JP7290446B2 - Curable resin composition and use thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition and technology for using the same.

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

Patent Documents 1 and 2 disclose a technique of dispersing fine polymer particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component in order to improve the toughness and impact resistance of the cured product. disclosed.

Patent Documents 1 and 2 also disclose a technique of adding an inorganic filler such as calcium carbonate to a curable resin composition containing an epoxy resin and fine polymer particles having a core-shell structure.

Patent Document 3 discloses a one-liquid heat-curable epoxy resin adhesive containing, in addition to an epoxy resin and core-shell acrylic particles, resin acid-treated calcium carbonate and the like.

Curable resin compositions containing epoxy resins are sometimes used as adhesives (eg, structural adhesives) (Patent Documents 4 to 8).

JP 2016-199738 A JP 2014-141604 A JP 2010-150401 A JP 2017-132953 A JP 2009-299028 A JP-A-8-302278 JP-A-4-88077 JP 2015-078280 A

However, the prior art as described above has room for further improvement from the viewpoint of the shear rate dependence of the viscosity of the curable resin composition and the impact resistance peel adhesion of the cured product.

One embodiment of the present invention has been made in view of the above-mentioned problems, and its object is to provide a curable resin that has excellent shear rate dependency of viscosity and that can provide a cured product having excellent impact peel adhesiveness. It is to provide the composition and its application technology.

As a result of intensive studies in order to solve such problems, the present inventors have found that in a curable resin composition containing an epoxy resin (A), polymer fine particles (B) and calcium carbonate, calcium carbonate is silane coupling The inventors have found that the above problems can be solved by using colloidal calcium carbonate (C) surface-treated with an agent, and have completed the present invention.

That is, one embodiment of the present invention includes the following configurations.
[1] A polymer containing an epoxy resin (A) and a rubber-containing graft copolymer having an elastic body and a graft part graft-bonded to the elastic body with respect to 100 parts by mass of the epoxy resin (A) A curable resin composition containing 1 to 100 parts by mass of fine particles (B) and 10 to 150 parts by mass of colloidal calcium carbonate (C) surface-treated with a silane coupling agent.
[2] The curable resin composition according to [1], which further contains 1 to 80 parts by mass of an epoxy curing agent (D) with respect to 100 parts by mass of the epoxy resin (A).
[3] The curable resin composition according to [1] or [2], which further contains 0.1 to 10.0 parts by mass of a curing accelerator (E) with respect to 100 parts by mass of the epoxy resin (A). thing.
[4] any one of [1] to [3], wherein the elastic body includes one or more selected from the group consisting of diene-based rubber, (meth)acrylate-based rubber and polysiloxane rubber-based elastic body; A curable resin composition as described.
[5] The curable resin composition according to any one of [1] to [4], wherein the elastic body is butadiene rubber and/or butadiene-styrene rubber.
[6] 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 aromatic vinyl monomers, vinyl cyanide monomers and (meth)acrylate monomers [ 1] The curable resin composition according to any one of [5].
[7] The curable resin composition according to any one of [1] to [6], wherein the graft portion is a polymer having an epoxy group.
[8] The curable resin composition according to any one of [1] to [7], wherein the graft portion is a polymer containing, as a structural unit, a structural unit derived from a monomer having an epoxy group.
[9] The graft portion is a polymer having an epoxy group, and the content of the epoxy group relative to the mass of the graft portion is 0.1 mmol/g to 5.0 mmol/g [1] to [8] The curable resin composition according to any one of.
[10] A one-component curable resin composition comprising the curable resin composition according to any one of [1] to [9].
[11] A structural adhesive comprising the curable resin composition according to any one of [1] to [9].
[12] A cured product obtained by curing the curable resin composition according to any one of [1] to [9].
[13] A laminate comprising the curable resin composition according to any one of [1] to [9].

According to one embodiment of the present invention, it is possible to provide a curable resin composition that has excellent shear rate dependency of viscosity and that can provide a cured product having excellent impact resistance to peeling adhesion.

An embodiment of the invention will be described below, but the invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible 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. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[1. Technical idea of one embodiment of the present invention]
As described in Patent Document 1, Patent Document 2, and Patent Document 3, it is impossible to add an inorganic filler such as calcium carbonate to a curable resin composition containing an epoxy resin and polymer fine particles having a core-shell structure. It is possible. However, when a large amount of inorganic filler is added to the curable resin composition, the problem is that the toughness of the curable resin composition is further reduced.

An adhesive using an epoxy resin composition having toughness and impact resistance (corresponding to a curable resin composition in one embodiment of the present invention) is suitably used as a structural adhesive such as a structural adhesive for vehicles. It is Epoxy resins have brittle properties, and therefore, curable resin compositions containing epoxy resins tend to have insufficient adhesiveness, and improvement in adhesiveness is desired. In the field of automotive structural adhesives, among adhesive properties, the impact peel strength (also referred to as impact peel adhesion) described in ISO 11343 is emphasized.

Further, for structural adhesives, as described in Patent Document 4, it is desired to improve the workability of the structural adhesive composition during application.

Further, as described in Patent Documents 5 to 7, a step of applying a curable resin composition (adhesive) to an object to be adhered and a step of curing the curable resin composition in a production line for vehicles and the like. There may be a flush shower step between. In conventional curable resin compositions, part of the uncured curable resin composition dissolves or part of the curable resin composition scatters due to the shower water pressure during the water washing shower process. There are problems such as washing off and deformation of the curable resin composition.

In order to reduce scattering and deformation of the uncured curable resin composition due to water pressure, conventionally, as disclosed in Patent Document 8, etc., studies have been made to improve the shear rate dependence of the viscosity of the curable resin composition. is done.

The present inventor studied the viscosity of the curable resin composition and made the following assumptions. That is, the phenomenon of deformation of the curable resin composition due to shower water pressure is deformation of the curable resin composition in a static state, and the viscosity of the curable resin composition in the low shear rate region is important. Then, the viscosity of the curable resin composition in the high shear rate range during application is reduced, and the viscosity of the curable resin composition in the low shear rate range is increased, that is, the viscosity of the curable resin composition is sheared The present inventor independently found that by increasing the speed dependence, it is possible to achieve both suppression of scattering and deformation of the curable resin composition in the washing shower process and coating workability.

Furthermore, the present inventors believe that the addition of an inorganic filler is important in order to increase the shear rate dependence of the viscosity of the curable resin composition, and the more the amount of the inorganic filler added, the more the curable resin composition. independently found that the shear rate dependence of the viscosity of However, as described above, the more the inorganic filler additive in the curable resin composition, the lower the impact resistance peel adhesion of the curable resin composition.

Conventionally, it has been recognized that providing a cured product with excellent impact peel adhesiveness and providing a curable resin composition with excellent shear rate dependence of viscosity are independent tasks. For example, in Patent Document 1, peel adhesion and impact-resistant peel adhesion are the subjects, and a composition obtained by adding surface-treated heavy calcium carbonate to a curable resin composition containing an epoxy resin and core-shell polymer fine particles. is exemplified. However, the shear rate dependency of the viscosity of the curable resin composition is not addressed, and no means for improving the shear rate dependency of the viscosity is taught. Further, in Patent Document 2, it is a subject to achieve both the shear rate dependence of viscosity and storage stability, and a technique of adding colloidal calcium carbonate to a curable resin composition containing an epoxy resin and core-shell polymer fine particles is disclosed. disclosed. However, impact peel adhesion is not addressed and no means of improving impact peel adhesion is taught.

Therefore, the present inventor set a new problem of providing a curable resin composition that can provide a cured product having excellent shear rate dependency of viscosity and excellent impact resistance to peeling adhesion.

In order to solve the above problems, the present inventors have made intensive studies on the types of calcium carbonate and the types of calcium carbonate surface treatment agents to be added to a curable resin composition containing an epoxy resin and fine polymer particles. perfected the invention.

[2. Curable resin composition]
Hereinafter, the curable resin composition according to one embodiment of the present invention will be described in detail.

The curable resin composition according to one embodiment of the present invention comprises 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), and silane coupling Contains 10 to 150 parts by mass of colloidal calcium carbonate (C) surface-treated with an agent. The fine polymer particles (B) contain a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body. "Curable resin composition according to one embodiment of the present invention", "epoxy resin (A)", "polymer fine particles (B)" and "Collective calcium carbonate surface-treated with a silane coupling agent (C)" , hereinafter, they may also be referred to as "main curable resin composition", "(A) component", "(B) component" and "(C) component", respectively. The curable resin composition can provide a cured product by curing the curable resin composition.

Since the present curable resin composition has the above structure, it is excellent in shear rate dependence of viscosity. In this specification, the shear rate dependence of viscosity is evaluated by the ratio of the viscosity at a shear rate of 5 s ⁻¹ to the viscosity at a shear rate of 50 s ⁻¹ . A method for measuring the viscosity will be described in detail in Examples.

Since the present curable resin composition has the above structure, it has the advantage of being able to provide a cured product having excellent impact resistance peel adhesion. In this specification, the impact resistance peel adhesion of the cured product is evaluated by the value of dynamic splitting resistance (kN/m) at 23°C and -40°C. A method for measuring the dynamic splitting resistance (kN/m) will be described in detail in Examples.

Although the reason why the cured product obtained by curing the present curable resin composition has excellent impact resistance peeling adhesion is not clear, it is presumed as follows.

Due to the toughness-improving effect of the fine polymer particles (B) contained in the curable resin composition, the cured product obtained by curing the curable resin composition is excellent in toughness and impact-resistant peel adhesion. However, an inorganic filler such as colloidal calcium carbonate used in combination with the polymer fine particles (B) is likely to cause cracks due to peeling at the interface between the epoxy resin (A), which is the matrix resin, and the inorganic filler. Therefore, the toughness of the obtained cured product is lowered due to the progress of the cracks. The silane coupling agent of the surface treatment agent used for component (C), which is a feature of one embodiment of the present invention, has two or more different reactive groups in the molecule. The silane coupling agent of the surface treatment agent has at least a silyl group that is a reactive group that chemically bonds with an inorganic material and an organic group that is a reactive group that chemically bonds with an organic material. Component (C) according to one embodiment of the present invention strongly binds to epoxy resin (A), which is a matrix resin, through the silane coupling agent of the surface treatment agent, and as a result, component (A) and component (C) It is presumed that the deterioration of the toughness of the cured product due to the extension of cracks at the interface with the component hardly occurs. The present invention is not limited to this reason (estimation).

(Epoxy resin (A))
It can also be said that the present curable resin composition contains the epoxy resin (A) as a main component. In this specification, the "epoxy resin (A)" is also referred to as "(A) component".

Various epoxy resins can be used as the epoxy resin (A). Examples of the epoxy resin (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, novolac type 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 esters of aliphatic polybasic acids, glycidyl ethers of dihydric or higher polyhydric aliphatic alcohols such as glycerin , chelate-modified epoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, hydantoin-type epoxy resins, epoxidized unsaturated polymers such as petroleum resins, aminoglycidyl ether resins, and bisphenol A in these epoxy resins. (or F) or epoxy compounds obtained by addition reaction of polybasic acids and the like are exemplified. The epoxy resin (A) is not limited to these, and commonly used epoxy resins can be used.

Examples of the polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of the aliphatic polybasic acid, and the glycidyl ether of the dihydric or higher polyhydric aliphatic alcohol include, for example, WO2016-163491. The resin described in paragraphs [0015] to [0017] of the specification can be used. These epoxy resins are epoxy resins with relatively low viscosities. When these epoxy resins are used in combination with other epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, these epoxy resins can function as reactive diluents. As a result, these epoxy resins 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 contain an epoxy resin that can function as a reactive diluent.

Examples of epoxy compounds obtained by addition reaction of polybasic acids and the like to epoxy resins include, for example, tall oil fatty acid dimer (dimer acid) and bisphenol A type epoxy, as described in WO2010-098950. An addition reaction product with a resin can be mentioned.

As the chelate-modified epoxy resin, for example, resins described in paragraphs [0018] to [0019] of the specification of WO2016-163491 can be used.

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, resins described in paragraphs 0133 to 0135 of the specification of WO2016-163491 can be used.

A rubber-modified epoxy resin or a urethane-modified epoxy resin can further improve properties such as toughness, impact resistance, shear adhesion and peel adhesion of the resulting cured product.

Among the epoxy resins described above, those having at least two epoxy groups in one molecule are preferred because they have high reactivity when cured and the resulting cured product can easily form a three-dimensional network.

