastic body is composed of a plurality of types of elastic bodies (for example, elastic body ₁ , elastic body ₂ , . . . , elastic body _{n 2} ). In this case, elastic body ₁ , elastic _{body 2} , . Good too. Alternatively, elastic body ₁ , elastic _{body 2} , .

Multistage polymerization of an elastic body will be specifically explained. For example, (1) elastic body ₁ is polymerized to obtain elastic body ₁ ; (2) elastic body ₂ is then polymerized in the presence of elastic body ₁ to obtain two-stage elastic body ₁₊₂ ; (3) then elastic body 1 is obtained by polymerizing elastic body 1; Polymerize elastic body ₃ in the presence of body ₁₊₂ to obtain three-stage elastic body ₁₊₂₊₃ ; (4) After carrying out the same procedure, in the presence of elastic body _{1+2+...+(n-1)} The elastic body _n is polymerized to obtain a multistage polymerized elastic body _1+2+...+n .

(Method for manufacturing the graft part)
The graft portion can be formed, for example, by polymerizing monomers used for forming the graft portion by known radical polymerization. When (a) the elastic body or (b) the polymer fine particle precursor containing the elastic body and a surface-crosslinked polymer is obtained as an aqueous latex, the polymerization of the graft portion is preferably carried out by an emulsion polymerization method. The graft portion can be manufactured, for example, according to the method described in WO2005/028546.

By using a hydroxy group-containing monomer in the production (polymerization) of the graft portion, a graft portion having a hydroxy group can be obtained.

A method for manufacturing a graft section will be described when the graft section is composed of a plurality of types of graft sections (for example, graft section ₁ , graft section ₂ , . . . , graft section _n ). In this case, graft part ₁ , graft part ₂ , ..., graft part _n are each separately polymerized by the above-mentioned method, and then mixed to produce a graft part having multiple types of graft parts. Good too. Alternatively, graft part ₁ , graft part ₂ , . . . , graft part _n may be sequentially polymerized in multiple stages to produce a graft part having multiple types of graft parts.

The multistage polymerization of the graft portion will be specifically explained. For example, (1) graft part ₁ is polymerized to obtain graft part ₁ ; (2) graft part ₂ is then polymerized in the presence of graft part ₁ to obtain two-stage graft part ₁₊₂ ; (3) then graft part 1 is obtained by polymerizing graft part 1; Polymerize graft part ₃ in the presence of part ₁₊₂ to obtain three-stage graft part ₁₊₂₊₃ ; (4) After carrying out the same procedure, in the presence of graft part _{1+2+...+(n-1)} Graft part _n is polymerized to obtain multi-stage polymerized graft parts _1+2+...+n .

When the graft portion is composed of multiple types of graft portions, the polymer particles (B) may be produced by polymerizing the graft portion having multiple types of graft portions and then graft polymerizing the graft portions onto an elastic body. Polymer fine particles (B) may be produced by sequentially performing multi-stage graft polymerization of a plurality of types of polymers constituting a plurality of types of graft portions to the elastic body in the presence of the elastic body.

(Method for producing surface crosslinked polymer)
The surface crosslinked polymer can be formed by polymerizing monomers used for forming the surface crosslinked polymer by known radical polymerization. When the elastomer is obtained as an aqueous latex, the surface crosslinked polymer is preferably polymerized by emulsion polymerization.

Surface-crosslinked polymers can be produced by adding the monomers used to form the surface-crosslinked polymer to an aqueous latex containing a polymerized elastomer all at once or continuously in a fixed amount, and then polymerizing. may be obtained. Such polymerization can also be said to be one-stage polymerization of a surface-crosslinked polymer. The surface crosslinked polymer may be polymerized in two or more stages. That is, it is also possible to adopt a method in which an aqueous latex containing a polymerized elastomer is added to a reactor previously charged with monomers used to form a surface-crosslinked polymer, and then polymerization is carried out.

(emulsifier)
When employing an emulsion polymerization method as a method for producing the polymer fine particles (B), a known emulsifier can be used for producing the polymer fine particles (B). Examples of emulsifiers that can be used in emulsion polymerization include various emulsifiers described in paragraph [0073] of the specification of WO2016-163491. These emulsifiers may be used alone or in combination of two or more. An emulsifier can also be called a dispersant.

It is preferable to use a small amount of emulsifier (dispersant) as long as it does not interfere with the dispersion stability of the polymer fine particles (B) in the aqueous latex. Moreover, the higher the water solubility of the emulsifier, the more preferable it is. When the emulsifier has high water solubility, the emulsifier can be easily removed by washing with water, and the adverse effect of the emulsifier (residual emulsifier) on the finally obtained cured product can be easily prevented.

(initiator)
When employing an emulsion polymerization method as a method for producing the polymer fine particles (B), a thermal decomposition type initiator can be used for producing the polymer fine particles (B). Examples of the thermal decomposition type initiator include known initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate.

A redox type initiator can also be used in the production of polymer fine particles (B). The redox-type initiator comprises (a) a peroxide such as an organic peroxide and an inorganic peroxide; (b) an optional reducing agent such as sodium formaldehyde sulfoxylate or glucose; It is an initiator that uses a transition metal salt such as iron (II) sulfate, and if necessary, a chelating agent such as disodium ethylenediaminetetraacetate, and further, if necessary, a phosphorus-containing compound such as sodium pyrophosphate. The organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl. Examples include peroxide. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like.

When a redox type initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set within a wide range. Therefore, it is preferable to use a redox type initiator. Among the redox type initiators, organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide and t-butyl hydroperoxide are preferably used as the redox type initiator. The amount of the initiator used, and when a redox type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, etc. used can be within known ranges.

When using a polyfunctional monomer in the polymerization of the elastic body, graft portion or surface cross-linked polymer for the purpose of introducing a crosslinked structure into the elastic body, graft portion or surface cross-linked polymer, a known chain transfer agent may be used in a known manner. A range of amounts can be used. By using a chain transfer agent, the molecular weight and/or degree of crosslinking of the resulting elastic body, graft portion, or surface crosslinked polymer can be easily adjusted.

In addition to the above-mentioned components, a surfactant can be used for producing the polymer fine particles (B). The type and amount of the surfactant used are within known ranges.

In the production of polymer fine particles (B), conditions such as polymerization temperature, pressure, and deoxidation during polymerization can be within a known range.

(2-1-3. Blocked urethane (C))
Blocked urethane (C) has the effect of improving the tensile failure strain (%) of the cured product of the curable resin composition, that is, it improves the physical properties of elongation of the cured product of the curable resin composition. It has an effect. Blocked urethane (C) also has the effect of improving the toughness of the cured product of the curable resin composition. Therefore, the present curable resin composition containing blocked urethane (C) can provide a cured product with excellent physical properties such as toughness and elongation.

The ratio (W1/W2) between the mass (W1) of the polymer fine particles (B) and the mass (W2) of the blocked urethane (C) is not particularly limited. The ratio (W1/W2) between the mass (W1) of the polymer fine particles (B) and the mass (W2) of the blocked urethane (C) is preferably 0.1 to 10.0, and preferably 0.2 to 7.0. It is more preferably 1.5 to 7.0, even more preferably 1.8 to 5.0, even more preferably 2.0 to 4.0, and particularly preferably 2.5 to 3.5. The W1/W2 may be 0.2 to 5.0, 0.3 to 4.0, 0.4 to 3.0, or 0.5 to 2. It may be .0. When W1/W2 is within the above range, there is an advantage that the temperature dependence of the viscosity of the resulting curable resin composition can be made smaller. Further, when W1/W2 is 1.5 or more, there is an advantage that the impact-resistant peel adhesion at low temperatures of the cured product obtained by curing the curable resin composition does not deteriorate.

Blocked urethane (C) is an elastomer type compound that contains a urethane group and/or a urea group and has an isocyanate group at the end, in which all or part of the terminal isocyanate group has an active hydrogen group. Compounds capped with various blocking agents. Particularly preferred is a compound in which all of the terminal isocyanate groups are capped with a blocking agent. Such a compound (i.e., blocked urethane (C)) can be obtained, for example, by the following method: (i) An excess polyisocyanate compound is added to an organic polymer having an active hydrogen-containing group at the end. React to produce a polymer (urethane prepolymer) having a urethane group and/or urea group in the main chain skeleton and an isocyanate group at the end; (ii) after (i) above, or after (i) above. At the same time, it is obtained by allowing a blocking agent having an active hydrogen group to act on all or a portion of the isocyanate groups of the urethane prepolymer, and capping all or a portion of the isocyanate groups with the blocking agent.

The blocked urethane (C) is represented by the following general formula (1), for example:
A-(NR ² -C(=O)-X) _a ... General formula (1);
(In the general formula (1), a number of R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms. a represents the average number of capped isocyanate groups per molecule, and 1 .1 or more, more preferably 1.5 to 8, even more preferably 1.7 to 6, particularly preferably 2 to 4. X is a residue obtained by removing the active hydrogen atom from the blocking agent. A is a residue obtained by removing the terminal isocyanate group from an isocyanate-terminated prepolymer (for example, a urethane prepolymer having an isocyanate group at the terminal).

The isocyanate groups capped with the blocking agent are regenerated by heating, and the regenerated isocyanate groups react with active hydrogen-containing compounds in the curable resin composition, improving the toughness of the resulting cured product. . The weight percent of isocyanate groups regenerated by heating with respect to 100 weight percent of blocked urethane (C) is defined as latent NCO%. Note that the reaction between the urethane prepolymer and the blocking agent is considered to proceed almost quantitatively. Therefore, when a blocking agent having an equivalent or more active hydrogen group is reacted with the isocyanate group of the urethane prepolymer, the latent NCO% can be calculated by NCO titration of the urethane prepolymer before capping with the blocking agent. . Further, when a blocking agent having less than the equivalent amount of active hydrogen groups is reacted with the isocyanate groups of the urethane prepolymer, the latent NCO% can be calculated based on the amount of the reacted blocking agent.