One of the epoxy resins described above may be used alone, or two or more thereof may be used in combination.

Among the epoxy resins described above, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable because they have a high elastic modulus and give a cured product having excellent heat resistance and adhesiveness, and are relatively inexpensive. type epoxy resins are particularly preferred.

Among the epoxy resins described above, epoxy resins having an epoxy equivalent of less than 220 are preferable because the elastic modulus and heat resistance of the resulting cured product are high. Among the epoxy resins described above, epoxy resins having an epoxy equivalent of 90 or more and less than 210 are more preferable, and epoxy resins having an epoxy equivalent of 150 or more and less than 200 are even more preferable.

In particular, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins having an epoxy equivalent of less than 220 are preferred because they are liquid at room temperature and the resulting curable resin composition is easy to handle.

A bisphenol A type epoxy resin and a bisphenol F type epoxy resin having an epoxy equivalent of 220 or more and less than 5000 are added in an amount of preferably 40% by mass or less, more preferably 20% by mass or less, based on 100% by mass of component (A). is preferred. According to the above configuration, there is an advantage that the resulting cured product has excellent impact resistance.

<Polymer fine particles (B)>
The curable resin composition according to one embodiment of the present invention is a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body, based on 100 parts by mass of component (A). Contains 1 to 100 parts by mass of polymer fine particles (B) containing Due to the toughness-improving effect of component (B), the resulting cured product is excellent in toughness and impact peel adhesion.

From the balance between the ease of handling of the resulting curable resin composition and the effect of improving the toughness of the resulting cured product, the amount of component (B) is preferably 1 to 100 parts by mass with respect to 100 parts by mass of component (A). 70 parts by weight is more preferred, 5 to 50 parts by weight is even more preferred, and 10 to 40 parts by weight is particularly preferred.

The volume average particle diameter (Mv) of the polymer fine particles (B) is not particularly limited, but considering 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 100 nm to 200 nm. is particularly preferred. According to the above configuration, there is also the advantage that a highly stable resin composition having a desired viscosity can be obtained. In this specification, the "volume average particle size (Mv) of the polymer fine particles (B)" means the volume average particle size 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 by using an aqueous latex containing the polymer fine particles (B) as a sample, and using a dynamic light scattering particle size distribution analyzer (for example, Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.)). can be measured using A method for measuring the volume average particle size of the polymer microparticles (B) will be described in detail in Examples below. In addition, the volume average particle diameter of the polymer fine particles (B) is obtained by cutting the cured product of the curable resin composition, imaging the cut surface using an electron microscope or the like, and using the obtained imaging data (captured image). can also be measured.

In the curable resin composition according to one embodiment of the present invention, the component (B) has a half 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. is preferable because the resulting curable resin composition has a low viscosity and is easy to handle.

From the viewpoint of easily realizing the specific particle size distribution described above, it is preferable that there are two or more maximum values in the number distribution of the volume average particle size of the component (B). , more preferably 2 to 3 maxima, and more preferably 2 maxima. Component (B) particularly contains 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% by mass of polymer fine particles (B) having a volume average particle size of 150 nm or more to 2000 nm or less. is preferred.

Component (B) is preferably dispersed in the form of primary particles in the curable resin composition. In one embodiment of the present invention, "the polymer fine particles (B) are dispersed in the curable resin composition in the form of primary particles" (hereinafter also referred to as primary dispersion) means the polymer fine particles (B) It means that they are substantially independently dispersed (without contact), and the dispersed state is obtained by, for example, dissolving a part of the curable resin composition in a solvent such as methyl ethyl ketone and dynamically It can be confirmed by measuring the volume average particle size (Mv)/number average particle size (Mn) of the fine polymer particles (B) with a light scattering type particle size distribution analyzer or the like.

The value of volume average particle size (Mv)/number average particle size (Mn) by particle size measurement is not particularly limited, but is preferably 3 or less, more preferably 2.5 or less, and still more preferably 2 or less. , 1.5 or less are particularly preferred. If the volume average particle size (Mv)/number average particle size (Mn) is 3 or less, it is considered that the particles are well dispersed. Conversely, when the curable resin composition has a particle size distribution of more than 3, the resulting cured product may have poor physical properties such as impact resistance and adhesiveness.

The volume average particle size (Mv)/number average particle size (Mn) is obtained by measuring the volume average particle size (Mv) and the number average particle size (Mn) using Microtrac UPA (manufactured by Nikkiso Co., Ltd.). , Mv by Mn.

Further, the "stable dispersion" of the polymer fine particles (B) means that the polymer fine particles (B) do not agglomerate, separate, or precipitate in the continuous layer, and are constantly dispersed under normal conditions. means a state of being dispersed over a long period of time. In addition, the distribution of the fine polymer particles (B) in the continuous layer does not substantially change, and the viscosity of the continuous layer can be increased by heating the continuous layer (for example, the curable resin composition) within a safe range. It is preferable that the "stable dispersion" of the fine polymer particles (B) is maintained even when the mixture is lowered and stirred.

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 includes diene rubber and (meth)acrylate rubber. and polysiloxane rubber-based elastic bodies. Elastic bodies can also be called rubber particles. (Meth)acrylate as used herein means acrylate and/or methacrylate. A polysiloxane rubber-based elastic body may also be referred to as an organosiloxane-based rubber.

(a) the effect of improving the toughness of the resulting cured product is high, and (b) the affinity with the matrix resin (e.g., epoxy resin (A)) is low, resulting in swelling of the elastic body in the resulting curable resin composition. The elastic body preferably contains a diene-based rubber, more preferably a diene-based rubber, because the viscosity is less likely to increase over time. 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.

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

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

Examples of vinyl-based monomers other than diene-based monomers copolymerizable with diene-based monomers (hereinafter also referred to as vinyl-based monomers A) include vinyl arenes such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene. vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; ethylene, propylene, butylene, isobutylene, etc. and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The vinyl-based monomers other than the diene-based monomers described above may be used alone or in combination of two or more. Among the vinyl-based monomers other than the diene-based monomers described above, styrene is particularly preferable.

The elastic body is preferably butadiene rubber and/or butadiene-styrene rubber, more preferably butadiene rubber. The butadiene rubber is 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 configuration, (a) the advantage that the toughness improving effect of the obtained cured product is higher, and (b) the affinity with the matrix resin (for example, the epoxy resin (A)) is lower. It has the advantage that the viscosity of the resin composition is less likely to increase over time due to swelling of the elastic body. In addition, butadiene-styrene rubber is more preferable in that the transparency of the resulting cured product can be enhanced by adjusting the refractive index.

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

The (meth)acrylate rubber is an elastic body containing 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 (meth)acrylate monomers in 100% by mass of structural units, and can be copolymerized with (meth)acrylate monomers. It may contain 0 to 50% by mass of constitutional units derived from vinyl-based monomers other than (meth)acrylate-based monomers. In Case B, the (meth)acrylate-based rubber may contain structural units derived from diene-based monomers as structural units in an amount smaller than the structural units derived from (meth)acrylate-based monomers.

(Meth)acrylate monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl Alkyl (meth)acrylates such as (meth)acrylate and behenyl (meth)acrylate; Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate , hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate; glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidylalkyl (meth)acrylate; alkoxyalkyl (meth)acrylates; allyl ( arylalkyl (meth)acrylates such as meth)acrylate and allylalkyl (meth)acrylate; (meth)acrylates and the like. 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.

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

When trying to improve the impact resistance of the cured product at low temperatures without lowering the heat resistance of the resulting cured product, the elastic body preferably contains a polysiloxane rubber-based elastic body. More preferably, it is an elastic body. A case (Case C) where the elastic body contains a polysiloxane rubber-based elastic body will be described below.

Examples of polysiloxane rubber-based elastic bodies include (a) composed of disubstituted alkyl or aryl silyloxy units such as dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy, etc. (b) a polysiloxane polymer composed of alkyl or aryl monosubstituted silyloxy units such as organohydrogensilyloxy in which a portion of the side chain alkyl is substituted with a hydrogen atom; is mentioned. These polysiloxane-based polymers may be used alone or in combination of two or more. Among these polysiloxane-based polymers, the curable resin composition obtained from (a) can provide a cured product having excellent heat resistance. Polymers composed of silyloxy-diphenylsilyloxy units are preferred, and (b) polymers composed of dimethylsilyloxy units are most preferred due to their ready availability and economics.

In case C, the polymer microparticles (B) preferably contain 80% by mass or more, more preferably 90% by mass or more, of the polysiloxane rubber-based elastic material in 100% by mass of the elastic material contained in the polymer microparticles (B). It is more preferable to have According to the configuration, the obtained curable resin composition can provide a cured product having 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-based rubbers, (meth)acrylate-based rubbers, and polysiloxane rubber-based elastic bodies include natural rubbers.

(Crosslinked structure of elastic body)
From the viewpoint of maintaining the dispersion stability of the polymer fine particles (B) in the curable resin composition, it is preferable that a crosslinked structure is introduced into the elastic body. As a method for introducing a crosslinked structure into the elastic body, a generally used method can be adopted, and examples thereof include the following methods. That is, in the production of the elastic body, a method of mixing a cross-linkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound with a monomer capable of constituting the elastic body, and then polymerizing the monomers. In this specification, manufacturing a polymer such as an elastomer is also referred to as polymerizing the polymer.

Methods for introducing a crosslinked structure into a polysiloxane rubber-based elastic body include the following methods: (a) when polymerizing a polysiloxane rubber-based elastic body, a polyfunctional alkoxysilane compound is (b) introducing a reactive group such as a vinyl reactive group or a mercapto group into a polysiloxane rubber elastomer, and then adding a vinyl polymerizable monomer or an organic peroxide; or (c) mixing a cross-linkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound with other materials when polymerizing a polysiloxane rubber-based elastomer, and then polymerizing how to do, etc.

A polyfunctional monomer can also be said to be a monomer having two or more radically polymerizable reactive groups in the same molecule. Said radically polymerizable reactive group is preferably a carbon-carbon double bond. Polyfunctional monomers include ethylenically unsaturated double bonds such as allyl(meth)acrylate, allylalkyl(meth)acrylates such as allylalkyl(meth)acrylates, and allyloxyalkyl(meth)acrylates. (Meth)acrylates having 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. 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, and the like. are exemplified. Further, as monomers having three (meth)acrylate groups, alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl) Examples include isocyanurate tri(meth)acrylate. Alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate and trimethylolpropane triethoxytri(meth)acrylate. Furthermore, examples of monomers having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, dipentaerythritol penta(meth)acrylate etc. are illustrated as a monomer which has five (meth)acrylic groups. Furthermore, examples of monomers having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Multifunctional monomers also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like. Among these, allyl methacrylate, triallyl isocyanurate, butanediol di(meth)acrylate, and divinylbenzene are particularly preferred as polyfunctional monomers.

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

(Gel content of elastic body)
The elastic body of the fine polymer particles (B) preferably has rubber properties in order to increase the toughness of the resulting cured product of the curable resin composition. Preferably, the elastomer is swellable in a suitable solvent, but substantially insoluble. An elastic body is preferably unnecessary for the thermosetting resin (B) used.

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

In the present specification, the method for calculating the 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. Specifically, the method for obtaining the powder of the polymer fine particles (B) from the aqueous latex includes (i) coagulating the polymer fine particles (B) in the aqueous latex, (ii) dehydrating the resulting aggregate, (iii) A method of obtaining a powder of fine polymer particles (B) by further drying the aggregates. Then, 0.5 g of fine polymer particles (B) powder is immersed in 100 g of toluene. The resulting mixture is then allowed to stand at 23° C. for 24 hours. Thereafter, the resulting mixture is separated into toluene-soluble components (toluene-soluble components) and toluene-insoluble components (toluene-insoluble components). The masses of the obtained toluene-soluble matter and toluene-insoluble matter 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 (hereinafter sometimes simply referred to as “Tg”) of the elastic body is preferably 0° C. or lower, more preferably −20° C. or lower, in order to increase the toughness of the resulting cured product. 40° C. or lower is more preferable, and −60° C. or lower is particularly preferable.

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

The Tg of the elastic body can be determined by the composition of the constituent units contained in the elastic body. In other words, the Tg of the resulting elastomer can be adjusted by changing the composition of the monomers used in manufacturing (polymerizing) the elastomer.

Here, a group of monomers that provide a homopolymer having a Tg of greater than 0° C. when only one type of monomer is polymerized is defined as monomer group a. Further, a group of monomers that provide a homopolymer having a Tg of less than 0° C. when polymerized from only one type of monomer is defined as a monomer group b. Polymers having a Tg of greater than 0° C. and capable of forming an elastic body capable of suppressing 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 Polymers containing 0 to 50% by mass (more preferably 1 to 35% by mass) of structural units that

Even when the Tg of the elastic body is higher than 0° C., it is preferable that the elastic body has a crosslinked structure. Methods for introducing the crosslinked structure include the methods described above.

Examples of monomers that can be included in the monomer group a include, but are not limited to, unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; vinyl-substituted aromatic compounds such as α-methylstyrene; ; ring-alkylated vinyl aromatic compounds such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene and 2,4,6-trimethylstyrene; ; ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; ring ester substitution such as 4-acetoxystyrene vinyl aromatic compounds; ring-hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; Aromatic monomers; Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and isopropyl methacrylate; Aromatic methacrylates such as phenyl methacrylate; Methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; monomers; certain acrylic acid esters such as isobornyl acrylate, tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile; Further, monomers that can be included in the monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl acrylate and 1 -Adamantyl methacrylate, etc., which can provide a homopolymer having a Tg of 120° C. or higher when converted into a homopolymer. Examples of monomers that can be included in the monomer group a include various compounds described in paragraph [0084] of the specification of WO2014-196607. These monomers a may be used alone or in combination of two or more.

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

(Volume average particle size of elastic body)
The volume average particle size 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 diameter of the elastic body is (a) 0.03 μm or more, an elastic body having a desired volume average particle diameter can be stably obtained. Good heat resistance and impact resistance. The volume average particle size of the elastic body can be measured by using an aqueous latex containing the elastic body as a sample and using a dynamic light scattering particle size distribution analyzer or the like. A method for measuring the volume average particle size of the elastic body will be described in detail in Examples below.

(Proportion (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, more preferably 70 to 93% by mass, based on 100% by mass of the polymer microparticles (B) as a whole. Preferably, 80 to 90 mass % is particularly preferred. When the proportion of the elastic body is (a) 40% by mass or more, there is no fear that the effect of improving the toughness of the cured product of the curable resin composition obtained is reduced, and (b) when it is 97% by mass or less, Since the fine polymer particles (B) are unlikely to aggregate, the curable resin composition does not become highly viscous, and as a result, the resulting curable resin composition can be easy to handle.

(Modified example of elastic body)
In one embodiment of the present invention, the elastic body is one selected from the group consisting of diene rubber, (meth)acrylate rubber and polysiloxane rubber, and has structural units of the same composition. It may consist of only one type of elastic body. In one embodiment of the present invention, the elastic body may consist of a plurality of types of elastic bodies having structural units with different compositions.

In one embodiment of the present invention, a case where the elastic body is composed of a plurality of types of elastic bodies will be described. In this case, each of the plurality of types of elastic bodies is defined as elastic body ₁ , elastic body ₂ , . . . , and elastic body _n . Here, n is an integer of 2 or more. The elastomer may comprise a mixture obtained by mixing each separately polymerized elastomer _{1 1} , elastomer _{2 2} , . . . , and elastomer _n . The elastic body may contain a polymer obtained by polymerizing elastic body ₁ , elastic body ₂ , . . . , and elastic body _n in order. Such polymerization of a plurality of polymers (elastic bodies) in order is also called multistage polymerization. A polymer obtained by multistage polymerization of a plurality of kinds of elastic bodies is also called a multistage polymerized elastic body. A method for producing the multi-stage polymer elastic body will be described in detail later.

A multistage polymerized elastic body composed of elastic body ₁ , elastic body ₂ , . . . , and elastic body _n will be described. In the multi-stage polymer elastic body, the elastic body _n may cover at least a portion of the elastic body _n-1 , or may cover the entirety of the elastic body _n-1 . In the multi-stage polymerized elastic body, part of the elastic body _n may be inside the elastic body _n-1 .

In the multi-stage polymer elastic body, each of the plurality of elastic bodies may have a layered structure. For example, when the multi-stage polymerized elastic body is composed of elastic bodies ₁ , ₂ , and ₃ , elastic body ₁ is the innermost layer, elastic body 2 is present outside elastic body ₁ , and elastic body ₂ is the outermost layer. A mode in which a layer of the elastic body ₃ exists as the outermost layer of the elastic body on the outer side of the _{layer 2} is also one mode of the present invention. Thus, a multi-stage polymerized elastic body in which each of a plurality of elastic bodies has a layered structure can also be called a multi-layered 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 multi-stage polymerized elastic body and/or a multi-layered elastic body.

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

Since the compatibility and dispersibility of the component (B) in the curable resin composition are improved, the graft portion is composed of aromatic vinyl monomers, vinyl cyanide monomers and (meth)acrylate monomers as structural units. It is preferably a polymer containing a structural unit derived from one or more selected monomers, and more preferably a polymer containing a structural unit derived from a (meth)acrylate monomer.

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

The content of the cyano group with respect to the total mass of the graft portion of the 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 cured product obtained by curing are good. Therefore, it is preferably 0.5 mmol/g to 15 mmol/g, more preferably 1 mmol/g to 13 mmol/g, still more preferably 2 mmol/g to 11 mmol/g, and particularly preferably 3 mmol/g to 9 mmol/g. When the content of the cyano group with respect to the total mass of the graft portion of the component (B) is 0.5 mmol/g or more (a), the temperature dependence of the viscosity of the resulting curable resin composition is reduced. If (b) it is 15 mmol/g or less, there is no possibility that the amount of the cyano group-containing monomer remaining in the fine polymer particles (B) will increase, resulting in an advantage of high safety.

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, butyl (meth)acrylate; and (b) hydroxyethyl (meth) and hydroxyalkyl (meth)acrylates such as acrylates and hydroxybutyl (meth)acrylate.

Of the one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and (meth)acrylate monomers, only one type may be used, or two or more types may be used in combination. good too.

In the graft portion, as structural units, a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyanide monomer, and a structural unit derived from a (meth)acrylate monomer are totaled, and in 100% by mass of all structural units, It preferably contains 10 to 95% by mass, more preferably 30 to 92% by mass, more preferably 50 to 90% by mass, particularly preferably 60 to 87% by mass, and 70 to 85% by mass. is most preferred.

The graft portion preferably contains, as a structural unit, a structural unit derived from a reactive group-containing monomer. The reactive group-containing monomer is a group consisting of an epoxy group, a hydroxy 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. It is preferably a monomer containing one or more reactive groups selected from, and is a monomer containing one or more reactive groups selected from the group consisting of epoxy groups, hydroxy groups and carboxylic acid groups. is more preferred, and a monomer containing an epoxy group is even more preferred. According to the above configuration, the grafted portion of the fine polymer particles (B) and the epoxy resin (A) can be chemically bonded in the curable resin composition and its cured product. Thereby, the fine polymer particles (B) can be maintained in a good dispersed state without aggregating the fine polymer particles (B) in the curable resin composition or the cured product thereof. That is, the graft portion is preferably a polymer having an epoxy group. Moreover, the graft portion is preferably a polymer containing, as a structural unit, a structural unit derived from a monomer having an epoxy group.

The graft portion is a polymer having an epoxy group, and the content of the epoxy group relative to the mass of the graft portion is preferably 0.1 mmol/g to 5.0 mmol/g, more preferably 0.2 mmol/g to 3.5 mmol. /g, more preferably 0.3 mmol/g to 3.0 mmol/g, particularly preferably 0.4 mmol/g to 2.5 mmol/g. According to this configuration, the resulting curable resin composition has the advantages of excellent temperature dependency of viscosity and excellent storage stability. The content of epoxy groups with respect to the mass of the graft portion can also be said to be the content of epoxy groups with respect to the total mass of the graft portion of component (B).

Specific examples of epoxy group-containing monomers 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 a hydroxy group include 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); caprolactone-modified hydroxy (meth)acrylate; hydroxy-branched alkyl (meth)acrylate such as α-(hydroxymethyl)methyl acrylate and α-(hydroxymethyl)ethyl acrylate; hydroxyl group-containing (meth)acrylates such as mono(meth)acrylates of polyester diols (especially saturated polyester diols) obtained from dihydric carboxylic acids (phthalic acid, etc.) and dihydric alcohols (propylene glycol, etc.); be done.

Specific examples of monomers having a carboxylic acid group 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 is preferably used.

Only one type of the above-described reactive group-containing monomer may be used, or two or more types may be used in combination.

The graft portion preferably contains 0.5 to 90% by mass, more preferably 1 to 50% by mass, and 2 to 35% by mass of a structural unit derived from a reactive group-containing monomer in 100% by mass of the graft portion. %, and particularly preferably 3 to 20% by mass. When the graft portion contains (a) 0.5% by mass or more of a structural unit derived from a reactive group-containing monomer in 100% by mass of the graft portion, the resulting curable resin composition has sufficient resistance. It is possible to provide a cured product having impact resistance, and when the content of (b) is 90% by mass or less, the resulting curable resin composition can provide a cured product having sufficient impact resistance. And, it has the advantage that the storage stability of the curable resin composition is improved.

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 a structural unit derived from a polyfunctional monomer as a structural unit. When the graft portion contains a structural unit derived from a polyfunctional monomer, (a) swelling of the polymer fine particles (B) in the curable resin composition can be prevented, and (b) the curable resin composition Since the viscosity is lowered, the curable resin composition tends to be easier to handle, and (c) the dispersibility of the polymer fine particles (B) in the thermosetting resin (B) is improved. have.

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 excellent in the effect of improving the toughness of the cured product and the effect of improving the impact peel adhesion resistance of the cured product.

Multifunctional monomers that can be used to polymerize the graft include the same multifunctional 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, 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. Only one type of these polyfunctional monomers may be used, or two or more types may be used in combination.

The graft portion may contain 0 to 20% by mass, preferably 1 to 20% by mass, and 5 to 15% by mass of a structural unit derived from a polyfunctional monomer in 100% by mass of the graft portion. is more preferred.

The graft part, in 100% by mass of all structural units as a structural unit, is preferably 0 to 50% by mass (more preferably 1 to 50% by mass, more preferably 1 to 50% by mass, more preferably 2 to 48% by mass), 0 to 50% by mass (more preferably 0 to 30% by mass, more preferably 10 to 25% by mass) of structural units derived from a vinyl cyanide monomer (especially acrylonitrile), (meth)acrylate monomer ( 0 to 90% by mass (more preferably 5 to 85% by mass, more preferably 20 to 80% by mass) of structural units derived from (especially methyl methacrylate), a monomer having an epoxy group (especially glycidyl methacrylate) derived from structural unit 5 90% by mass (more preferably 10 to 50% by mass, more preferably 15 to 30% by mass), totaling 100% by mass. According to this configuration, a curable resin composition having low temperature dependence of viscosity can be obtained.

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

The graft portion may contain, as structural units, structural units derived from other monomers in addition to the structural units derived from the monomers described above.

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

In the present specification, the ratio of the polymer graft-bonded to the elastic body, that is, the graft portion, out of the polymer produced in the polymerization of the graft portion is referred to as the graft rate. The graft ratio can also be said to be a value represented by (mass of grafted portion)/(mass of grafted portion)+(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 the present 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. As a method for obtaining a powder of fine polymer particles (B) from an aqueous latex, the method described in the section (Gel content of elastic body) can be used. 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). The resulting mixture is then allowed to stand at 23° C. for 24 hours. The resulting mixture is then separated into components soluble in MEK (MEK solubles) and components insoluble in MEK (MEK insolubles). Furthermore, the methanol-insoluble matter is separated from the MEK-soluble matter by, for example, mixing the MEK-soluble matter with methanol. Then, the weights of the obtained MEK-insoluble matter and methanol-insoluble matter are measured, and the ratio of the MEK-insoluble matter to the total amount of the MEK-insoluble matter and the methanol-insoluble matter is calculated to calculate the graft ratio. Specifically, the graft rate is calculated by the following formula.
Graft 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 present invention, the graft portion may consist of only one type of graft portion having structural units of the same composition. In one embodiment of the present invention, the graft portion may consist of a plurality of types of graft portions each having a different composition of structural units.