In one embodiment of the present invention, the latent NCO% of component (C) is 0.1%, although there is no particular limitation, from the viewpoint of the temperature dependence of the viscosity of the resulting curable resin composition and the toughness of the cured product. ~10.0% is preferred, 0.1% ~ 5.0% is more preferred, 0.1% ~ 4.0% is more preferred, and 0.1% ~ 3.5% is more preferred.

In one embodiment of the present invention, it is further preferred that the blocked urethane (C) has a latent NCO% of 0.1% to 2.9%. When the latent NCO% of component (C) is 0.1 to 2.9%, a curable resin composition with low temperature dependence of viscosity can be obtained. When the latent NCO% of component (C) is (a) 0.1% or more, there is no risk that the toughness of the cured product obtained by curing the curable resin composition will deteriorate, and (b) 2.9%. % or less, the temperature dependence of the viscosity of the resulting curable resin composition tends to decrease.

In one embodiment of the present invention, the latent NCO% of component (C) is 0.3% to 2.8% from the viewpoint of the temperature dependence of the viscosity of the resulting curable resin composition and the toughness of the cured product. is even more preferred, 0.5% to 2.7% is even more preferred, 1.0% to 2.5% is even more preferred, and 1.5% to 2.3% is particularly preferred.

In one embodiment of the present invention, the potential NCO% of component (C) may be 0.5% to 5.0%, 1.0% to 4.0%, and 1. It may be 5% to 3.5%.

Potential NCO% can also be expressed using the unit "mmol/g". Regarding latent NCO, the unit "mmol/g" means the molar amount (mmol) of isocyanate groups regenerated by heating per 1 g of blocked urethane (C). Regarding potential NCO, "%" and "mmol/g" are interchangeable.

The number average molecular weight of the blocked urethane (C) is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, particularly from 4,000 to 20,000 in terms of polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). preferable. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of the blocked urethane (C) is preferably 1 to 4, more preferably 1.2 to 3, particularly preferably 1.5 to 2.5.

The weight average molecular weight of blocked urethane (C) can be measured by a GPC method.

The "organic polymer having an active hydrogen-containing group at the terminal", "polyisocyanate compound" and "blocking agent having an active hydrogen group" used in the production of blocked urethane (C) will be explained.

(Organic polymer with active hydrogen-containing group at the end)
The main chain skeletons constituting organic polymers having active hydrogen-containing groups at the ends include polyether polymers, polyacrylic polymers, polyester polymers, polydiene polymers, and saturated hydrocarbon polymers (polyolefins, etc.). ), polythioether polymers, etc.

(active hydrogen group)
Examples of the active hydrogen-containing groups constituting the organic polymer having an active hydrogen-containing group at the end include a hydroxyl group, an amino group, an imino group, and a thiol group. Among these, hydroxyl group, amino group and imino group are preferred from the viewpoint of availability, and hydroxyl group is more preferred from the viewpoint of ease of handling (viscosity) of the obtained blocked urethane.

Examples of organic polymers having an active hydrogen-containing group at the end include polyether polymers having a hydroxyl group at the end (polyether polyol), polyether polymers having an amino group and/or imino group at the end (polyether amine), ), polyacrylic polyols, polyester polyols, diene polymers having hydroxyl groups at the ends (polydiene polyols), saturated hydrocarbon polymers having hydroxyl groups at the ends (polyolefin polyols), polythiol compounds, polyamine compounds, etc. Among these, polyether polyol, polyether amine, and polyacrylic polyol have excellent compatibility with component (A), the Tg of the organic polymer is relatively low, and the resulting cured product has low impact resistance at low temperatures. It is preferable because it has excellent properties. In particular, polyether polyols and polyether amines are more preferred because the resulting organic polymers have low viscosity and good workability, and polyether polyols are particularly preferred.

The organic polymer having an active hydrogen-containing group at the end used when preparing the urethane prepolymer which is the precursor of blocked urethane (C) may be used alone or in combination of two or more. You may do so.

The number average molecular weight of the organic polymer having an active hydrogen-containing group at the end is preferably 800 to 7,000, more preferably 1,500 to 5,000, and particularly preferably 2,000 to 4,000 in terms of polystyrene equivalent molecular weight measured by GPC.

(Polyether polymer)
The polyether polymer is a polymer having 40% by mass or more of repeating units represented by the following general formula (2) based on 100% by mass of the organic polymer:
-R ¹ -O- ... General formula (2)
(In general formula (2), R ¹ is a linear or branched alkylene group having 1 to 14 carbon atoms.)

R ¹ in the general formula (2) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by general formula (2) include -CH ₂ O-, -CH ₂ CH ₂ O-, -CH ₂ CH(CH ₃ )O-, -CH ₂ CH(C ₂ H ₅ )O-, -CH ₂ C(CH ₃ ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O-, and the like. The main chain skeleton of the polyether polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In particular, polyether polymers consisting of polypropylene glycol as a main component having 50% by mass or more of propylene oxide repeating units in 100% by mass of the organic polymer have a cured product with a T-peel adhesive strength. It is preferable because it has excellent properties. Further, polytetramethylene glycol (PTMG) obtained by ring-opening polymerization of tetrahydrofuran is preferable because the resulting cured product has excellent dynamic splitting resistance.

The polyether polymer preferably contains 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more of the repeating unit of general formula (2) based on 100% by mass of the organic polymer. is even more preferable.

The blocked urethane (C) is preferably a compound obtained by capping a urethane prepolymer containing a polyalkylene glycol structure with a blocking agent, and preferably a compound obtained by capping a urethane prepolymer containing a polypropylene glycol structure with a blocking agent. This is more preferred because the temperature-sensitive viscosity of the resulting curable resin composition is small.

"The temperature-sensitive property of viscosity is small" means "the temperature dependence of viscosity is small."

(Polyether polyol and polyether amine)
The polyether polyol is a polyether polymer having a hydroxyl group at the end. The polyether amine is a polyether polymer having an amino group or an imino group at the end.

(Polyacrylic polyol)
Examples of the polyacrylic polyol include polyols having a skeleton of an alkyl (meth)acrylic ester (co)polymer and having a hydroxyl group in the molecule. As the polyacrylic polyol, particularly preferred is a polyacrylic polyol obtained by copolymerizing a hydroxyl group-containing (meth)acrylic acid alkyl ester monomer such as 2-hydroxyethyl methacrylate.

The polyester polyol includes (i) one or more selected from the group consisting of polybasic acids such as maleic acid, fumaric acid, adipic acid, and phthalic acid, and acid anhydrides thereof; and (ii) ethylene glycol and propylene. one or more selected from the group consisting of polyhydric alcohols such as glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and neopentyl glycol in the presence of an esterification catalyst. , polymers obtained by polycondensation at a temperature range of 150 to 270°C. Also included are (a) ring-opening polymers such as ε-caprolactone and valerolactone, and (b) active hydrogen compounds having two or more active hydrogens such as polycarbonate diol and castor oil.

(Polydiene polyol)
Examples of the polydiene polyol include polybutadiene polyol, polyisoprene polyol, polychloroprene polyol, and the like. Particularly preferred is polybutadiene polyol.

(Polyolefin polyol)
Examples of the polyolefin polyol include polyisobutylene polyol, hydrogenated polybutadiene polyol, and the like.

(Polyisocyanate compound)
Specific examples of the polyisocyanate compounds include (a) aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; (b) isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated toluene diisocyanate, and hydrogen. Examples include aliphatic polyisocyanates such as diphenylmethane diisocyanate. Among these, aliphatic polyisocyanates are preferred in terms of heat resistance, and isophorone diisocyanate and hexamethylene diisocyanate are more preferred in terms of availability.

(Blocking agent with active hydrogen group)
The blocking agents include, for example, primary amine blocking agents, secondary amine blocking agents, oxime blocking agents, lactam blocking agents, active methylene blocking agents, alcohol blocking agents, mercaptan blocking agents, and amide blocking agents. Examples include blockers based on imide-based blocking agents, blocking agents based on heterocyclic aromatic compounds, hydroxy-functional (meth)acrylate-based blocking agents, and phenol-based blocking agents. Among these, oxime-based blocking agents, lactam-based blocking agents, hydroxy-functional (meth)acrylate-based blocking agents and phenolic-based blocking agents are preferred, and hydroxy-functional (meth)acrylate-based blocking agents and phenolic-based blocking agents are more preferred. , phenolic blocking agents are more preferred.

(Primary amine blocking agent)
Examples of the primary amine blocking agent include various compounds described in paragraph [0098] of the specification of WO2016-163491.

(Hydroxy functional (meth)acrylate blocking agent)
The hydroxy-functional (meth)acrylate blocking agent is a (meth)acrylate having one or more hydroxyl groups. Specific examples of the hydroxy-functional (meth)acrylate blocking agent include various compounds described in paragraph [0099] of the specification of WO2016-163491.

(phenolic blocking agent)
The phenolic blocking agent contains at least one phenolic hydroxyl group. "Phenolic hydroxyl group" means a hydroxyl group directly bonded to a carbon atom of an aromatic ring. The phenolic compound may have two or more phenolic hydroxyl groups. The phenolic compound preferably contains only one phenolic hydroxyl group. The phenolic compound may contain other substituents. Other substituents include (a) alkyl groups such as linear, branched, or cycloalkyl; (b) aromatic groups (e.g., phenyl, alkyl-substituted phenyl, alkenyl-substituted phenyl, etc.); c) Aryl-substituted alkyl group; (C) phenol-substituted alkyl group, (e) alkenyl group, and (f) allyl group. Other substituents are preferably substituents that do not react with isocyanate groups under the conditions of the capping reaction, and more preferably alkenyl groups and allyl groups. Specific examples of the phenolic blocking agent include various compounds described in paragraph [0100] of the specification of WO2016-163491.

Preferably, the blocking agent is bonded to the end of the polymer chain of the urethane prepolymer in such a manner that the end to which it is bonded no longer has a reactive group. It can also be said that the polymer terminal obtained by bonding the blocking agent to the terminal of the polymer chain of the urethane prepolymer preferably does not have a reactive group.

The blocking agent may be used alone or in combination of two or more.

The blocked urethane (C) may contain a crosslinking agent residue, a chain extender residue, or both.

(Crosslinking agent)
The molecular weight of the crosslinking agent is preferably 750 or less, more preferably 50 to 500. The crosslinking agent is a polyol or polyamine compound having at least three hydroxyl, amino and/or imino groups per molecule. The crosslinking agent is useful for imparting branching to the blocked urethane (C) and increasing the functionality (ie, number of capped isocyanate groups per molecule) of the blocked urethane (C).

(chain extender)
The molecular weight of the chain extender is preferably 750 or less, more preferably 50 to 500. The chain extender is a polyol or polyamine compound having two hydroxyl, amino and/or imino groups per molecule. Chain extenders are useful in increasing the molecular weight of blocked urethane (C) without increasing functionality.

Specific examples of the crosslinking agent and chain extender include various compounds described in paragraph [0106] of the specification of WO2016-163491.

(Content of blocked urethane (C))
The present curable resin composition preferably contains 5 parts by mass to 60 parts by mass, and more preferably 5 parts by mass to 50 parts by mass of component (C) per 100 parts by mass of component (A). It is more preferable to contain from 10 parts by weight to 45 parts by weight, and particularly preferably from 20 parts by weight to 40 parts by weight. When the content of component (C) is 5 parts by mass or more of component (a) relative to 100 parts by mass of component (A), the resulting curable resin composition provides a cured product with excellent physical properties such as toughness and elongation. (b) When the amount is 60 parts by mass or less, the resulting curable resin composition can provide a cured product with a high Tg and excellent heat resistance and elastic modulus (rigidity).

Component (C) may be used alone or in combination of two or more.

(2-1-4. Dicyandiamide (D))
Dicyandiamide (D) can function as an epoxy resin curing agent. Dicyandiamide can be said to be a latent epoxy curing agent because it becomes active when heated. Since this curable resin composition contains dicyandiamide (D), which is a latent curing agent, it can be used as a one-component curable resin composition.

The present inventor has discovered that by including the component (D) in addition to the components (B) and (C), the curable resin composition has excellent elongation properties and Tg We have obtained new knowledge that it is possible to provide a cured product with high More specifically, the present inventor found that among many epoxy resin curing agents, dicyandiamide improves the elongation of the cured product without reducing the elastic modulus and tensile strength of the cured product provided by the curable resin composition. We have discovered new knowledge that physical properties can be improved.

The present curable resin composition preferably contains 9.0 parts by mass to 17.0 parts by mass, and 10.0 parts by mass to 16.0 parts by mass of component (D) per 100 parts by mass of component (A). It is more preferable to contain 11.0 parts by weight to 15.0 parts by weight. When the content of component (D) is 9.0 parts by mass or more based on 100 parts by mass of component (A), the curable resin composition obtained has good curability, and the curable resin composition obtained This product can provide a cured product with excellent elongation properties. When the content of component (D) is 17.0 parts by mass or less based on 100 parts by mass of component (A), the resulting curable resin composition has a high Tg and has low heat resistance and elastic modulus (rigidity). Excellent cured products can be provided.

In the curable resin composition in the second laminate, the content of component (D) is not particularly limited. It is essential that the curable resin composition in the first laminate contains 9.0 parts by mass to 17.0 parts by mass of component (D) per 100 parts by mass of component (A).

The epoxy resin curing agent is typically used in an amount sufficient to cure the curable resin composition. Regarding dicyandiamide, typically, due to changes in its mechanical properties, it is sufficient to blend dicyandiamide in an amount of 0.7 equivalent per equivalent of epoxy group present in the curable resin composition. Even when 0.7 equivalent or more is blended, the obtained results are the same. Note that most of the epoxide groups present in the curable resin composition are derived from component (A). Therefore, the amount necessary for consumption of epoxide groups can be determined based on the content of component (A). A case (case G) in which a bisphenol A type epoxy resin having an epoxy equivalent of 186 is used as the epoxy resin (A) will be described. In case G, 0.7 equivalent of dicyandiamide is 7.9 parts by mass based on 100 parts by mass of bisphenol A epoxy resin. Therefore, in case G, those skilled in the art would normally not use more than 7.9 parts by weight of dicyandiamide per 100 parts by weight of the epoxy resin (A).

The present curable resin composition may further contain an epoxy resin curing agent other than dicyandiamide.

A case (case E) in which the present curable resin composition is used as a one-component composition (for example, a one-component curable resin composition) will be described. In case E, the type and amount of the epoxy resin curing agent other than dicyandiamide is adjusted so that the curable resin composition is rapidly cured when heated to a temperature of 80° C. or higher, preferably 140° C. or higher. Preferably. In other words, in case E, the epoxy resin other than dicyandiamide is used such that the curable resin composition cures very slowly, if at all, at room temperature (approximately 22°C) and at temperatures up to at least 50°C. It is preferable to select the type and amount of the curing agent and component (G) described below.

In case E, as the epoxy resin curing agent other than dicyandiamide, a component that becomes active upon heating (sometimes referred to as a latent epoxy curing agent) can be used. As such a latent epoxy curing agent, a nitrogen (N)-containing curing agent such as a specific amine-based curing agent (including an imine-based curing agent) can be used. Latent epoxy curing agents other than dicyandiamide include, for example, boron trichloride/amine complexes, boron trifluoride/amine complexes, melamine, diallylmelamine, guanamines (e.g. acetoguanamine and benzoguanamine), aminotriazoles (e.g. 3- amino-1,2,4-triazole), hydrazides (e.g. adipic dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide), cyanoacetamides, as well as aromatic polyamines (e.g. metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone). etc.). As the latent epoxy curing agent other than dicyandiamide, it is more preferable to use isophthalic acid dihydrazide, adipic acid dihydrazide, and 4,4'-diaminodiphenylsulfone because they have excellent adhesive properties.

Furthermore, among epoxy resin curing agents other than dicyandiamide, acid anhydrides and phenols can also be used as latent epoxy curing agents. Acid anhydrides and phenols require higher temperatures than amine curing agents, but they have a longer pot life and the resulting cured product has a good balance of physical properties such as electrical, chemical, and mechanical properties. becomes good. Examples of acid anhydrides include various compounds described in paragraph [0117] of the specification of WO2016-163491.

A case (case F) in which the present curable resin composition is used as a two-component or multi-component composition will be described. In case F, as the epoxy resin curing agent other than dicyandiamide, a curing agent that is active at a relatively low temperature of about room temperature (sometimes referred to as a room temperature curing agent) can be selected. Examples of the room temperature curing agent include amine curing agents (including imine curing agents) and/or mercaptan curing agents other than those mentioned above.

Examples of room temperature curing agents include amine curing agents such as polyamide amines, amine-terminated polyethers, amine-terminated rubbers, modified aliphatic polyamines, modified alicyclic polyamines and polyamides, and WO2016-163491. Examples include various compounds described in paragraph [0113] of the specification of the publication.

Amine-terminated polyethers containing a polyether backbone and having on average 1 to 4 (preferably 1.5 to 3) amino and/or imino groups per molecule are also suitable as room temperature curing curing agents. Can be used as Commercially available amine-terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-5000, and the like manufactured by Huntsman.

Furthermore, an amine-terminated rubber containing a conjugated diene polymer main chain and having an average of 1 to 4 (more preferably 1.5 to 3) amino groups and/or imino groups per molecule can also be used at room temperature. Can be used as a hardening agent. Here, the rubber main chain, that is, the conjugated diene polymer main chain, is preferably a polybutadiene homopolymer or copolymer, more preferably a polybutadiene/acrylonitrile copolymer, and the acrylonitrile monomer content is 5 to 40% by mass (more preferably 10 to 35% by mass). % by weight, more preferably from 15 to 30% by weight). Examples of commercially available amine-terminated rubbers include Hypro 1300X16 ATBN manufactured by CVC.

Among the above amine-based curing agents in the room temperature curing agent, polyamide amines, amine-terminated polyethers, and amine-terminated rubbers are more preferable, and polyamide amines, amine-terminated polyethers, and amine-terminated rubbers are used in combination. is particularly preferred.

Among epoxy resin curing agents other than dicyandiamide, latent epoxy curing agents other than dicyandiamide are preferred because they enable the present curable resin composition to be used as a one-component curable resin composition.

Epoxy resin curing agents other than dicyandiamide may be used alone or in combination of two or more.

In the present curable resin composition, the total content of dicyandiamide and an epoxy resin curing agent other than dicyandiamide is preferably 9.0 parts by mass to 80.0 parts by mass, and 10 parts by mass, based on 100 parts by mass of component (A). It is more preferably from .0 parts by weight to 40.0 parts by weight, even more preferably from 11.0 parts by weight to 30.0 parts by weight, and particularly preferably from 11.0 parts by weight to 20.0 parts by weight. When the total content of dicyandiamide and an epoxy resin curing agent other than dicyandiamide is 9.0 parts by mass or more based on 100 parts by mass of component (A), the resulting curable resin composition has good curability. When the total content of dicyandiamide and an epoxy resin curing agent other than dicyandiamide is 80 parts by mass or less based on 100 parts by mass of component (A), (a) the resulting curable resin composition has good storage stability. (b) The resulting curable resin composition can be easily handled, and (b) the resulting curable resin composition can provide a cured product with a high Tg and excellent heat resistance and elastic modulus (rigidity).

(2-1-5. Inorganic filler (E))
This curable resin composition may contain an inorganic filler (E). "Inorganic filler (E)" may be hereinafter referred to as "component (E)."

The inorganic filler (E) can improve (increase) the shear rate dependence of the viscosity of the curable resin composition. Moreover, when the present curable resin composition further contains an inorganic filler (E), the curable resin composition can provide a cured product with excellent adhesiveness. On the other hand, the inorganic filler (E) can reduce the tensile fracture strain of the cured product of the curable resin composition. Therefore, when it is important that the cured product of the curable resin composition has excellent elongation properties, it is preferable that the amount of the inorganic filler (E) in the curable resin composition is as small as possible. Preferably, it does not contain an inorganic filler (E).

Examples of the inorganic filler (E) include silicic acid, silicate, dolomite, reinforcing filler, calcium carbonate, magnesium carbonate, titanium oxide, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, etc. It will be done.

Silicic acids include wet silica and dry silica.