In one embodiment of the present invention, a case where the graft portion is composed of a plurality of types of graft portions will be described. In this case, each of the plurality of types of graft portions is designated as graft portion ₁ , graft portion ₂ , . . . , graft portion _n (n is an integer of 2 or more). The graft portion may comprise a mixture obtained by mixing separately polymerized graft portion _{1 1} , graft portion ₂ , . . . , and graft portion _n . The graft portion may contain a polymer obtained by multistage polymerization of the graft portion _{1 1} , the graft portion _{2 2} , . . . , and the graft portion _n . A polymer obtained by multistage polymerization of a plurality of types of graft portions is also referred to as a multistage polymerization graft portion. A method for producing the multistage polymerized graft portion will be described in detail later.

When the graft portion is composed of multiple types of graft portions, not all of these multiple types of graft portions may be graft-bonded to the elastic body. At least a part of at least one type of graft portion may be graft-bonded to the elastic body, and other types (a plurality of other types) of graft portions are graft portions that are graft-bonded to the elastic body. may be grafted to. In addition, when the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers that are polymers having the same configuration as the plurality of types of graft portions and are not graft-bonded to the elastic body (non-graft polymer ).

A multistage polymerized graft portion composed of graft portion ₁ , graft portion ₂ , . . . , and graft portion _n will be described. In the multi-stage polymerized graft portion, the graft portion _n may cover at least a portion of the graft portion _n-1 , or may cover the entirety of the graft portion _n-1 . In the multi-stage polymerized graft portion, a portion of the graft portion _n may enter the inside of the graft portion _n−1 .

In the multi-stage polymerized graft portion, each of the plurality of graft portions may have a layered structure. For example, when the multistage polymerized graft portion is composed of graft portion ₁ , graft portion ₂ , and graft portion ₃ , graft portion ₁ is the innermost layer in the graft portion, and graft portion ₂ is present outside graft portion ₁ , Furthermore, an aspect in which the layer of the graft portion ₃ exists as the outermost layer outside the layer of the graft portion ₂ is also one aspect of the present invention. Thus, a multi-stage polymerized graft portion in which each of a plurality of graft portions has a layered structure can also be called a multi-layer graft portion. That is, in one embodiment of the present invention, the graft portion may include a mixture of graft portions, a multi-stage polymerization graft portion and/or a multi-layer graft portion.

When the elastic body and the graft portion are polymerized in this order in the production of the polymer microparticles (B), at least a portion of the graft portion may cover at least a portion of the elastic body in the resulting polymer microparticles (B). In other words, the elastic body and the graft portion are polymerized in this order, which means that the elastic body and the graft portion are polymerized in multiple stages. The fine polymer particles (B) obtained by multi-stage polymerization of the elastic body and the graft portion can also be said to be a multi-stage polymer.

When the polymer fine particle (B) is 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 particle (B) is a multi-stage polymer, a part of the graft part may enter the inside of the elastic body.

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

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

(Surface cross-linked polymer)
The fine polymer particles (B) preferably have a surface-crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. According to the above configuration, (a) in the production of the polymer fine particles (B), the blocking resistance can be improved, and (b) the polymer fine particles (B) have better dispersibility in the thermosetting resin (B). becomes. These reasons are not particularly limited, but can be presumed as follows: by covering at least a part of the elastic body with the surface cross-linked polymer, the exposure of the elastic part of the fine polymer particles (B) is reduced, As a result, the elastic bodies are less likely to stick to each other, thereby improving the dispersibility of the fine polymer particles (B).

When the fine polymer particles (B) have a surface-crosslinked polymer, the following effects can also be obtained: (a) the effect of lowering the viscosity of the curable resin composition, and (b) the effect of increasing the crosslink density in the elastic body. and (c) the effect of increasing the graft efficiency of the graft. The crosslink density in the elastic body means the degree of the number of crosslinked structures in the whole elastic body.

The fine polymer particles (B) preferably do not contain a surface-crosslinked polymer because the resulting cured product is excellent in toughness and impact-resistant peel adhesion.

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

Multifunctional monomers that can be used to polymerize the surface-crosslinked polymer include the same multifunctional monomers described above. Among these polyfunctional monomers, polyfunctional monomers that can be preferably used for polymerization of the surface-crosslinked polymer include allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, 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.

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 fine polymer particles (B) may be a multi-stage polymer obtained by multi-stage 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 can cover at least a portion of the elastic body.

Surface cross-linked polymers can also be considered part of the elastomer. 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) to the surface-crosslinked polymer. It may be graft-bonded, or (c) it may be graft-bonded to both an elastic body other than the surface-crosslinked polymer and the surface-crosslinked polymer. When the fine polymer particles (B) contain a surface-crosslinked polymer, the volume-average particle diameter of the elastic body mentioned above means the volume-average particle diameter of the elastic body containing the surface-crosslinked polymer.

A case (Case D) in which the fine polymer particles (B) are a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface-crosslinked polymer, and a graft portion in this order will be described. In Case D, the surface cross-linked polymer may cover a portion of the elastic or may cover the entire elastic. In case D, part of the surface-crosslinked polymer may be embedded inside the elastic body. In Case D, the graft portion may cover a portion of the surface cross-linked polymer or may cover the entire surface cross-linked polymer. In Case D, part of the graft portion may be embedded inside the surface-crosslinked polymer. In Case D, the elastic body, the surface-crosslinked polymer and the 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 outside the elastic body, and the graft portion layer is the outermost layer (shell layer) outside the surface-crosslinked polymer. The present aspect is also an aspect of the invention.

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

Polymer microparticles (B) can be produced by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. Specifically, polymerization of the elastic body, polymerization of the graft portion (graft polymerization), and polymerization of the surface-crosslinked polymer in the fine polymer particles (B) are performed by known methods such as emulsion polymerization, suspension polymerization, and microsuspension polymerization. It can be manufactured by the method of Among these, in particular, an aqueous latex of the polymer fine particles (B), which facilitates compositional design of the polymer fine particles (B), facilitates industrial production, and can be suitably used in the production of the present resin composition, is easily obtained. Therefore, emulsion polymerization is preferable as the method for producing the polymer fine particles (B). The method for producing the elastic body, the graft portion, and the surface-crosslinked polymer having any configuration that can be contained in the fine polymer particles (B) will be described below.

(Manufacturing method of elastic body)
Consider the case where the elastic body contains at least one selected from the group consisting of diene-based rubbers and (meth)acrylate-based rubbers. In this case, the elastic body can be produced, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. .

Consider a case where the elastic body includes a polysiloxane rubber-based elastic body. In this case, the elastic body can be produced, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. .

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

A specific description will be given of the multi-stage polymerization of the elastic body. For example, (1) elastic ₁ is polymerized to obtain elastic ₁ ; (2) elastic ₂ is then polymerized in the presence of elastic 1 to obtain a two-step elastic _{1+2 ;} Polymerize elastic ₃ in the presence of body ₁₊₂ to obtain three-stage elastic 1 _{+2+ 3} ; The elastic body _n is polymerized to obtain a multistage polymerized elastic body _{1+2+ . . . +n} .

(Manufacturing method of graft portion)
The graft portion can be formed, for example, by polymerizing a monomer 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 the 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.

A method of manufacturing a graft portion when the graft portion is composed of a plurality of types of graft portions (for example, graft portion _{1 1} , graft portion _{2 2} , . . . , graft portion _{n 2} ) will be described. In this case, the graft portion ₁ , the graft _{portion 2} , . good too. Alternatively, the graft portion _{1 1} , the graft portion _{2 2 ,} .

The multi-stage polymerization of the graft portion will be specifically described. For example, (1) graft section ₁ is polymerized to obtain graft section ₁ ; (2) graft section ₂ is then polymerized in the presence of graft section ₁ to obtain a two-step graft section ₁₊₂ ; (3) graft section is then grafted. Polymerize the graft portion ₃ in the presence of the portion ₁₊₂ to obtain a three-stage graft portion _{1+2+ 3} ; The graft portion _n is polymerized to obtain a multistage polymerized graft portion _{1+2+ . . . +n} .

When the graft portion is composed of a plurality of types of graft portions, the polymer fine particles (B) may be produced by polymerizing the graft portions having a plurality of types of graft portions and then graft-polymerizing the graft portions onto the elastic body. The polymer microparticles (B) may be produced by sequentially performing multistage graft polymerization of a plurality of types of polymers forming a plurality of types of graft portions on the elastic body in the presence of the elastic body.

(Method for producing surface-crosslinked polymer)
A surface-crosslinked polymer can be formed by polymerizing a monomer used for forming the surface-crosslinked polymer by known radical polymerization. When the elastic body is obtained as an aqueous latex, the polymerization of the surface-crosslinked polymer is preferably carried out by an emulsion polymerization method.

The surface-crosslinked polymer is produced by adding a monomer used for forming the surface-crosslinked polymer to an aqueous latex containing a polymerized elastic body at once, or continuously adding a constant amount of the monomer, and then polymerizing the monomer. may be obtained. Such polymerization can also be said to be polymerization of a surface-crosslinked polymer carried out in one step. Polymerization of the surface-crosslinked polymer may be carried out in two or more steps. That is, it is also possible to employ a method in which an aqueous latex containing a polymerized elastic body is added to a reactor in which the monomers used for forming the surface-crosslinked polymer are charged in advance, and then the polymerization is carried out.

(emulsifier)
When the emulsion polymerization method is adopted as the method for producing the polymer fine particles (B), a known emulsifier can be used for the production of 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 singly or in combination of two or more. An emulsifier can also be called a dispersant.

The amount of the emulsifier (dispersant) used is preferably small as long as it does not impede the dispersion stability of the fine polymer particles (B) in the aqueous latex. Further, the emulsifier is preferably as high in water solubility as possible. When the emulsifier is highly water soluble, the emulsifier can be easily removed by washing, and the adverse effects of the emulsifier (residual emulsifier) on the finally obtained cured product can be easily prevented.

(initiator)
When an emulsion polymerization method is employed as the method for producing the polymer fine particles (B), a thermally decomposable initiator can be used for the production of 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 initiator can also be used in the production of the polymer microparticles (B). The redox type initiator comprises (a) peroxides such as organic and inorganic peroxides, (b) optionally a reducing agent such as sodium formaldehyde sulfoxylate, glucose, and optionally It is an initiator used in combination with a transition metal salt such as iron (II) sulfate, a chelating agent such as disodium ethylenediaminetetraacetate as necessary, and a phosphorus-containing compound such as sodium pyrophosphate as necessary. Examples of the organic peroxide include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and t-hexyl. and peroxides. Examples of the inorganic peroxides include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

When a redox 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 in a wide range. Therefore, it is preferable to use a redox initiator. Among redox initiators, organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide and t-butyl hydroperoxide are preferably used as redox initiators. The amount of the initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox initiator is used, can be used within a known range.

For the purpose of introducing a crosslinked structure into the elastic body, the grafted part or the surface crosslinked polymer, when using a polyfunctional monomer for the polymerization of the elastic body, the grafted part or the surface crosslinked polymer, a known chain transfer agent is used. A range of amounts can be used. By using a chain transfer agent, the molecular weight and/or the degree of cross-linking of the resulting elastic body, graft portion or surface-crosslinked polymer can be easily adjusted.

In addition to the components described above, a surfactant can be used for the production of the polymer microparticles (B). The types and amounts of the surfactants used are within known ranges.

In the production of the polymer microparticles (B), conditions such as polymerization temperature, pressure and deoxidation in polymerization can be applied within the known range.

(Collective calcium carbonate (C) surface-treated with a silane coupling agent)
This curable resin composition must contain 10 to 150 parts by mass of colloidal calcium carbonate (C) surface-treated with a silane coupling agent per 100 parts by mass of component (A). Component (C) is added in an amount of 10 to 150 parts by mass with respect to 100 parts by mass of component (A). Due to the effect of the combination with component (B), the impact resistant peel adhesion of the cured product can be maintained. It remarkably improves the shear rate dependence of the viscosity of the curable resin composition. "Maintaining the impact resistance peeling adhesion of the cured product" means that a cured product having equivalent impact resistance peeling adhesion can be provided as compared with a curable resin composition that does not contain the component (C). .

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

Colloidal calcium carbonate is generally surface-treated with fatty acids such as saturated fatty acids and unsaturated fatty acids, or resin acids, from the viewpoint of dispersibility in component (A). It is essential that the component (C) according to one embodiment of the present invention is colloidal calcium carbonate surface-treated with a silane coupling agent. When colloidal calcium carbonate surface-treated with a fatty acid or a resin acid is used in a curable resin composition, the impact resistance peeling adhesion of the resulting cured product is remarkably lowered. On the other hand, in the curable resin composition, when the colloidal calcium carbonate (C) surface-treated with the silane coupling agent according to one embodiment of the present invention is used, the shear rate dependence of viscosity in the curable resin composition is excellent. and high impact peel adhesion resistance in the resulting cured product.