The dry silica is also called fumed silica. The dry silica includes surface-untreated hydrophilic fumed silica and hydrophobic fumed silica produced by chemically treating the silanol group portion of hydrophilic fumed silica with silane and/or siloxane. Can be mentioned. The dry silica is preferably hydrophilic fumed silica because (a) it has excellent workability, and (b) it has excellent dispersibility in component (A), and the resulting curable resin composition has storage stability. Hydrophobic fumed silica is preferred because it has excellent properties.

Methods for producing dry silica include (a) the Aerosil method in which it is produced by decomposing silicon halide, and (b) the arc method in which silica sand is heated and reduced and then oxidized with air to produce silicic acid. Examples include, but there are no particular limitations. As a method for producing dry silica, the Aerosil method is preferred from the viewpoint of availability.

Examples of surface treatment agents for hydrophobic fumed silica include silane coupling agents, octamethyltetracyclosiloxane, and polydimethylsiloxane. Examples of the silane coupling agent include dimethyldichlorosilane, (meth)acrylicsilane, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, and methacrylsilane. Hydrophobic fumed silica surface-treated with polydimethylsiloxane is preferred because it has excellent dispersion stability in component (A) and storage stability of the resulting curable resin composition.

When the present curable resin composition contains dry silica as an inorganic filler, the viscosity of the curable resin composition becomes highly dependent on shear rate.

Examples of the silicates include aluminum silicate, magnesium silicate, calcium silicate, wollastonite, and talc.

Examples of calcium carbonate include heavy calcium carbonate and colloidal calcium carbonate.

Colloidal calcium carbonate can generally be produced by reacting milk of lime, which is made by adding water to quicklime, with carbon dioxide gas. Colloidal calcium carbonate is calcium carbonate in uniform particles and is sometimes referred to as "precipitated calcium carbonate," "colloidal calcium carbonate," or "synthetic calcium carbonate."

From the viewpoint of economic efficiency, the inorganic filler (E) preferably contains calcium carbonate.

The inorganic filler (E) is preferably surface-treated with a surface treatment agent. The surface treatment improves the dispersibility of the inorganic filler (E) into the curable resin composition, and as a result, various physical properties of the resulting cured product are improved.

Examples of the surface treatment agent for the inorganic filler (E) include fatty acids such as saturated fatty acids and unsaturated fatty acids, resin acids, and silane coupling agents.

The content of the inorganic filler (E) in 100% by mass of the curable resin composition is preferably 0.1% by mass to 15.0% by mass, and preferably 0.5% by mass to 10.0% by mass. More preferably, the amount is from 1.0% by mass to 5.0% by mass. When the content of the inorganic filler (E) in 100% by mass of the curable resin composition is 0.1% by mass or more, the curable resin composition can provide a cured product with excellent adhesiveness. When the content of the inorganic filler (E) in 100% by mass of the curable resin composition is 15.0% by mass or less, the physical property of elongation due to the inorganic filler (E) does not deteriorate significantly, The curable resin composition can provide a cured product with excellent elongation properties.

The inorganic filler (E) may be used alone or in combination of two or more.

(calcium oxide)
The present curable resin composition may contain calcium oxide as an inorganic filler (E). When the present curable resin composition contains calcium oxide as the inorganic filler (E), the calcium oxide removes water from the curable resin composition by reacting with the water in the curable resin composition. It can solve various physical property problems caused by its presence. Calcium oxide functions as an anti-bubble agent by removing water, for example, and can suppress a decrease in adhesive strength of the resulting cured product.

Calcium oxide can be surface treated with a surface treatment agent. The surface treatment improves the dispersibility of calcium oxide in the curable resin composition. As a result, when surface-treated calcium oxide is used, physical properties such as adhesive strength of the resulting cured product are improved compared to when surface-treated calcium oxide is used. In particular, surface-treated calcium oxide can significantly improve the T-peel adhesion and impact-resistant peel adhesion of the resulting cured product. The surface treatment agent that can be used for surface treatment of calcium oxide is not particularly limited, but fatty acids are preferred.

When the present curable resin composition contains calcium oxide as the inorganic filler (E), the content of calcium oxide in the curable resin composition is 0.1 parts by mass to 100 parts by mass of component (A). It is preferably 10 parts by weight, more preferably 0.2 to 5 parts by weight, even more preferably 0.5 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight. When the content of calcium oxide is (a) 0.1 parts by mass or more with respect to 100 parts by mass of component (A), the water removal effect is sufficient, and (b) when it is 10 parts by mass or less, the result is obtained. There is no risk that the strength of the cured product will decrease.

One type of calcium oxide may be used alone, or two or more types may be used in combination.

This curable resin composition can use a dehydrating agent other than calcium oxide. Examples of dehydrating agents other than calcium oxide include various compounds described in paragraph [0155] of the specification of WO2014-196607.

(2-1-6. Curing accelerator (F))
In one embodiment of the present invention, a curing accelerator (F) can be used if necessary. "Curing accelerator (F)" may be hereinafter referred to as "component (F)."

Component (F) is used to promote the reaction between the epoxy group in component (A) and the epoxide-reactive group contained in the epoxy resin curing agent and components other than the epoxy resin curing agent in the curable resin composition. It is a catalyst for

As the component (F), for example, (a) p-chlorophenyl-N,N-dimethylurea (trade name: Monuron), 3-phenyl-1,1-dimethylurea (trade name: Fenuron), 3,4- Dichlorophenyl-N,N-dimethylurea (trade name: Diuron), N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea (trade name: Chlortoluron), 1,1-dimethylphenylurea (trade name: Dyhard); (b) benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol, poly(p-vinylphenol) matrix; Incorporated tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, N,N-dimethylpiperidine; (c) C1-C12 alkylene imidazole, N-arylimidazole, 2-methyl Imidazole such as imidazole, 2-ethyl-2-methylimidazole, N-butylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, addition product of epoxy resin and imidazole; (d) 6-caprolactam Examples include. The catalyst may be encapsulated or it may be a latent catalyst that becomes active only at elevated temperatures.

In addition, tertiary amines and imidazoles can be used in combination with amine-based curing agents other than dicyandiamide, such as epoxy resin curing agents (for example, room temperature curing curing agents), to improve the curing speed and the physical properties and heat resistance of the resulting cured product. etc. can be improved.

Component (F) may be used alone or in combination of two or more.

The present curable resin composition preferably further contains 0.1 to 10.0 parts by mass, and 0.2 to 5.0 parts by mass, of a curing accelerator (F) per 100 parts by mass of the epoxy resin (A). It is more preferable to contain 0 parts by weight, even more preferably to contain 0.5 to 3.0 parts by weight, and particularly preferably to contain 0.8 to 2.0 parts by weight. When the content of component (F) is 0.1 part by mass or more of (a) based on 100 parts by mass of component (A), the resulting curable resin composition has good curability, and (b) When the amount is 10.0 parts by mass or less, the storage stability of the resulting curable resin composition will be good, and the resulting curable resin composition will be easy to handle.

(2-1-7. Other ingredients)
In one embodiment of the present invention, other formulation components can be used as needed. Other ingredients include radical curable resin, monoepoxide, photopolymerization initiator, organic filler, pigment, flame retardant, dispersant, antifoaming agent, plasticizer, solvent, tackifier, leveling agent, and thixotropic agent. properties imparting agent, antioxidant, light stabilizer, ultraviolet absorber, silane coupling agent, titanate coupling agent, aluminate coupling agent, mold release agent, antistatic agent, lubricant, low shrinkage agent, azo type chemical Expanding agents such as a mechanical foaming agent and thermally expandable microballoons, fiber pulps such as aramid pulps, thermoplastic resins, and the like can be mentioned.

Specific examples of the radical curable resin, monoepoxide, and photopolymerization initiator include paragraphs [0143] to [0144], [0146], and [0148] of the specification of WO2016-163491, respectively. Examples include various compounds described in . Specific examples of pigments, flame retardants, dispersants, antifoaming agents, plasticizers, solvents, tackifiers, leveling agents, thixotropic agents, antioxidants, light stabilizers, ultraviolet absorbers, and silane coupling agents For example, [0124], [0126] to [0127], [0129] to [0130], [0132], [0134], [0136], and [0139] in the specification of WO2014-196607, respectively. ], [0141], [0143], [0147], [0149], [0151], and various compounds described in each paragraph of [0153].

The present curable resin composition may contain a rubber-modified epoxy resin and/or a urethane-modified epoxy resin as other ingredients. When the present curable resin composition contains a rubber-modified epoxy resin and/or a urethane-modified epoxy resin, the curable resin composition has properties such as toughness, impact resistance, shear adhesion, and peel adhesion. An even better cured product can be provided. The rubber-modified epoxy resin and/or the urethane-modified epoxy resin can also be said to be a reinforcing agent.

The reinforcing agents may be used alone or in combination of two or more.

As the rubber-modified epoxy resin, for example, resins described in paragraphs [0124] to [0132] of the specification of WO2016-163491 can be used.

As the urethane-modified epoxy resin, for example, the resins described in paragraphs [0133] to [0135] of the specification of WO2016-163491 can be used.

(2-1-8. Method for producing curable resin composition)
The present curable resin composition includes a composition containing polymer fine particles (B) in a curable resin mainly composed of component (A), and preferably, polymer fine particles (B) are present in component (A). contains a composition dispersed in the form of primary particles. "A composition in which polymer fine particles (B) are dispersed in component (A) in the form of primary particles" may be hereinafter referred to as a "polymer fine particle composition."

Various methods can be used to obtain the polymer fine particle composition. Examples of such methods include (a) a method of bringing polymer fine particles (B) obtained in an aqueous latex state into contact with component (A), and then removing unnecessary components such as water from the mixture; and (b) Examples include a method in which the polymer fine particles (B) are once extracted into an organic solvent, the extracted polymer fine particles (B) are mixed with the component (A), and then the organic solvent is removed from the mixture. As the method, it is preferable to use the method described in WO2005/028546.