The silane coupling agent used as the component (C) surface treatment agent is not particularly limited. Specific examples of the silane coupling agent include (a) γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatomethyl (b) γ-aminopropyltrimethoxysilane, γ- aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2 -aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltri Isopropoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Amino group-containing such as aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine silanes; (c) ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine; (d) γ-mercaptopropyltrimethoxysilane, γ- mercapto group-containing silanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; (e) γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl) Epoxy group-containing silanes such as ethyltriethoxysilane; (f) β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ- Carboxysilanes such as aminopropyltrimethoxysilane; (g) vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, etc. (h) halogen-containing silanes such as γ-chloropropyltrimethoxysilane; (i) isocyanurate silanes such as tris(3-trimethoxysilylpropyl)isocyanurate; be able to. Among these, amino group-containing silanes, mercapto group-containing silanes, and epoxy group-containing silanes are preferred as the silane coupling agent because they are excellent in reactivity with the component (A), and epoxy group-containing silanes are preferred. more preferred.

The method for producing component (C) is not particularly limited, but methods described in, for example, WO2004/009711, JP-A-2003-112920, JP-A-2005-048102, etc. can be used.

The average particle size of component (C) is not particularly limited, but is preferably 0.03 μm to 0.30 μm, more preferably 0.05 μm to 0.20 μm, even more preferably 0.07 μm to 0.15 μm. It is speculated that the smaller the average particle size of the component (C), the more excellent the shear rate dependency of the viscosity of the resulting curable resin composition. The average particle size of component (C) may be 0.03 μm to 0.15 μm, 0.03 μm to 0.10 μm, or 0.03 μm to 0.05 μm.

The treatment amount of the silane coupling agent is preferably in the range of 0.1% by mass to 20% by mass, more preferably in the range of 1% by mass to 5% by mass, based on 100% by mass of colloidal calcium carbonate. is more preferred. When the treatment amount of the silane coupling agent is (a) 0.1% by mass or more, the effect of improving impact resistance peel adhesion in the resulting cured product is sufficient, and (b) when it is 20% by mass or less. , there is no possibility that the storage stability of the curable resin composition is lowered.

The amount of component (C) used is 10 parts by mass to 150 parts by mass, preferably 20 parts by mass to 120 parts by mass, more preferably 30 parts by mass to 100 parts by mass, based on 100 parts by mass of component (A). , 40 to 80 parts by weight are particularly preferred. When the amount of component (C) used is (a) 10 parts by mass or more, the effect of imparting shear rate dependency of viscosity in the curable resin composition is sufficient, and when it is (b) 150 parts by mass or less, Since the curable resin composition does not become highly viscous, it has the advantage of being easy to handle. The "use amount" can be said to be the "added amount", and can also be said to be the "content" in the curable resin composition.

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

In one embodiment of the present invention, colloidal calcium carbonate other than component (C), that is, colloidal calcium carbonate surface-treated with a non-silane coupling agent and/or surface A small amount of untreated colloidal calcium carbonate can be included.

The content of colloidal calcium carbonate other than component (C) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, and 10 parts by mass with respect to 100 parts by mass of component (C). Part or less is particularly preferable, and it is most preferable to contain substantially no colloidal calcium carbonate other than the component (C). When the amount of colloidal calcium carbonate other than component (C) is 100 parts by mass or less per 100 parts by mass of component (C), there is no possibility that the resulting cured product will have reduced impact resistance peel adhesion.

(Epoxy resin curing agent (D))
In one embodiment of the present invention, an epoxy resin hardener (D) can be used as needed. "Epoxy resin curing agent (D)" may be hereinafter referred to as "(D) component".

If the present curable resin composition is temporarily used as a one-component composition (such as a one-component curable resin composition), the curable resin composition is cured by heating to a temperature of 80 ° C. or higher, preferably 140 ° C. or higher. It is preferable to select the type and amount of component (D) so that the flexible resin composition cures rapidly. Conversely, component (D) and (E) described below are combined so that the curable resin composition cures very slowly, if at all, at room temperature (about 22°C) and temperatures up to at least 50°C. The type and amount of ingredients are preferably selected.

As component (D), a component that exhibits activity upon heating (sometimes referred to as a latent epoxy curing agent) can be used. As such latent epoxy curing agents, N-containing curing agents such as specific amine curing agents (including imine curing agents) can be used. Component (D) includes, for example, boron trichloride/amine complex, boron trifluoride/amine complex, dicyandiamide, melamine, diallylmelamine, guanamine (e.g., acetoguanamine and benzoguanamine), aminotriazole (e.g., 3-amino- 1,2,4-triazoles), hydrazides (e.g. adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide), cyanoacetamides, as well as aromatic polyamines (e.g. metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.) is mentioned. As component (D), dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide, and 4,4'-diaminodiphenylsulfone are more preferably used, and dicyandiamide is particularly preferably used.

Among the component (D), the latent epoxy curing agent is preferable because it enables the present curable resin composition to be used as a one-component curable resin composition.

On the other hand, when the present curable resin composition is used as a two-component or multi-component composition, amine-based curing agents (including imine-based curing agents) and/or mercaptan-based curing agents (room-temperature-curing curing agents) other than the above agent) can be selected as the component (D) that exhibits activity at relatively low temperatures such as room temperature.

Examples of the component (D) that exhibits activity at relatively low temperatures such as room temperature include various compounds described in paragraph [0113] of the specification of WO2016-163491.

Amine-terminated polyethers containing a polyether backbone and having an average of 1 to 4 (preferably 1.5 to 3) amino and/or imino groups per molecule are also used as component (D). can. Commercially available amine terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-5000, manufactured by Huntsman.

Furthermore, an amine-terminated rubber containing a conjugated diene-based polymer backbone and having an average of 1 to 4 (more preferably 1.5 to 3) amino and/or imino groups per molecule (D ) component. Here, the main chain of the rubber, that is, the conjugated diene polymer main chain is preferably a homopolymer or copolymer of polybutadiene, more preferably a polybutadiene/acrylonitrile copolymer, and the acrylonitrile monomer content is 5 to 40% by mass (more preferably 10 to 35%). %, more preferably 15-30% by weight) are particularly preferred. Commercially available amine terminated rubbers include Hypro 1300X16 ATBN from CVC.

Among the amine-based curing agents that are active at relatively low temperatures such as room temperature, polyamidoamines, amine-terminated polyethers, and amine-terminated rubbers are more preferable. It is particularly preferable to use together.

Acid anhydrides and phenols can also be used as component (D). Acid anhydrides and phenols require a higher temperature 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.

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

Component (D) can be used in an amount sufficient to cure the curable resin composition. Typically, a sufficient amount of component (D) can be used to consume at least 80% of the epoxide groups present in the curable resin composition. A large excess of component (D) over the amount required to consume the epoxide groups is usually not necessary.

The present curable resin composition preferably further contains 1 to 80 parts by mass of an epoxy curing agent (D), more preferably 2 to 40 parts by mass, relative to 100 parts by mass of the epoxy resin (A). It is more preferably contained in an amount of 3 to 30 parts by mass, and particularly preferably in an amount of 5 to 20 parts by mass. When the content of component (D) is 1 part by mass or more of (a) with respect to 100 parts by mass of component (A), there is no fear that the curability of the present curable resin composition will deteriorate, and (b) When it is 80 parts by mass or less, the curable resin composition has good storage stability and is easy to handle.

(Curing accelerator (E))
In one embodiment of the present invention, a curing accelerator (E) can be used as needed. "Curing accelerator (E)" may be hereinafter referred to as "(E) component".

Component (E) is a catalyst for promoting the reaction between epoxy groups and epoxide-reactive groups contained in the curing agent and other components of the curable resin composition.

Examples of components (E) include (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) and other ureas; Tertiary amines such as incorporated 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, N,N-dimethylpiperidine; (c) C1-C12 alkyleneimidazole, N-arylimidazole, 2-methyl imidazoles such as imidazole, 2-ethyl-2-methylimidazole, N-butylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, addition products of epoxy resins and imidazole; (d) 6-caprolactam etc. The catalyst may be encapsulated or it may be a latent catalyst that becomes active only when the temperature is raised.

Tertiary amines and imidazoles can be used in combination with the amine-based curing agent (D) to improve the curing speed and the physical properties and heat resistance of the resulting cured product.

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

This curable resin composition preferably further contains 0.1 to 10.0 parts by mass of a curing accelerator (E) with respect to 100 parts by mass of the epoxy resin (A). It is more preferably contained in an amount of 0 parts by mass, more preferably in an amount of 0.5 to 3.0 parts by mass, and particularly preferably in an amount of 0.8 to 2.0 parts by mass. When the content of component (E) is 0.1 parts by mass or more (a) with respect to 100 parts by mass of component (A), there is no possibility that the curability of the present curable resin composition will deteriorate, and ( b) When it is 10.0 parts by mass or less, the curable resin composition has good storage stability and is easy to handle.

(Reinforcing agent other than component (B))
In one embodiment of the present invention, blocked urethane is added as a reinforcing agent other than the component (B) for the purpose of further improving properties such as toughness, impact resistance, shear adhesion and peel adhesion of the resulting cured product. , can be used as desired.

The blocked urethane may be used alone or in combination of two or more.

As blocked urethane, for example, resins described in paragraphs [0079] to [0103] of WO2016-163491 can be used.

(Inorganic filler other than colloidal calcium carbonate)
Inorganic fillers other than colloidal calcium carbonate can be used in the present curable resin composition.

Specific examples of inorganic fillers other than colloidal calcium carbonate include dry silica, wet silica, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, dolomite, carbon black, ground calcium carbonate, and magnesium carbonate. , titanium oxide, ferric oxide, fine aluminum powder, zinc oxide, and active zinc white.

Said fumed silica is also called fumed silica. Examples of the dry silica include 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. mentioned. As the dry silica, hydrophobic fumed silica is preferable because it is excellent in dispersibility in the component (A).

Inorganic fillers other than colloidal calcium carbonate are preferably surface-treated with a surface-treating agent. The surface treatment improves the dispersibility of the inorganic filler in the curable resin composition, and as a result, various physical properties of the obtained cured product are improved.

The amount of inorganic fillers other than colloidal calcium carbonate used is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, and even more preferably 5 to 40 parts by mass, relative to 100 parts by mass of component (A). 7 to 20 parts by weight is particularly preferred.

Inorganic fillers other than colloidal calcium carbonate may be used singly or in combination of two or more.

(calcium oxide)
Calcium oxide can be used in the present curable resin composition.

Calcium oxide removes water from the curable resin composition by reacting with the water in the curable resin composition and solves various physical property problems caused by the presence of water. Calcium oxide functions, for example, as an anti-foaming agent by removing moisture, and suppresses a decrease in adhesive strength of the obtained 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 obtained cured product are improved as compared with the case of using unsurface-treated calcium oxide. Surface-treated calcium oxide can significantly improve the T-peel adhesion and impact resistance peel adhesion of the resulting cured product. The surface treatment agent that can be used for the surface treatment of calcium oxide is not particularly limited, but fatty acids are preferred.

The amount of calcium oxide used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of component (A). 1 to 2 parts by weight is particularly preferred. When the amount of calcium oxide used is (a) 0.1 parts by mass or more, the effect of removing water is sufficient, and when it is (b) 10 parts by mass or less, there is no fear that the strength of the resulting cured product will be lowered. .

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.

(Other ingredients)
In one embodiment of the present invention, other formulation ingredients may be used as desired. Other ingredients include radical curing resins, monoepoxides, photopolymerization initiators, organic fillers, pigments, flame retardants, dispersants, antifoaming agents, plasticizers, solvents, tackifiers, leveling agents, thixotropic properties imparting agents, antioxidants, light stabilizers, ultraviolet absorbers, silane coupling agents, titanate coupling agents, aluminate coupling agents, release agents, antistatic agents, lubricants, low shrinkage agents, azo type chemicals expansion agents such as thermal foaming agents and thermally expandable microballoons; fiber pulps such as aramid pulp; and thermoplastic resins.

Specific examples of radical curable resins, monoepoxides and photopolymerization initiators include, for example, paragraphs [0143] to [0144], [0146], and [0148] of the specification of WO2016-163491. and various compounds described in. Specific examples of pigments, flame retardants, dispersants, defoamers, 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], [0139] in the specification of WO2014-196607, respectively ], [0141], [0143], [0147], [0149], [0151], and [0153].

(Method for producing curable resin composition)
The present curable resin composition is a composition containing fine polymer particles (B) in a curable resin composition containing component (A) as a main component. Preferably, fine polymer particles (B) contain (A) It is a composition dispersed in the form of primary particles in the ingredients. The "composition in which the fine polymer particles (B) are dispersed in the component (A) in the form of primary particles" is hereinafter sometimes referred to as the "fine polymer particle composition".

Various methods can be used to obtain such a polymer fine particle composition. Examples of such methods include (a) a method of contacting polymer fine particles (B) obtained in an aqueous latex state with component (A), and then removing unnecessary components such as water from the mixture, and (b) For example, the polymer fine particles (B) are once extracted into an organic solvent, then 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.

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

It is preferable that the component (A) is liquid at 23° C. so that the third step can be easily performed. The term "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 obtained through the above steps is further added with components (A) and (C), optionally (D), (E), and the other ingredients, By further adding and mixing if necessary, the present curable resin composition in which the fine polymer particles (B) are dispersed in the state of primary particles in the component (A) can be obtained.

On the other hand, using an aqueous latex containing the polymer fine particles (B), after coagulating the polymer fine particles (B) by a method such as salting out, the resulting coagulate is dried to obtain powdery polymer fine particles (B ) can be obtained. The powdery polymer fine particles (B) can be re-dispersed in the component (A) using a dispersing machine having a high mechanical shearing force such as a three-roll paint roll, roll mill or kneader. At this time, component (B) can be efficiently dispersed in component (A) by applying a mechanical shearing force at a high temperature to the mixture of component (A) and component (B). The temperature when dispersing (the temperature when shearing force is applied) 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 component (B) are There is no risk of thermal deterioration.

(Shear rate dependence of viscosity)
The shear rate dependence of the viscosity of the present curable resin composition can be evaluated by the ratio of the viscosity at a shear rate of 5 s ⁻¹ and the viscosity at a shear rate of 50 s ⁻¹ . The “ratio of the viscosity at a shear rate of 5 s ⁻¹ and the viscosity at a shear rate of 50 s ⁻¹ ” is sometimes simply referred to as “viscosity ratio (5 s ⁻¹ /50 s ⁻¹ )”. A larger viscosity ratio (5s ^-1 /50s ^-1 ) means better workability.

The viscosity ratio (5s ^-1 /50s ^-1 ) of the curable resin composition is preferably 1.6 or more, more preferably 1.7 or more, more preferably 1.8 or more, and still more preferably 1.9 or more. , more preferably 2.0 or more, particularly preferably 2.1 or more, and most preferably 2.2 or more.

[One-component curable resin composition]
The one-component curable resin composition according to one embodiment of the present invention includes the curable resin composition described in the section [Curable resin composition]. The one-component curable resin composition is intended to be a curable resin composition that is cured by heating and/or light irradiation after being applied. In other words, the one-component curable resin composition is a curable resin composition that can be sealed and stored without curing after previously blending all the ingredients contained in the curable resin composition. Intend. Since the present curable resin composition is excellent in storage stability, it is particularly useful when used as a one-component curable resin composition.

The present curable resin composition can also be used as a two-component or multi-component curable resin composition. That is, A liquid containing (A) component as a main component, and further containing (B) component and optionally (C) component, (D) component and / or (E) component, and further optionally Prepare a solution A and at least one separately prepared B solution containing the (B) component and / or (C) component according to the requirements, and mix the A solution and the B solution before use They can also be mixed and used. Here, the components (B) and (C) may be contained in at least one of liquid A and liquid B, respectively, and may be contained only in liquid A or only in liquid B. , may be contained in both the A liquid and the B liquid.

The present curable resin composition is preferably a one-liquid curable resin composition from the viewpoint of handleability.

[Cured product]
A cured product according to one embodiment of the present invention is a cured product obtained by curing the curable resin composition described in the section [Curable resin composition]. The cured product according to one embodiment of the present invention is also simply referred to as the main cured product. Since the cured product has the above structure, it has (a) a beautiful surface, (b) high rigidity and high elastic modulus, and (c) excellent toughness and adhesiveness (especially impact-resistant peeling adhesiveness). It is.

In this curable resin composition, the fine polymer particles (B) are uniformly dispersed in the form of primary particles. Therefore, by curing the present curable resin composition, a cured product in which the fine polymer particles (B) are uniformly dispersed can be easily obtained. Further, in the present curable resin composition, the fine polymer particles (B) are less likely to swell and the viscosity of the curable resin composition is low, so that a cured product can be obtained with good workability.

The present cured product can be produced from the present curable resin composition using the present curable resin composition. The method for producing the cured product, in other words, the method for curing the curable resin composition is not particularly limited, and known methods can be used.

(curing temperature)
The curing temperature of the present curable resin composition is not particularly limited. When the present curable resin composition is used as a one-component curable resin composition, the curing temperature is preferably 50° C. to 250° C., more preferably 80° C. to 220° C., even more preferably 100° C. to 200° C., 130° C. to 180° C. is particularly preferred. When the present curable resin composition is used as a two-component curable resin composition, the curing temperature is preferably 0° C. to 150° C., more preferably 10° C. to 100° C., even more preferably 15° C. to 80° C., 20° C. to 60° C. is particularly preferred.

(Dynamic splitting resistance)
The impact resistance peel adhesion of the cured product can be evaluated by the value of dynamic split resistance (kN/m) at 23°C and -40°C. It is intended that the larger the value of the dynamic splitting resistance (kN/m), the better the impact resistance peel adhesion.

The dynamic splitting resistance (kN/m) of the cured product at 23°C is preferably 35 kN/m or more, more preferably 36 kN/m or more, still more preferably 37 kN/m or more, and even more preferably 38 kN/m or more. , 39 kN/m or more is particularly preferred, and 40 kN/m or more is most preferred.

The dynamic split resistance (kN/m) at −40° C. of the hardened product is preferably 25 kN/m or more, more preferably 26 kN/m or more, still more preferably 27 kN/m or more, and even more preferably 28 kN/m or more. It is preferably 29 kN/m or more, particularly preferably 30 kN/m or more, and most preferably 30 kN/m or more.

[Structural adhesive]
A structural adhesive according to one embodiment of the present invention includes the curable resin composition described in the section [Curable resin composition]. The structural adhesive according to one embodiment of the present invention is also simply referred to as the structural adhesive. Since the structural adhesive has the above structure, it has excellent adhesiveness. In the description of the [Structural Adhesive] section below, the terms "curable resin composition" and "structural adhesive" can be interchanged, and the aspect relating to the curable resin composition is also the aspect relating to the structural adhesive. I can say.

This curable resin composition is excellent in adhesion performance and flexibility not only at low temperature (about -20°C) to normal temperature but also at high temperature (about 80°C). Therefore, the present curable resin composition can be used more preferably as a structural adhesive.

The curable resin composition is used as an adhesive for structural members in, for example, automobiles and vehicles (bullet trains, trains, etc.), civil engineering, architecture, building materials, woodworking, electricity, wind power generation, electronics, aircraft, and the space industry. be able to. The adhesive is particularly useful as a structural adhesive for vehicles. Automobile-related applications include adhesion of interior materials such as ceilings, doors, and sheets, and adhesion of automotive lighting fixtures such as lamps and exterior materials such as side moldings.

Since the curable resin composition has excellent toughness, it is suitable for joining different types of base materials having different coefficients of linear expansion.

Further, the present curable resin composition can be suitably used for bonding aerospace components, particularly exterior metal components.

A method of using the present curable resin composition as a structural adhesive will be described by citing a method of bonding any two substrates (which can also be called objects to be adhered) using the present curable resin composition. That is, the present curable resin composition is applied to one or both substrates, the substrates are brought into contact so that the curable resin composition is disposed between the substrates to be bonded, and then the curable resin composition is applied. The substrates can be bonded by curing.

(Application method)
The method of applying the curable resin composition to the object to be adhered is not particularly limited. The curable resin composition can be applied by any method. The curable resin composition can be applied at a low temperature of about room temperature, and can be applied after heating the curable resin composition, if necessary. Since the present curable resin composition is excellent in storage stability, it is particularly useful in a method of heating and applying.

The curable resin composition can also be applied by extruding onto the substrate in beads, monofilaments or swirls using an application robot, mechanical application methods such as caulking guns and other manual application methods. Application means can also be used. The curable resin composition can also be applied to a substrate using a jet spray method or a streaming method.

The viscosity of the curable resin composition is not particularly limited, and is preferably about 150 to 600 Pa s at 45° C. in the extrusion bead method, and about 100 Pa s at 45° C. in the swirl coating method. Preferably, in a high-volume coating method using a high-speed flow apparatus, the viscosity is preferably about 20 to 400 Pa·s at 45°C.

As described above, in the conventional curable resin composition, part of the uncured curable resin composition dissolves or part of the curable resin composition dissolves due to the shower water pressure during the water washing shower process. There are problems such as scattering and washing off, and deformation of the curable resin composition.

When the curable resin composition is used as a vehicle adhesive, the above-mentioned "hardness to wash off the curable resin composition in the water washing shower process" (hereinafter referred to as "hardness to wash off") is effective to increase the viscosity of the curable resin composition. Since the present curable resin composition has a high shear rate dependence of viscosity and tends to be highly viscous, it has excellent "hardness to be washed off". Therefore, the present curable resin composition can be suitably used as a structural adhesive. When the curable resin composition has a high viscosity, the viscosity of the curable resin composition can be adjusted to a viscosity that allows application by heating the curable resin composition.

In addition, in order to improve "hardness to be washed off", the present curable resin composition is a polymer having a crystal melting point near the application temperature of the curable resin composition, as described in WO2005-118734. Preferably, it further contains a compound. The curable resin composition further containing a polymer compound having a crystalline melting point near the application temperature of the curable resin composition is (a) easy to apply due to its low viscosity at the application temperature, and (For example, at a temperature lower than the application temperature), the viscosity becomes high and the "difficulty in washing off" is improved. Generally, the application temperature is higher than the washing shower temperature. Various polyester resins such as crystalline or semi-crystalline polyester polyols can be used as the polymer compound having a crystalline melting point near the application temperature of the curable resin composition.

Furthermore, as another method for improving the "hardness to be washed off", as described in WO2006-093949, the curable resin composition is made into a two-component curable resin composition and cured using As a curing agent, a small amount of a room temperature curing agent such as an amine curing agent having an amino group or an imino group (room temperature curing agent) is used, and a latent curing agent such as dicyandiamide that is active at high temperatures is used for room temperature curing. and a method of using it in combination with a hardening agent. By using two or more kinds of curing agents having significantly different curing temperatures in combination, partial curing proceeds immediately after application of the curable resin composition, and the viscosity becomes high at the time of the water washing shower process, so the curable resin composition can be cured. "Difficult to wash off" is improved.

When the present curable resin composition is used as a structural adhesive, for example, an automotive adhesive, the structural adhesive is applied (applied) to an automobile member, then a coating is applied to the automobile member, and the coating is baked and cured. It is preferable to cure the structural adhesive at the same time from the viewpoint of shortening the process and simplifying the process.

The curing temperature of the structural adhesive includes the curing temperature described in the section [Cured product].

The structural adhesive can be produced from the curable resin composition using the curable resin composition. The method for producing this structural adhesive is not particularly limited, and known methods can be used.

[Laminate]
A laminate according to an embodiment of the present invention contains the curable resin composition described in the section [Curable resin composition]. The laminate according to one embodiment of the present invention is also simply referred to as the present laminate. Since the present laminate has the above structure, it exhibits high adhesive strength.

The laminate may include at least two members and the curable resin composition. Said members are intended to be substrates or objects to be adhered as described above.

Materials 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 composite materials such as CFRP and GFRP. various plastic substrates such as materials;

This curable resin composition has excellent adhesiveness. Therefore, the curable resin composition is sandwiched between a plurality of members containing an aluminum base material, and then the curable resin composition is cured to obtain a laminate obtained by bonding the members. Bodies are preferred because they exhibit high adhesive strength.

The method for manufacturing the laminate is not particularly limited. The laminate, for example, after the curable resin composition is applied to one or both of a plurality of members, the curable resin composition is sandwiched between the members and laminated, and then the curable resin composition is cured. By doing so, it is possible to obtain by joining the members.

Curing conditions are not particularly limited. For example, when using a one-component curable resin composition, by heating the curable resin composition to a temperature of 80 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, the curable resin composition The product is preferably cured within 30 minutes, more preferably within 20 minutes, to obtain a laminate in which a plurality of members are joined.