A specific method for producing the polymer fine particle composition is as follows: (1) an aqueous latex containing polymer fine particles (B) (specifically, a reaction mixture after producing polymer fine particles (B) by emulsion polymerization); , a first step of aggregating the polymer fine particles (B) by mixing with an organic solvent having a water solubility of 5% by mass or more and 40% by mass or less at 20° C., and then further mixing the resulting mixture with excess water; (2) After separating and recovering the aggregated polymer particles (B) from the liquid phase, the polymer particles (B) are mixed with an organic solvent again to obtain an organic solvent solution in which the polymer particles (B) are dispersed. A method including a second step and (3) a third step of further mixing the obtained organic solvent solution with component (A) and then distilling off the organic solvent from the mixture is mentioned. Preferably, the polymer particulate composition is prepared by the method.

In order to facilitate the third step, the component (A) is preferably liquid at 23°C. "Liquid at 23°C" means that the softening point is 23°C or lower, and exhibits fluidity at 23°C.

The polymer fine particle composition can also be produced by a method other than the method including the above steps (first to third steps). For example, there is a method using powdered polymer fine particles (B). Specifically, first, the polymer fine particles (B) are coagulated by a method such as salting out using an aqueous latex containing the polymer fine particles (B), and then the resulting coagulated product is dried to form a powder. Polymer fine particles (B) are obtained. By redispersing the powdered polymer fine particles (B) into the component (A) using a dispersing machine having high mechanical shearing force such as a three-roll paint roll, a roll mill, or a kneader, a polymer fine particle composition is obtained. It is also possible to manufacture At this time, by applying mechanical shearing force at high temperature to the mixture of components (A) and (B), component (B) can be efficiently dispersed in component (A). The temperature during dispersion (temperature when applying shearing force) is preferably 50 to 200°C, more preferably 70 to 170°C, even more preferably 80 to 150°C, and particularly preferably 90 to 120°C. When the temperature during dispersion is (a) 50°C or higher, component (B) can be sufficiently dispersed, and (b) when it is 200°C or lower, component (A) and (B) can be dispersed. There is no risk of thermal deterioration.

By further adding and mixing components (C) and (D) to the polymer fine particle composition obtained by the above method, the polymer fine particles (B) are contained in component (A) in the state of primary particles. A dispersed curable resin composition is obtained. In the production of the present curable resin composition, component (A) may be further added to the polymer fine particle composition and mixed if necessary. In addition, in the production of the present curable resin composition, an epoxy resin curing agent other than dicyandiamide, component (E), component (F), and the other components listed above are further added to the polymer fine particle composition as necessary. May be added and mixed.

(2-1-9. Applications of curable resin composition)
This curable resin composition can be used as a one-component curable resin composition. A one-component curable resin composition including the present curable resin composition described above can also be considered as an embodiment of the present invention. A one-component curable resin composition is one that (i) can be sealed and stored without curing after all ingredients have been blended in advance, and (ii) after the curable resin composition is applied, it can be heated and /Or refers to a curable resin composition that is cured by light irradiation.

Further, the present curable resin composition can also be used as a two-component or multi-component curable resin composition. That is, (i) prepare liquid A containing component (A), component (B) and component (C) as main components, and (ii) component (D) and optionally component (E) and/or A solution B containing component (F) and, if necessary, component (B) and/or component (C) is prepared separately from solution A, and (iii) the solution A and the B solution are prepared separately. It can also be used by mixing it with a liquid before use. At least one type of liquid A and liquid B may be prepared, and a plurality of types of either one or both liquids may be prepared. In addition, the component (B) and the component (C) may each be contained in at least one of the A liquid and the B liquid. Component (B) and component (C) may be contained, for example, only in liquid A or only in liquid B, or may be contained in both liquid A and liquid B, respectively.

Since the present curable resin composition has excellent storage stability, it is particularly useful when used as a one-component curable resin composition. The present curable resin composition is preferably a one-component curable resin composition because of its excellent handling properties.

This curable resin composition is useful as an adhesive. This curable resin composition has excellent adhesive performance and flexibility not only at low temperatures (about -20°C) to room temperature, but also at high temperatures (about 80°C). Further, the present curable resin composition can provide a cured product with excellent elongation properties and a high Tg. Therefore, the present curable resin composition can be used more preferably as a structural adhesive, and even more preferably as a structural adhesive for different types of adherends having different coefficients of linear expansion. Adhesives and structural adhesives containing the above-mentioned curable resin composition can also be considered as embodiments of the present invention.

(2-2. Cured product)
The present laminate has a cured product made of the present curable resin composition. In this laminate, at least two adherends having different coefficients of linear expansion are bonded together via a cured product, so the cured product can also be called an adhesive layer. The cured product of the present laminate, that is, the cured product made of the present curable resin composition, can also be said to be an embodiment of the present invention.

Since the cured product according to one embodiment of the present invention is made of the above-mentioned curable resin composition, (a) it has a beautiful surface, (b) it has high Tg, so it has high rigidity and high elastic modulus, and (c) it has excellent physical properties such as toughness, adhesiveness (particularly impact-resistant peeling adhesiveness), and elongation.

The cured product according to an embodiment of the present invention has a Tg (°C) of preferably 109°C or higher, more preferably 110°C or higher, more preferably 112°C or higher, more preferably 113°C or higher, and even more preferably 115°C or higher. The temperature is preferably 117°C or higher, even more preferably 120°C or higher. According to this configuration, the cured product has higher rigidity and higher elastic modulus.

The cured product according to one embodiment of the present invention has a tensile strength (MPa) of preferably 31.0 MPa or more, more preferably 31.5 MPa or more, more preferably 32.0 MPa, more preferably 32.5 MPa or more, 33.0 MPa is more preferable, 34.0 MPa is even more preferable, and 35.0 MPa is particularly preferable. This configuration has the advantage that the bonding strength (adhesive strength) of the resulting laminate including the cured product is high.

The cured product according to one embodiment of the present invention preferably has a tensile strain at failure (%) of 20.5% or more, more preferably 21.0% or more, more preferably 23.0% or more, and 24.0%. More preferably, 25.0% or more, more preferably 28.0% or more, more preferably 30.0% or more, more preferably 33.0% or more, even more preferably 35.0% or more, It is even more preferably 38.0% or more, particularly preferably 40.0% or more. According to this configuration, the cured product has better elongation.

The cured product according to an embodiment of the present invention has a tensile modulus (GPa) of preferably 1.1 GPa or more, more preferably 1.2 GPa or more, further preferably 1.3 GPa or more, particularly preferably 1.4 GPa or more. . This configuration has the advantage that the bonding rigidity (adhesive rigidity) of the resulting laminate including the cured product is high.

In this specification, the tensile strength, tensile fracture strain, and tensile modulus of the cured product according to one embodiment of the present invention are values obtained by a method based on JIS K 7113, respectively.

The method for producing a cured product according to an embodiment of the present invention is as follows [3. The method described in the section "Method for producing a laminate" can be mentioned.

(2-3. Adherent)
This laminate has at least two adherends having different coefficients of linear expansion. In other words, the present curable resin composition can be used to adhere various adherends having different coefficients of linear expansion to produce various laminates. The "adherent" may also be referred to as a "substrate" or "adhesive substrate." The shape of the adherend is typically a plate, but is not limited thereto.

Examples of adherends include wood, metal, plastic, and glass. More specifically, the adherends include (i) steel materials such as cold-rolled steel and hot-dip galvanized steel, (ii) aluminum materials such as aluminum and coated aluminum, and (iii) general-purpose plastics, engineering plastics, and CFRP. and various plastic materials (substrates) such as composite materials such as GFRP.

The linear expansion coefficient of steel material (steel plate) is approximately 12×10 ⁻⁶ /K, the linear expansion coefficient of magnesium material is approximately 26×10 ⁻⁶ /K, and the linear expansion coefficient of aluminum material (aluminum plate) is approximately 23×10 ⁻⁶ /K, and the linear expansion coefficient of CFRP is about 0/K to 5×10 ⁻⁶ /K.

Since the present curable resin composition has excellent elongation properties and toughness, it can be suitably used for joining (adhering) different types of adherends having different coefficients of linear expansion. Suitable combinations of at least two adherends having different coefficients of linear expansion include steel and magnesium materials, steel and aluminum materials, steel and CFRP, CFRP and magnesium materials, CFRP and aluminum materials, aluminum materials and magnesium materials, etc. Can be mentioned. Furthermore, high-strength steel and general rolled steel may also have different coefficients of linear expansion. The present curable resin composition can also be suitably used for joining high-strength steel and general rolled steel. This curable resin composition is also suitable for joining adherends with small differences in linear expansion coefficients, such as general steel, carbon steel, high-strength steel, high-strength steel, ultra-strong steel, corrosion-resistant steel, and alloy steel. Available for In this text, the terms "bonding" and "adhesion" have the same meaning and are interchangeable.

In one embodiment of the present invention, the absolute value of the difference in linear expansion coefficients of at least two adherends included in the laminate may be 1×10 ⁻⁶ or more, and may be 3×10 ⁻⁶ or more. may be 5×10 ⁻⁶ or more, 7×10 ⁻⁶ or more, 8×10 ⁻⁶ or more, 9×10 ⁻⁶ or more Often, it may be 10 × 10 ^-6 or more, 11 × 10 ^-6 or more, 12 × 10 ^-6 or more, 13 × 10 ^-6 or more, It may be 14×10 ⁻⁶ or more, 16×10 ⁻⁶ or more, 18×10 ⁻⁶ or more, 20×10 ⁻⁶ or more, 22× It may be 10 ⁻⁶ or more, or it may be 24×10 ⁻⁶ or more. Even if the coefficients of linear expansion of at least two adherends are significantly different, as in this configuration, by using the present curable resin composition, a laminate formed by adhering the two adherends. can be obtained.

Further, as the adherend, structural materials for aerospace, in particular, exterior metal structural materials are also suitably mentioned.

(2-4. Laminate)
This curable resin composition has excellent adhesive properties. Therefore, a laminate in which a cured product made of the present curable resin composition is laminated between at least two adherends having different coefficients of linear expansion, such as steel, aluminum, and CFRP, exhibits high adhesive strength. It has the advantage of The present laminate can also be said to be a laminate in which at least two adherends having different linear expansion coefficients, such as steel material, aluminum material, and CFRP, are adhered by a cured product made of the present curable resin composition. A laminate can also be called a structure.