The thickness of the adhesive layer of this laminate is preferably 0.001 to 5 mm, more preferably 0.01 to 1 mm, and particularly preferably 0.1 to 0.3 mm, from the viewpoint of the adhesive strength of the laminate. The adhesive layer of the laminate can also be said to be the thickness of the cured product of the present curable resin composition.

[Use]
The present curable resin composition and the cured product obtained from the curable resin composition can be used for various uses other than those described above, and the uses are not particularly limited. The present curable resin composition and cured products obtained from the curable resin composition are adhesives, ink binders, wood chip binders, rubber chip binders, foam chip binders, casting binders, bedrocks for floor materials and ceramics. Consolidation materials, paints, coating materials, binders for reinforcing fibers, composite materials, molding materials for 3D printers, materials for lamination with glass fibers and materials for printed wiring boards, electronic substrates, solder resists, interlayer insulation films, build-up materials , FPC adhesives, die bond materials, underfills, semiconductor packaging materials such as ACF, ACP, NCF, and NCP, sealing materials, and the like.

(glue)
The present curable resin composition and the cured product obtained from the curable resin composition are not limited to structural adhesives, and can be suitably used simply as adhesives. The adhesive containing the curable resin composition described in the section [Curable resin composition] can also be said to be the adhesive according to one embodiment of the present invention. The adhesive according to one embodiment of the present invention is also simply referred to as the present adhesive. Since the present adhesive has the above structure, it is excellent in adhesiveness.

The present adhesive can be suitably used in various applications such as automotive interior materials, general woodwork, furniture, interior decoration, wall materials, and food packaging.

The adhesive can bond wood, metal, plastic, glass, and the like. The adhesive is suitable for panels of cured thermosetting resins such as cold rolled steel, aluminum, fiberglass reinforced polyester (FRP), carbon fiber reinforced epoxy resin, carbon fiber reinforced heat Various substrates such as plastic sheet panels, sheet molding compound (SMC), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride (PVC), polycarbonate, polypropylene, TPO, wood and glass, etc. shows good adhesion to

The present adhesive can be produced from the present resin composition using the present resin composition. The method for producing the present adhesive is not particularly limited, and known methods can be used.

(coating material)
The coating material containing the curable resin composition described in the section [Curable resin composition] can also be said to be the coating material according to one embodiment of the present invention. The coating material according to one embodiment of the present invention is also simply referred to as the present coating material. Since the present coating material has the above structure, it can provide a coating film having excellent load resistance and abrasion resistance.

When the present coating material is applied to, for example, floors or corridors, a commonly practiced application method can be applied. For example, after applying a primer to the groundwork prepared, the coating material is uniformly applied using a trowel, roller, rake, spray gun, or the like, depending on the application conditions. After applying this coating material, it hardens and a pavement film with good performance can be obtained. A coating film obtained by curing the present coating material can be a coating film having excellent load resistance and abrasion resistance.

Depending on the application method of the present coating material, the viscosity of the resin composition used for the coating material may be adjusted. For example, when a trowel or rake is used to apply the coating material, the viscosity of the resin composition used for the coating material can generally be adjusted to about 500 to 9,000 cps/25°C. When a roller or spray is used to apply the present coating material, the viscosity of the resin composition used for the coating material can generally be adjusted to about 100 to 3,000 cps/25°C.

There is no particular limitation on the substrate (in other words, the material of the floor or corridor) to which the present coating material is applied. Specific examples of the substrate include (a) a concrete wall, a concrete plate, a concrete block, a CMU (Concrete Masonry Unit), a mortar plate, an ALC (Autoclaved Light-weight Concrete) plate, and a gypsum plate (Dens Glass Gold: Georgia). Pacific, etc.), inorganic substrates such as slate boards, (b) wooden substrates (wood, plywood, OSB (Oriented Strand Board), etc.), asphalt, modified bitumen waterproof sheets, ethylene-propylene-diene rubber (EPDM) waterproof sheet, TPO waterproof sheet, plastic, FRP, organic base such as urethane foam heat insulating material, and (c) metal base such as metal panel.

A case where the present coating material is applied to a metal substrate or a porous substrate will be described. The laminate obtained by curing the coating material after the coating has excellent anti-corrosion properties to the base. In addition, the coating film obtained by curing the coating material after the application can impart excellent crack resistance and load resistance to the substrate. Therefore, the embodiment in which the present coating material is applied to a metal substrate or a porous substrate is a particularly preferred embodiment.

The coating method of the present coating material is not particularly limited, but can be carried out by known coating methods such as trowel, rake, brush, roller, air spray, and airless spray.

Applications of this coating material are not particularly limited, but are for automobiles, electrical equipment, business machines, building materials, lumber, painted floors, paving, heavy-duty anti-corrosion, concrete anti-corrosion, roof and roof waterproofing. for roofs and roofs, corrosion-resistant coatings for underground waterproofing, automotive repair, can coating, top coating, intermediate coating, undercoating, primer, electrodeposition coating, high weather-resistant coating, For non-yellowing paint, etc. When used as a floor coating material and pavement coating material, it can be used in factories, laboratories, warehouses, clean rooms, and the like.

The present coating material can be produced from the present resin composition using the present resin composition. The method for producing the present coating material is not particularly limited, and known methods can be used.

(composite material)
The composite material containing the curable resin composition described in the section [Curable resin composition] can also be said to be a composite material according to one embodiment of the present invention. A composite material according to one embodiment of the present invention is also simply referred to as the present composite material. Since the composite material has the above structure, it has the advantage of being excellent in toughness and impact resistance.

The composite may contain reinforcing fibers. Examples of the reinforcing fiber include, but are not limited to, glass fiber, long glass fiber, carbon fiber, natural fiber, metal fiber, thermoplastic resin fiber, boron fiber, aramid fiber, polyethylene fiber, Zylon reinforcing fiber, and the like. Among these reinforcing fibers, glass fibers and carbon fibers are particularly preferred.

The manufacturing method (molding method) of the present composite material is not particularly limited, but an autoclave molding method using prepreg, a filament winding molding method, a hand lay-up molding method, a vacuum bag molding method, a resin transfer molding (RTM) method, Vacuum assist resin injection molding (VARTM) method, pultrusion molding method, injection molding method, sheet winding molding method, spray-up method, BMC (Bulk Molding Compound) method, SMC (Sheet Molding Compound) method, and the like.

In particular, when carbon fiber is used as the reinforcing fiber, the manufacturing method of this composite material includes an autoclave molding method using prepreg, a filament winding molding method, a hand lay-up molding method, a vacuum bag molding method, a resin injection molding (RTM ) method, vacuum assisted resin injection molding (VARTM) method, etc. are preferably used.

Applications of this composite material include, but are not limited to, aircraft, spacecraft, automobiles, bicycles, ships, weapons, windmills, sporting goods, containers, building materials, waterproof materials, printed circuit boards, electrical insulating materials, and the like. .

The composite material can be produced from the resin composition using the resin composition. For more detailed information about this composite material, such as reinforcing fibers, manufacturing methods (molding methods), manufacturing conditions (molding conditions), compounding agents, applications, etc. No., Japanese Patent Publication No. 2002-530445 (International Publication No. WO2000/029459), Japanese Patent Application Laid-Open No. 55-157620 (US Patent No. 4251428), Japanese Patent Publication No. 2013-504007 (International Publication No. WO2011/028271 JP 2007-125889 A (US 2007/0098997) and JP 2003-220661 (US 2003/0134085).

(Molding materials for 3D printers)
The 3D printer modeling material containing the curable resin composition described in the section [Curable resin composition] can also be said to be the 3D printer modeling material according to one embodiment of the present invention. The modeling material for the 3D printer according to one embodiment of the present invention is also simply referred to as the present modeling material. Since the present molding material has the above structure, it has the advantage of being excellent in toughness and impact resistance.

Applications of this molding material are not particularly limited, but include prototypes for the purpose of design verification and functional verification before actually making products, aircraft parts, building parts, medical equipment parts, etc.

The present modeling material can be produced from the present resin composition using the present resin composition. A method for manufacturing the present modeling material is not particularly limited, and a known method can be used.

(sealant)
The encapsulant containing the curable resin composition described in the section [Curable resin composition] can also be said to be the encapsulant according to one embodiment of the present invention. The encapsulant according to one embodiment of the present invention is also simply referred to as the main encapsulant. Since the present sealing material has the above structure, it has the advantage of being excellent in toughness and impact resistance.

Applications of the present encapsulant are not particularly limited, but include encapsulants for display devices such as liquid crystal panels, OLED lighting, and OLED displays, and encapsulants for lighting devices. Further, the present sealing material includes sealing for various electric devices such as semiconductors and LEDs, electronic components, power devices, and the like. When used for sealing electrical equipment, electronic components, power devices, etc., the sealing material can also be said to be an electrical insulating material.

The present sealing material can be produced from the present resin composition using the present resin composition. A method for producing the sealing material is not particularly limited, and a known method can be used.

(Electronic substrate)
The electronic substrate containing the curable resin composition described in the section [Curable resin composition] can also be said to be an electronic substrate according to an embodiment of the present invention. The electronic board according to one embodiment of the present invention is also simply referred to as the present electronic board. Since the electronic board has the structure described above, it has the advantage of being excellent in toughness and impact resistance.

Applications of the present electronic board are not particularly limited, but include printed circuits, printed wiring, printed circuit boards, printed circuit mounted products, printed wiring boards and printed boards.

The present electronic board can be produced from the present resin composition using the present resin composition. A method for manufacturing the present electronic substrate is not particularly limited, and a known method can be used.

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 to these. One embodiment of the present invention can be carried out by appropriately changing the following examples as long as it is compatible with the above and the gist of the postscript. Any embodiment implemented by appropriately modifying the following examples is included in the technical scope of the present invention. In the following examples, comparative examples and tables, "parts" and "%" mean parts by mass or % by mass.

(Evaluation method)
First, methods for evaluating the curable resin compositions produced in Examples and Comparative Examples will be described below.

[1] Measurement of Volume Average Particle Size The volume average particle size (Mv) of the polymer fine particles (B) dispersed in the aqueous latex was measured using Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). An aqueous latex diluted with deionized water was used as a measurement sample. For the measurement, the refractive index of water and the refractive index of the polymer fine particles (B) obtained in each production example are input, the measurement time is 600 seconds, and the Signal Level is within the range of 0.6 to 0.8. was performed by adjusting the sample concentration.

[2] Measurement of Viscosity Using a rheometer, the viscosity at 50° C. of each curable resin composition obtained in Examples and Comparative Examples was measured at shear rates of 5 s ⁻¹ and 50 s ⁻¹ . In this specification, when the value of the ratio of the viscosity at 5s ^-1 and the viscosity at 50s ^-1 (viscosity ratio (5s ^-1 /50s ^-1 )) is 1.8 or more, it is regarded as ○ (good), and 1 When it was less than 0.8, it was evaluated as x (defective).

[3] Measurement of dynamic splitting resistance (impact peel adhesion resistance) Each curable resin composition obtained in Examples and Comparative Examples was applied to two SPCC steel plates, and the adhesive layer thickness was 0.25 mm. After superimposing them so that they were aligned, the curable resin composition was cured under the conditions of 170° C. for 30 minutes to obtain a laminate. The resulting laminate was used to measure dynamic split resistance (impact peel adhesion) at 23°C and -40°C according to ISO 11343. In this specification, when the dynamic splitting resistance (kN/m) at 23° C. was 38 or more, it was evaluated as ◯ (good), and when it was less than 38, it was evaluated as x (poor). In this specification, the dynamic splitting resistance (kN/m) at −40° C. was evaluated as ◯ (good) when it was 28 or more, and as × (poor) when it was less than 28.

(1. Polymerization of elastic body)
(Production Example 1-1; Preparation of polybutadiene rubber latex (R-1))
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) in a pressure-resistant polymerization machine with a volume of 100 L. , 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, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials. After that, 100 parts by mass of butadiene (BD) was charged into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.015 parts by mass of paramenthane hydroperoxide (PHP) was charged into the pressure-resistant polymerization vessel, and then 0.04 parts by mass of sodium formaldehyde sulfoxylate (SFS) was charged into the pressure-resistant polymerization vessel to initiate polymerization. started. After 10 hours from the initiation of the polymerization, devolatilization was carried out under reduced pressure to devolatilize and remove residual monomers that were not used in the polymerization, thereby completing the polymerization. During polymerization, each of PHP, EDTA and FE was added into the pressure-resistant polymerization vessel at arbitrary amounts and at arbitrary times. 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 size 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 as a solid content, 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by weight of EDTA and 0.001 parts by weight of FE were added. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the introduced raw materials. After that, 93 parts by mass of BD was charged into the pressure-resistant polymerization vessel, and the temperature inside the pressure-resistant polymerization vessel was raised to 45°C. After that, 0.02 parts by mass of PHP was charged into the pressure-resistant polymerization vessel, and then 0.10 parts by mass of SFS was charged into the pressure-resistant polymerization vessel to initiate polymerization. After 30 hours from the start of the polymerization, the polymerization was completed by devolatilizing under reduced pressure to devolatilize and remove residual monomers that were not used in the polymerization. During polymerization, each of PHP, EDTA and FE was added into the pressure-resistant polymerization vessel at arbitrary amounts and at arbitrary times. 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 size of the polybutadiene rubber particles contained in the obtained latex was 0.20 μm.

(2. Preparation of fine polymer particles (B) (polymerization of graft portion))
(Production Example 2-1; Preparation of polymer fine particle latex (L-1))
256 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (polybutadiene rubber particles 85 parts by mass) and 61 parts by mass of deionized water were added. Here, the glass reactor contained a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the introduced raw materials were stirred at 60° C. while replacing the gas with nitrogen. Next, 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added into the glass reactor. Then, monomers for polymerizing the graft portion (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 4 parts by mass of glycidyl methacrylate (GMA)) and , and 0.04 parts by mass of cumene hydroperoxide (CHP) were continuously added into a glass reactor over 80 minutes. After the addition was completed, 0.04 part by mass of CHP was added into the glass reactor, and the mixture in the glass reactor was stirred for another 2 hours to complete the polymerization. Aqueous latex (L-1) containing fine polymer particles (B) was obtained by the above operation. The polymerization conversion rate of the monomer component 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.

(Production Example 2-2; Preparation of polymer fine particle latex (L-2))
In Production Example 2-1, <ST7 parts by mass, MMA 4.5 parts by mass> instead of <ST7 parts by mass, MMA 1.5 parts by mass, AN 2.5 parts by mass, and GMA 4 parts by mass> as monomers for polymerizing the graft portion , 2.5 parts by mass of AN and 1 part by mass of GMA>, an aqueous latex (L-2) containing fine polymer particles (B) was obtained in the same manner as in Production Example 2-1. The volume average particle diameter of the polymer fine particles (B) contained in the obtained aqueous latex was 0.21 μm.

(Production Example 2-3; Preparation of polymer fine particle latex (L-3))
In Production Example 2-1, <ST7 parts by mass, MMA 3.5 parts by mass> instead of <ST7 parts by mass, MMA 1.5 parts by mass, AN 2.5 parts by mass, and GMA 4 parts by mass> as monomers for polymerizing the graft portion , AN 2.5 parts by mass, and GMA 2 parts by mass> were used in the same manner as in Production Example 2-1 to obtain an aqueous latex (L-3) containing polymer fine particles (B). The volume average particle diameter of the polymer fine particles (B) contained in the obtained aqueous latex was 0.21 μm.

(Production Example 2-4; Preparation of polymer fine particle latex (L-4))
In Production Example 2-1, instead of <ST7 parts by weight, MMA 1.5 parts by weight, AN 2.5 parts by weight and GMA 4 parts by weight> as monomers for polymerizing the graft portion, <ST6 parts by weight, MMA 0 parts by weight, AN7 A water-based latex (L-4) containing fine polymer particles (B) was obtained in the same manner as in Production Example 2-1, except that 2 parts by mass of GMA> was used. 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 fine polymer particles (B) are dispersed in a 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 the MEK, 132 g of the aqueous latex (L-1) containing the polymer fine particles (B) obtained in Production Example 2-1 (corresponding to 40 g of the 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 introduced into the mixing tank at a supply rate of 80 g/min while stirring the raw materials in the mixing tank. After the supply of water was completed, the stirring was promptly stopped to obtain a slurry liquid consisting of an aqueous phase containing aggregates containing polymer fine particles (B) and a small amount of organic solvent. The aggregates were buoyant. Next, 360 g of the water phase was discharged from the discharge port at the bottom of the mixing tank so that the aggregate containing a part of the water phase remained in the mixing tank. 90 g of MEK was added to the obtained agglomerates, and they were uniformly mixed to obtain a dispersion in which the fine polymer particles (B) were uniformly dispersed in MEK. 60 g of the epoxy resin (A-1) as the component (A) was added to the obtained dispersion, and they were uniformly mixed. The epoxy resin (A-1) will be detailed below. MEK was removed from the resulting mixture using a rotary evaporator. Thus, a dispersion (M-1) in which the fine polymer particles (B) are dispersed in the epoxy resin (A) was obtained.

(Production Example 3-2; Preparation of Dispersion (M-2))
Production Example 3 except that 132 g of (L-2) (corresponding to 40 g of polymer fine particles (B)) was used instead of 132 g of (L-1) as the aqueous latex containing polymer fine particles (B) in Production Example 3-1. A dispersion (M-2) in which the fine polymer particles (B) are dispersed in the epoxy resin (A) was obtained in the same manner as in dispersion-1.

(Production Example 3-3; Preparation of Dispersion (M-3))
Production Example 3 except that 132 g of (L-3) (corresponding to 40 g of polymer fine particles (B)) was used instead of 132 g of (L-1) as the aqueous latex containing polymer fine particles (B) in Production Example 3-1. A dispersion (M-3) in which the polymer fine particles (B) are dispersed in the epoxy resin (A) was obtained in the same manner as in -1.

(Production Example 3-4; Preparation of Dispersion (M-4))
Production Example 3 except that 132 g of (L-4) (equivalent to 40 g of polymer fine particles (B)) was used instead of 132 g of (L-1) as the aqueous latex containing polymer fine particles (B) in Production Example 3-1. A dispersion (M-4) in which the fine polymer particles (B) are dispersed in the epoxy resin (A) was obtained in the same manner as in -1.

In Dispersions (M-1) to (M-4), component (A) is 60 parts by mass in 100 parts by mass of dispersions.

(Examples 1 to 6, Comparative Examples 1 to 18)
According to the formulations (formulations) shown in Tables 1 to 3, each component was weighed and thoroughly mixed to obtain a curable resin composition. Tables 1 to 3 show the test results of viscosity and dynamic split resistance (impact peel adhesion resistance) of the obtained curable resin compositions.

Various components in Tables 1 to 3 were used as shown below.
<<Epoxy resin (A)>>
Epoxy resin (A-1): JER828 (manufactured by Mitsubishi Chemical, bisphenol A type epoxy resin liquid at room temperature, epoxy equivalent: 184 to 194)
Reactive diluent (A-2): Cardula E10P (manufactured by Momentive, versatic acid glycidyl ester)
<<Dispersion (M) in which fine polymer particles (B) are dispersed in epoxy resin (A)>>
M-1 to 4: Dispersions obtained in Production Examples 3-1 to 3-4 <<Collective calcium carbonate surface-treated with a silane coupling agent (C)>>
RK-100BR (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate surface-treated with a silane coupling agent)
≪Surface untreated heavy calcium carbonate≫
Whiten SB (manufactured by Shiraishi Calcium, untreated heavy calcium carbonate, average particle size: 1.8 μm)
≪Surface treated heavy calcium carbonate≫
Ryton A (manufactured by Shiraishi Calcium, heavy calcium carbonate surface-treated with modified fatty acid, average particle size: 1.8 μm)
≪Collective calcium carbonate surface-treated with fatty acid≫
Shiroenka CCR (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate surface-treated with saturated fatty acid)
Shiraenka CCR-S (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate surface-treated with unsaturated fatty acid)
Vigot-10 (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid)
Vigot-15 (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid)
Calfain 200M (made by Maruo Calcium, colloidal calcium carbonate surface-treated with fatty acid)
Calfain 200 (made by Maruo Calcium, colloidal calcium carbonate surface-treated with fatty acid)
MSK-PO (made by Maruo Calcium, colloidal calcium carbonate surface-treated with fatty acid)
Carfosil 15B (manufactured by Maruo Calcium, colloidal calcium carbonate surface-treated with fatty acid)
≪Blocked urethane≫
QR-9466 (made by ADEKA, blocked urethane)
≪Fumed Silica≫
CAB-O-SIL TS-720 (manufactured by CABOT, fumed silica surface treated with polydimethylsiloxane),
≪Calcium oxide≫
CML#31 (manufactured by Ohmi Chemical Industry, calcium oxide surface-treated with fatty acid)
<<Epoxy curing agent (D)>>
Dyhard 100S (manufactured by AlzChem, dicyandiamide)
<<Curing accelerator (E)>>
Dyhard UR300 (manufactured by AlzChem, 1,1-dimethyl-3-phenylurea)
Dyhard UR200 (manufactured by AlzChem, 1,1-dimethyl-3-(3,4-dichlorophenyl)urea)

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 for component (A), that is, the amount of component (A) added as an epoxy resin. It is the sum of the amount and the amount described in the column of (A) component + (B) component, that is, the amount of component (A) contained in dispersion (M) of fine polymer particles (B).

From Tables 1 to 3, the curable resin compositions of Examples 1 to 6 containing the (A) component, (B) component and (C) component of the present invention have a viscosity ratio (5s ^-1 /50s ^-1 ) , the dynamic split resistance at 23° C. and the dynamic split resistance at −40° C. were all above a good level. Therefore, the curable resin composition according to one embodiment of the present invention is excellent in workability and impact-resistant peel adhesiveness because the shear rate dependency of viscosity is large. The curable resin compositions of Examples 1 to 6 are particularly excellent in impact-resistant peel adhesion at low temperatures (-40°C).

According to one embodiment of the present invention, it is possible to provide a curable resin composition capable of providing a cured product having excellent impact peel adhesiveness. Therefore, the curable resin composition according to one embodiment of the present invention and the cured product of the curable resin composition are adhesives, ink binders, wood chip binders, rubber chip binders, foam chip binders, casting binders, Rock consolidation materials for flooring and ceramics, paints, coating materials, binders for reinforcing fibers, composite materials, molding materials for 3D printers, materials for lamination with glass fibers and materials for printed wiring boards, electronic substrates, solder resists , interlayer insulating films, build-up materials, FPC adhesives, die-bonding materials, underfills, semiconductor packaging materials such as ACF, ACP, NCF, and NCP, and sealing materials. It can be used more preferably as a structural adhesive for vehicles.

Claims (14)

Epoxy resin (A), and fine polymer particles (B ) 1 to 100 parts by mass, and 10 to 150 parts by mass of colloidal calcium carbonate (C) surface-treated with a silane coupling agent. The curable resin composition according to claim 1, further comprising 1 to 80 parts by mass of an epoxy curing agent (D) with respect to 100 parts by mass of the epoxy resin (A). 3. The curable resin composition according to claim 1, further comprising 0.1 to 10.0 parts by mass of a curing accelerator (E) with respect to 100 parts by mass of the epoxy resin (A). The curable resin according to any one of claims 1 to 3, wherein the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber and polysiloxane rubber elastic body. Composition. The curable resin composition according to any one of claims 1 to 4, wherein the elastic body is butadiene rubber and/or butadiene-styrene rubber. The graft portion is a polymer containing, as structural units, structural units derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers and (meth)acrylate monomers. 6. The curable resin composition according to any one of 5. The curable resin composition according to any one of claims 1 to 6, wherein the graft portion is a polymer having an epoxy group. The curable resin composition according to any one of claims 1 to 7, wherein the graft portion is a polymer containing, as a structural unit, a structural unit derived from a monomer having an epoxy group. 9. Any one of claims 1 to 8, wherein the graft portion is a polymer having an epoxy group, and the content of the epoxy group relative to the mass of the graft portion is 0.1 mmol/g to 5.0 mmol/g. The curable resin composition according to . The curable resin composition according to any one of claims 1 to 9, wherein a cured product obtained by curing the curable resin composition has a dynamic splitting resistance at 23°C of 35 kN/m or more. A one-component curable resin composition comprising the curable resin composition according to any one of claims 1 to 10 . A structural adhesive comprising the curable resin composition according to any one of claims 1-10 . A cured product obtained by curing the curable resin composition according to any one of claims 1 to 10 . A laminate comprising the curable resin composition according to any one of claims 1 to 10 .