[3. Method for manufacturing laminate]
One embodiment of the present invention provides a method for manufacturing a first laminate. The method for manufacturing the first laminate includes a bonding step of applying a curable resin composition to a first adherend, bonding a second adherend to the first adherend, and a step of applying a curable resin composition to the first adherend. and a curing step of curing the composition. In the first laminate manufacturing method, the first adherend and the second adherend have different linear expansion coefficients. In the first method for producing a laminate, the curable resin composition includes an epoxy resin (A), and 1 to 100 parts by mass of polymer fine particles (B) per 100 parts by mass of the epoxy resin (A); Contains 5 to 50 parts by weight of blocked urethane (C) and 9.0 to 17.0 parts by weight of dicyandiamide (D). In the first method for producing a laminate, the polymer fine particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.

The method for manufacturing the first laminate is described in [2. Curable resin composition] can be suitably used to produce the first laminate described in the section ``Curable resin composition''.

The method for manufacturing the first laminate has the above-mentioned configuration, and in particular, the curable resin composition contains specific amounts of each of component (A), component (B), component (C), and component (D). It has the advantage of being able to provide a laminate containing a cured product that has excellent elongation properties and a high glass transition temperature (Tg).

Another embodiment of the present invention provides a method for manufacturing the second laminate. The method for manufacturing the second laminate includes a bonding process in which a curable resin composition is applied to a first adherend, the second adherend is bonded to the first adherend, and a curable resin composition is applied to the first adherend. and a curing step of curing the composition. In the second method for manufacturing a laminate, the first adherend and the second adherend have different coefficients of linear expansion. In the second method for producing a laminate, the curable resin composition contains an epoxy resin (A), polymer particles (B), blocked urethane (C), and dicyandiamide (D). In the second method for producing a laminate, the polymer particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body. In the second laminate manufacturing method, the cured product has a glass transition temperature (Tg) of 110°C or higher, and a tensile fracture strain of the cured product obtained by a method based on JIS K 7113 is 23.0% or higher. be.

The second laminate manufacturing method is described in [2. It can be suitably used to produce the second laminate described in the section "Curable resin composition".

Since the second laminate manufacturing method has the above-mentioned configuration, the curable resin composition contains the (A) component, the (B) component, the (C) component, and the (D) component, and the curing Since the product has specific physical properties, it has the advantage of being able to provide a laminate containing a cured product that has excellent elongation properties and a high glass transition temperature (Tg). In the second method for producing a laminate, the content of each of component (A), component (B), component (C), and component (D) in the curable resin composition is as long as the cured product has specific physical properties. is not particularly limited and can be set as appropriate.

The first method for manufacturing a laminate and the second method for manufacturing a laminate are both methods for manufacturing a laminate according to an embodiment of the present invention. The "method for manufacturing a laminate according to an embodiment of the present invention" may also be referred to as the "present manufacturing method."

In this curable resin composition, the polymer fine particles (B) are uniformly dispersed in the component (A) in the form of primary particles. Therefore, by curing the curable resin composition, a cured product in which the polymer fine particles (B) are uniformly dispersed can be easily obtained. Furthermore, in the present curable resin composition, the polymer particles (B) are difficult to swell, and the curable resin composition has low viscosity. Therefore, a cured product can be obtained with good workability. In other words, by using the present curable resin composition, adherends can be adhered with good workability, that is, a method for manufacturing a laminate with good workability can be provided.

Each process related to this manufacturing method will be explained below, except for matters detailed below. Curable resin composition] is incorporated herein by reference.

(3-1. Bonding process)
The bonding step is a step in which the curable resin composition is applied to the first adherend, and then the second adherend is bonded to the first adherend. In the respective bonding steps of the first laminate manufacturing method and the second laminate manufacturing method, the composition of the curable resin composition used may differ, but The aspects are the same.

In the bonding step, the curable resin composition applied to the first adherend is sandwiched between the first adherend and the second adherend. Attach the body. Moreover, at this time, the curable resin composition sandwiched between the first adherend and the second adherend may protrude from the first adherend and/or the second adherend. . Furthermore, in addition to being applied to the first adherend, the curable resin composition may be applied to a second adherend, if necessary.

This curable resin composition can be applied by any method.

The curable resin composition can also be applied by extrusion onto a substrate in the form of a bead, monofilament or swirl using a coating robot, mechanical application methods such as a caulking gun, and other manual methods. Application means can also be used. Further, the curable resin composition can also be applied to the substrate using a jet spray method or a streaming method.

Note that the viscosity of the present curable resin composition is not particularly limited, and can be appropriately set depending on the coating method. The viscosity of the present curable resin composition is preferably about 150 to 600 Pa·s at 45°C in (a) extrusion bead method, and preferably about 100 Pa·s at 45°C in (b) swirl coating method. , (c) In the high-volume coating method using a high-speed flow device, the temperature is preferably about 20 to 400 Pa·s at 45°C.

In the bonding step, the temperature of the curable resin composition applied to the first adherend is also referred to as "first temperature." In the bonding step, the curable resin composition may be heated to a first temperature and applied to the first adherend.

The first temperature may be room temperature. Preferably, the first temperature is higher than room temperature. As used herein, "room temperature" is generally 5°C to 45°C, preferably 10°C to 40°C, more preferably 15°C to 34°C, and most preferably 20°C to 30°C. It is.

In the bonding step, the first temperature (temperature of the curable resin composition applied to the first adherend) is, for example, preferably 35°C to 80°C, and preferably 40°C to 70°C. The temperature is more preferably 45°C to 60°C, particularly preferably 45°C to 60°C. When the first temperature is (a) 35°C or higher, the viscosity of the curable resin composition becomes low, which has the advantage of making the coating work easier, and (b) when it is 80°C or lower, the epoxy It has the advantage that there is no risk that a part of the compound will start to react and the viscosity will increase, making the coating work easier.

The thickness of the curable resin composition applied to the first adherend is also referred to as "first thickness." In the bonding step, it can be said that the curable resin composition is applied to the first adherend to a first thickness.

The first thickness is, for example, preferably 0.5 mm to 10 mm, more preferably 1 mm to 7 mm, even more preferably 1.5 mm to 5 mm, and particularly preferably 2 mm to 4 mm.

In the bonding process, the curable resin composition applied to the first adherend to a first thickness is It is thinner than the thickness and may be stretched. The thickness of the curable resin composition after being stretched is also referred to as "second thickness."

The second thickness is not particularly limited as long as it is thinner than the first thickness. The second thickness is, for example, preferably 0.001 mm to 5 mm, more preferably 0.01 mm to 1 mm, particularly preferably 0.1 mm to 0.3 mm.

In the bonding step, the specific method of stretching the curable resin composition applied to the first thickness to the second thickness is not particularly limited. The method includes, for example, (i) a method in which the curable resin composition applied to a first thickness is stretched to a second thickness using a spatula, and (ii) a method in which the curable resin composition is applied in a first thickness. When attaching the second adherend to the first adherend, the two adherends are brought close to each other with the curable resin composition sandwiched between them, so that the first thickness is applied. Examples include a method of spreading and stretching the curable resin composition to a second thickness using two adherends.

The environmental temperature (room temperature) when performing the bonding process is also referred to as "second temperature."

Preferably, the second temperature is lower than the first temperature. The second temperature may be room temperature.

The second temperature is, for example, preferably 0°C to 34°C, more preferably 5°C to 30°C, particularly preferably 10°C to 25°C. When the second temperature is (a) 0°C or higher, the viscosity of the curable resin composition becomes low, which has the advantage of making it easier to stretch the composition to the second thickness, and (b) 34°C or lower. In this case, there is no risk that the storage stability of the curable resin composition will deteriorate when stored for a long period of time.

The bonding step may further include a step of stretching the curable resin composition applied to the first thickness to a second thickness in an environment at a second temperature.

(3-2. Curing process)
The curing step is a step of curing the curable resin composition sandwiched between the two bonded adherends. Through the curing process, a laminate in which two adherends are bonded together with a curable resin composition, in other words, a cured product made of a curable resin composition is formed between at least two adherends having different coefficients of linear expansion. It is possible to obtain a laminate formed by laminating layers. In the respective curing steps of the first laminate manufacturing method and the second laminate manufacturing method, the composition of the curable resin composition used and the physical properties of the resulting cured product may differ; Aspects other than the composition of the resin composition and the physical properties of the obtained cured product are the same.

In the curing step, the curable resin composition can be cured by heating the curable resin composition.

(Curing temperature)
In the curing step, the heating temperature of the curable resin composition is also referred to as curing temperature. The curing temperature can also be said to be the temperature exhibited by a heated curable resin composition, or the temperature of the curable resin composition when curing the curable resin composition. In the curing step, the curing temperature of the present curable resin composition is not particularly limited. In the curing step, the curing temperature of the curable resin composition is preferably 50°C to 250°C, more preferably 80°C to 220°C, even more preferably 100°C to 200°C, Particularly preferred is a temperature of 130°C to 180°C. When the curing temperature is 50° C. or higher, a good balance between storage stability and curability is obtained when the curable resin composition is used as a one-component curable resin composition. When the curing temperature is 250° C. or lower, the resulting laminate will have good adhesive properties.

When manufacturing a laminate using at least two adherends having different coefficients of linear expansion, a dimensional difference occurs between the two adherends due to the difference in coefficient of linear expansion. Such dimensional differences become more noticeable at high temperatures. In the production of a laminate using at least two adherends with different linear expansion coefficients and a conventional curable resin composition, when the curing process is performed at a high temperature of 50°C to 250°C, Therefore, it was not possible to obtain a laminate having good adhesive properties. This curable resin composition has the above-mentioned structure. Therefore, in the production of a laminate using at least two adherends with different linear expansion coefficients and the present curable resin composition, even when the curing process is performed at a high temperature of 50°C to 250°C, the performance is good. A laminate having excellent adhesive properties can be obtained.

(3-3. Cleaning process)
This manufacturing method may further include a cleaning step of cleaning the bonded body obtained in the bonding step.

In the cleaning step, the cleaning liquid for cleaning the bonded body is not particularly limited. Preferred examples of the cleaning liquid include water, an aqueous solution containing an acid, or an alkali.

The temperature of the cleaning liquid is not particularly limited. The temperature of the cleaning liquid may be 20°C to 80°C, more preferably 30°C to 70°C, and may be 40°C to 60°C. The higher the temperature of the cleaning liquid, the more (a) a higher cleaning effect can be obtained, and (b) the risk of scattering and deformation of the applied curable resin composition increases. Therefore, the temperature of the cleaning liquid can be appropriately determined in consideration of the balance between the cleaning effect and the scattering and deformation of the curable resin composition. This curable resin composition has the advantage that its viscosity has little temperature dependence and has a high viscosity even at high temperatures. Therefore, in this manufacturing method, a higher temperature cleaning liquid can be used compared to the case where a conventional curable resin composition is used.

The method for cleaning the bonded body is not particularly limited, and examples include a method of immersing the bonded body in a cleaning liquid, and a method of spraying (showering) the bonded body with a cleaning liquid.

The pressure of the cleaning liquid when spraying the cleaning liquid onto the bonded body is not particularly limited. The pressure (water pressure) of the cleaning liquid may be 0.1 MPa to 1.0 MPa, 0.1 MPa to 0.5 MPa, or 0.2 MPa to 0.4 MPa. The higher the pressure of the cleaning liquid, the more (a) a higher cleaning effect can be obtained, and (b) the risk of scattering and deformation of the applied curable resin composition increases. Therefore, the pressure of the cleaning liquid can be appropriately determined in consideration of the balance between the cleaning effect and the scattering and deformation of the curable resin composition. This curable resin composition has the advantage of having a high shear rate dependence of viscosity and a high yield stress value. Therefore, in this manufacturing method, compared to the case of using a conventional curable resin composition, the cleaning liquid can be sprayed onto the adherend under higher pressure conditions.

In the cleaning step, the object to be cleaned, that is, to be washed off, is not particularly limited. In the cleaning step, examples of objects to be washed off include rust preventive oil that has been applied in advance to the raw material of the adherend.

(3-4. Paint application process)
This manufacturing method may further include a paint application step of applying paint to the bonded body. The coating process can be performed at any stage. The coating step is preferably performed after the cleaning step and before the curing step. When the coating process is performed after the cleaning process, there is an advantage that the coating properties are improved. When the coating liquid contains a curable resin and the coating step is performed before the curing step, the coating material can be cured simultaneously with the curing of the curable resin composition.

Examples of paints include, but are not limited to, the following: rust inhibitors, pigments, matting agents, gloss-imparting agents, antireflection agents, and the like.

[4. Use]
Examples of the laminate (structure) according to an embodiment of the present invention include automobiles and vehicles (Shinkansen, trains, etc.), aircraft, spacecraft, space stations, buildings, structures, wooden structures, and electrical facilities. , wind power plants, electrical related parts, electronic related parts, electronics related facilities, electronics related parts, etc. Examples of automotive-related applications include interior materials such as ceilings, doors, and seats, automotive lighting fixtures such as lamps, and exterior materials such as side moldings.

EXAMPLES Hereinafter, one embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. One embodiment of the present invention can be implemented by appropriately modifying the following example within a range that is compatible with the spirit described above and below. All embodiments implemented by appropriately modifying the following examples are included in the technical scope of the present invention. In the Examples, Comparative Examples, and Tables below, "parts" and "%" mean parts by mass and % by mass, respectively.

(Measurement method and evaluation method)
First, methods for measuring and evaluating each physical property will be explained below.

[1] Measurement of volume average particle diameter The volume average particle diameter (Mv) of the polymer fine particles (B) dispersed in the aqueous latex was measured using Microtrack UPA150 (manufactured by Nikkiso Co., Ltd.). Aqueous latex diluted with deionized water was used as a measurement sample. The measurement was performed by inputting the refractive index of water and the refractive index of the polymer fine particles (B) obtained in each production example, measuring time 600 seconds, and making sure that the Signal Level was within the range of 0.6 to 0.8. The sample concentration was adjusted accordingly.

[2] Measurement of dumbbell tensile properties Each of the curable resin compositions obtained in Examples and Comparative Examples was poured between two glass plates with a 3 mm thick spacer sandwiched therebetween. The glass plate containing the obtained curable resin composition was left in a hot air oven at a predetermined temperature (curing temperature) for 1 hour to cure the curable resin composition and obtain a plate-shaped cured product with a thickness of 3 mm. Ta. Here, each of the curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6 had a hot air oven temperature, that is, a curing temperature of 170° C. (Tables 1 and 2). On the other hand, each of the curable resin compositions obtained in Examples 10 to 12 had a hot air oven temperature, that is, a curing temperature of 180° C. (Table 3). The obtained cured product was cut into the shape of a JIS K 7113 No. 1 test piece to obtain a test piece. Using the obtained test piece, a tensile test was conducted according to JIS K 7113 to obtain tensile strength, tensile fracture strain, and tensile modulus. The test conditions were: distance between chucks: 115 mm, distance between marked lines: 50 mm, measurement temperature: 23° C., and test speed: 5 mm/min.

[3] Measurement of glass transition temperature (Tg) Each of the curable resin compositions obtained in Examples and Comparative Examples was cured at 170°C or 180°C for 1 hour to obtain a cured product. Using the obtained cured product, the temperature was raised at 4° C./min using a dynamic viscoelasticity measuring machine to obtain a tan δ curve. The peak temperature of the obtained tan δ curve was defined as the glass transition temperature (Tg).

(1. Formation of elastic body)
(Production Example 1-1; Preparation of polybutadiene rubber latex (R-1))
In a pressure-resistant polymerization machine with a volume of 100 L, 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.25 parts by mass of potassium dihydrogen phosphate, and 0.002 parts by mass of disodium ethylenediaminetetraacetate (EDTA). , 0.001 parts by mass of ferrous sulfate heptahydrate (FE), and 1.5 parts by mass of sodium dodecylbenzenesulfonate (SDS) as an emulsifier were added. Next, while stirring the charged raw materials, the gas inside the pressure polymerization vessel was replaced with nitrogen to sufficiently remove oxygen from the inside of the pressure polymerization vessel. Thereafter, 100 parts by mass of butadiene (BD) was charged into the pressure polymerization vessel, and the temperature inside the pressure polymerization vessel was raised to 45°C. Thereafter, 0.015 parts by mass of paramenthane hydroperoxide (PHP) was charged into a pressure-resistant polymerization vessel, followed by 0.04 parts by mass of sodium formaldehyde sulfoxylate (SFS) into the pressure-resistant polymerization vessel, and the polymerization was continued. It started. Ten hours after the start of polymerization, the polymerization was completed by devolatilizing under reduced pressure to remove the remaining monomers that were not used in the polymerization. During the polymerization, each of PHP, EDTA, and FE was added in an arbitrary amount and at an arbitrary time into a pressure-resistant polymerization vessel. Through the polymerization, a latex (R-1) containing an elastic body (polybutadiene rubber particles) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.10 μm.

(Production Example 1-2; Preparation of polybutadiene rubber latex (R-2))
In a pressure-resistant polymerization machine with a volume of 100 L, 7 parts by mass of the polybutadiene rubber latex (R-1) obtained in Production Example 1-1 in terms of solid content, 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of EDTA and 0.001 parts by mass of FE were added. Next, while stirring the charged raw materials, the gas inside the pressure polymerization vessel was replaced with nitrogen to sufficiently remove oxygen from the inside of the pressure polymerization vessel. Thereafter, 93 parts by mass of BD was charged into a pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. Thereafter, 0.02 parts by mass of PHP was charged into a pressure-resistant polymerization vessel, and then 0.10 parts by mass of SFS was charged into the pressure-resistant polymerization vessel to start polymerization. Thirty hours after the start of the polymerization, the polymerization was completed by devolatilizing the monomer under reduced pressure to remove the remaining monomers that were not used in the polymerization. During the polymerization, each of PHP, EDTA, and FE was added in an arbitrary amount and at an arbitrary time into a pressure-resistant polymerization vessel. Through the polymerization, a latex (R-2) containing an elastic body (polybutadiene rubber particles) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.20 μm.

(2. Preparation of polymer fine particles (B) (formation of graft portion))
(Production Example 2-1; Preparation of polymer fine particle latex (L-1))
A glass reactor was charged with 256 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (including 85 parts by mass of polybutadiene rubber particles) and 61 parts by mass of deionized water. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and while the nitrogen replacement was being performed, the raw materials introduced were stirred at 60°C. Next, 0.004 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.2 parts by mass of SFS were added into the glass reactor. Thereafter, monomers for forming a graft portion (hereinafter also referred to as graft monomers) (7 parts by mass of styrene (ST), 1.5 parts by mass of methyl methacrylate (MMA), 2.5 parts by mass of acrylonitrile (AN), and glycidyl A mixture of 4 parts by mass of methacrylate (GMA) and 0.04 parts by mass of cumene hydroperoxide (CHP) was continuously added into a glass reactor over 80 minutes. After the addition was completed, 0.04 parts by mass of CHP was added into the glass reactor, and the mixture in the glass reactor was continued to be stirred for an additional 2 hours to complete the polymerization. Through the above operations, an aqueous latex (L-1) containing polymer fine particles (B) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the polymer fine particles (B) contained in the obtained aqueous latex was 0.21 μm.

(3. Preparation of dispersion (M) in which polymer fine particles (B) are dispersed in curable resin composition)
(Production Example 3-1; Preparation of dispersion (M-1))
132 g of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank at 25°C. Next, while stirring MEK, 132 g of the aqueous latex (L-1) containing the polymer fine particles (B) obtained in Production Example 2-1 (equivalent to 40 g of polymer fine particles (B)) was put into the mixing tank. . After uniformly mixing the raw materials in the mixing tank, 200 g of water was poured into the mixing tank at a feed rate of 80 g/min while stirring the raw materials in the mixing tank. After the water supply was completed, the stirring was immediately stopped to obtain a slurry liquid consisting of an aqueous phase containing aggregates containing the polymer fine particles (B) and a small amount of organic solvent. The aggregates were buoyant. Next, 360 g of the aqueous phase was discharged from the outlet at the bottom of the mixing tank so that aggregates containing some of the water phase remained in the mixing tank. 90 g of MEK was added to the obtained aggregate and mixed uniformly to obtain a dispersion in which polymer fine particles (B) were uniformly dispersed in MEK. 60 g of epoxy resin (A-1) as component (A) was added to the obtained dispersion and mixed uniformly. The epoxy resin (A-1) will be detailed below. MEK was removed from the resulting mixture using a rotary evaporator. In this way, a dispersion (M-1) in which polymer fine particles (B) were dispersed in an epoxy resin (A) was obtained.

(Production Example 3-2; Preparation of dispersion (M-2))
In Production Example 3-1, epoxy A dispersion (M-2) in which fine polymer particles (B) were dispersed in resin (A) was obtained. The epoxy resin (A-2) will be detailed below.

(Examples 1 to 12, Comparative Examples 1 to 6)
According to the formulations (mixtures) shown in Tables 1 to 3, each component was weighed and thoroughly mixed to obtain a curable resin composition. Test results of the dumbbell tensile physical properties (tensile strength, tensile breaking strain, tensile modulus) and glass transition temperature (Tg) of the obtained curable resin composition are shown in Tables 1 to 3.

The various compounding agents in Tables 1 to 3 were as shown below.
≪Epoxy resin (A)≫
Epoxy resin (A-1): JER828 (manufactured by Mitsubishi Chemical, bisphenol A type epoxy resin that is liquid at room temperature, epoxy equivalent: 184-194)
Epoxy resin (A-2): JER806 (manufactured by Mitsubishi Chemical, bisphenol F type epoxy resin that is liquid at room temperature, epoxy equivalent: 160-170)
≪Dispersion (M) in which polymer particles (B) are dispersed in epoxy resin (A)≫
M-1~2: Dispersion obtained in Production Examples 3-1~2 <<Blocked urethane (C)>>
QR-9466 (made by ADEKA, block urethane)
≪Epoxy curing agent (D)≫
Dyhard 100S (manufactured by AlzChem, dicyandiamide)
≪Inorganic filler (E)≫
(Surface-untreated heavy calcium carbonate)
Whiten SB (manufactured by Shiraishi Calcium, surface-untreated heavy calcium carbonate, average particle size: 1.8 μm)
(calcium oxide)
CML #31 (manufactured by Ohmi Chemical Industry, calcium oxide surface treated with fatty acid)
≪Curing accelerator (F)≫
Dyhard UR200 (manufactured by AlzChem, 1,1-dimethyl-3-(3,4-dichlorophenyl)urea)

Note that the amount (parts by mass) of component (A) contained in the curable resin compositions in Tables 1 to 3 is the amount described in the column of component (i) (A), that is, the amount of (A) added as an epoxy resin. ) component and (ii) the amount described in the column of (A) component + (B) component, that is, the amount of component (A) contained in the dispersion (M) of polymer fine particles (B). This is the amount.

From Tables 1 to 3, it is found that the composition contains the (A) component, (B) component, (C) component, and 9.0 parts by mass to 17.0 parts by mass of the (D) component according to one embodiment of the present invention. It can be seen that the curable resin compositions of Examples 1 to 12 can provide cured products with excellent elongation properties (high tensile fracture strain values) and high glass transition temperatures (Tg). Therefore, the curable resin composition according to one embodiment of the present invention is suitable for bonding different types of base materials with different linear expansion coefficients, and is also capable of providing a cured product (adhesive layer) with excellent heat resistance and elastic modulus. It turns out that it is a drug.

The curable resin compositions of Comparative Example 6, which does not contain polymer fine particles (B), and Comparative Example 3, which does not contain blocked urethane (C), produce cured products with poor elongation physical properties (low tensile failure strain value). Therefore, it is considered difficult to be suitable for joining different types of substrates. The curable resin compositions of Comparative Examples 4 and 5 containing more than 50 parts by mass of blocked urethane (C) had a low Tg value and insufficient heat resistance and elastic modulus (adhesive layer). ) is an adhesive that provides

The curable resin composition of Comparative Example 1 containing less than 9 parts by mass of dicyandiamide (D) provides a cured product with poor elongation physical properties (low tensile failure strain value), and therefore is suitable for joining dissimilar substrates. It seems difficult to suit. The curable resin composition of Comparative Example 2 containing more than 17 parts by mass of dicyandiamide (D) is an adhesive that provides a cured product (adhesive layer) with a low Tg value and insufficient heat resistance and elastic modulus. be.

According to one embodiment of the present invention, it is possible to provide a laminate containing a cured product that has excellent elongation properties and a high glass transition temperature, and a method for manufacturing the laminate. Therefore, the laminate according to one embodiment of the present invention and the method for manufacturing the laminate can be suitably used in fields such as vehicles, aircraft, space, machinery, electricity, architecture, and civil engineering.

Claims (15)

It has at least two adherends having different coefficients of linear expansion and a cured product made of a curable resin composition,
The cured product is laminated between the at least two adherends,
The curable resin composition comprises an epoxy resin (A), and a graft in which an elastic body and a polymer having an epoxy group are graft-bonded to the epoxy resin (A) and 100 parts by mass of the epoxy resin (A). 1 to 100 parts by weight of polymer fine particles (B) containing a rubber-containing graft copolymer having parts of Contains 17.0 parts by mass,
The at least two adherends are one selected from the group consisting of steel and magnesium materials, steel and aluminum materials, steel and CFRP, CFRP and magnesium materials, CFRP and aluminum materials, and aluminum materials and magnesium materials. A laminate including a combination of the above. The laminate according to claim 1, wherein the graft portion to which the polymer having an epoxy group is graft-bonded has a content of the epoxy group based on the mass of the graft portion from 0.1 mmol/g to 5.0 mmol/g. . The laminate according to claim 1 or 2, wherein the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and polysiloxane rubber elastic body. The laminate according to claim 3, wherein the diene rubber is a butadiene rubber and/or a butadiene-styrene rubber . It has at least two adherends having different coefficients of linear expansion and a cured product made of a curable resin composition,
The cured product is laminated between the at least two adherends,
The curable resin composition includes an epoxy resin (A) and an elastic body containing butadiene rubber and/or butadiene-styrene rubber as a diene rubber based on 100 parts by mass of the epoxy resin (A). 1 to 100 parts by mass of polymer fine particles (B) containing a rubber-containing graft copolymer having a graft moiety grafted to an elastic body, 5 parts to 50 parts by mass of blocked urethane (C), and Contains 9.0 parts by mass to 17.0 parts by mass of dicyandiamide (D),
The at least two adherends are one selected from the group consisting of steel and magnesium materials, steel and aluminum materials, steel and CFRP, CFRP and magnesium materials, CFRP and aluminum materials, and aluminum materials and magnesium materials. A laminate including a combination of the above. The laminate according to claim 5, wherein the graft portion is a polymer having an epoxy group. The laminate according to claim 5 or 6, wherein the graft portion is a polymer having an epoxy group, and the content of the epoxy group with respect to the mass of the graft portion is 0.1 mmol/g to 5.0 mmol/g. . Any one of claims 1 to 7 , wherein the cured product has a glass transition temperature of 110° C. or higher, and a tensile failure strain of the cured product obtained by a method compliant with JIS K 7113 is 23.0% or higher. The laminate described in . The epoxy resin (A) contains a bisphenol F-type epoxy resin (A1), and the content of the bisphenol F-type epoxy resin (A1) in 100 mass% of the epoxy resin (A) is 1% by mass to 100% by mass. %, the laminate according to any one of claims 1 to 8 . Claims 1 to 3, further comprising an inorganic filler (E), wherein the content of the inorganic filler (E) in 100% by mass of the curable resin composition is 0.1% by mass to 15% by mass. 9. The laminate according to any one of 9 . Any one of claims 1 to 10 , wherein the curable resin composition further contains 0.1 parts by mass to 10 parts by mass of a curing accelerator (F) based on 100 parts by mass of the epoxy resin (A). The laminate according to item 1. 1. The graft portion is a polymer containing, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer. The laminate according to any one of items 1 to 11 . a bonding step of applying a curable resin composition to a first adherend and bonding a second adherend to the first adherend;
a curing step of curing the curable resin composition,
The first adherend and the second adherend have different linear expansion coefficients,
The curable resin composition comprises an epoxy resin (A), and a graft in which an elastic body and a polymer having an epoxy group are graft-bonded to the epoxy resin (A) and 100 parts by mass of the epoxy resin (A). 1 to 100 parts by weight of polymer fine particles (B) containing a rubber-containing graft copolymer having parts of Contains 17.0 parts by mass,
The first adherend and the second adherend are made of steel and magnesium materials, steel and aluminum materials, steel and CFRP, CFRP and magnesium materials, CFRP and aluminum materials, and aluminum materials and magnesium materials. A method for manufacturing a laminate, which is a combination of one or more selected from the group consisting of: a bonding step of applying a curable resin composition to a first adherend and bonding a second adherend to the first adherend;
a curing step of curing the curable resin composition,
The first adherend and the second adherend have different linear expansion coefficients,
The curable resin composition includes an epoxy resin (A) and an elastic body containing butadiene rubber and/or butadiene-styrene rubber as a diene rubber based on 100 parts by mass of the epoxy resin (A). 1 to 100 parts by mass of polymer fine particles (B) containing a rubber-containing graft copolymer having a graft moiety grafted to an elastic body, 5 parts to 50 parts by mass of blocked urethane (C), and Contains 9.0 parts by mass to 17.0 parts by mass of dicyandiamide (D),
The first adherend and the second adherend are made of steel and magnesium materials, steel and aluminum materials, steel and CFRP, CFRP and magnesium materials, CFRP and aluminum materials, and aluminum materials and magnesium materials. A method for manufacturing a laminate, which is a combination of one or more selected from the group consisting of: The method for producing a laminate according to claim 13 or 14 , wherein in the curing step, the curing temperature of the curable resin composition is 130°C or higher.