WO2020218552A1 - Structure production method - Google Patents

Abstract

The objective of the invention is to provide a production method for a structure having excellent workability. The structure production method comprises: an adhesion step of coating a curable resin composition onto a first adherend and adhering a second adherend onto the first adherend; a washing step of washing the adhered body, and a curing step of curing the curable resin composition, wherein the curable resin composition contains an epoxy resin (A), a specific polymer microparticle (B), and a fumed silica (C), respectively in specific amounts.

Description

Structure manufacturing method

The present invention relates to a method for manufacturing a structure.

The cured epoxy resin is excellent in many respects such as dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, and chemical resistance. However, the cured product of the epoxy resin has low fracture toughness and may exhibit a very brittle property, and such a property is often a problem in a wide range of applications. Various techniques have been disclosed for this problem.

Patent Document 1 and Patent Document 2 disclose a technique for dispersing polymer fine particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component.

The curable resin composition containing an epoxy resin may be used as an adhesive (for example, a structural adhesive) (Patent Documents 1 and 3).

JP-A-2015-07280 International Publication WO2016 / 163491 Special table 2017-529417

However, there is room for further improvement in the production of the structure using the curable resin composition disclosed in the prior art as described above from the viewpoint of workability.

One embodiment of the present invention has been made in view of the above problems, and an object of the present invention is to provide a method for manufacturing a structure having excellent workability.

As a result of diligent studies to solve such a problem, the present inventor has cured the epoxy resin (A), the polymer fine particles (B) containing a hydroxy group in the graft portion, and the fumed silica (C) in specific amounts. We have found that the above problems can be solved by using the sex resin composition, and have completed the present invention.

That is, in the method for producing a structure according to an embodiment of the present invention, the curable resin composition is applied to the first adherend, and the second adherend is bonded to the first adherend. The curable resin composition comprises an epoxy resin (a bonding step, a cleaning step of cleaning the bonded body obtained in the bonding step, and a curing step of curing the curable resin composition. A rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body and containing a hydroxy group with respect to 100 parts by mass of the epoxy resin (A). It contains 1 part to 100 parts by mass of the polymer fine particles (B) and 1 part to 30 parts by mass of the fumed silica (C).

According to one embodiment of the present invention, it is possible to provide a method for manufacturing a structure having excellent workability.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

[1. Technical Thought of One Embodiment of the Invention]
A case where the curable resin composition is used as a structural adhesive in the manufacture of vehicles and the like will be described. In a production line such as a vehicle, there is a cleaning step (for example, a washing shower step) between the step of applying the curable resin composition (adhesive) to the object to be adhered and the step of curing the curable resin composition. May be done. In the conventional curable resin composition, (a) a part of the uncured curable resin composition is dissolved or (b) the uncured curable resin composition is dissolved by the shower water pressure during the cleaning step. There are problems such as a part of the resin being scattered and washed away, or (c) the uncured curable resin composition being deformed.

In order to reduce scattering and deformation of the uncured curable resin composition due to water pressure, studies have been conventionally made to improve the shear rate dependence of the viscosity of the curable resin composition (for example, Patent Document 1).

The present inventor examined the viscosity of the curable resin composition and inferred as follows. That is, the phenomenon that the curable resin composition is deformed by the shower water pressure is the deformation of the curable resin composition in a stationary state, and it is considered that the viscosity of the curable resin composition in the low shear rate range is important. Then, the viscosity of the curable resin composition in the high shear rate range at the time of application is lowered, 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 has independently found that by increasing the speed dependence, (a) suppression of scattering and deformation of the curable resin composition in the washing shower step and (b) coating workability can be achieved at the same time.

An object according to an embodiment of the present invention is to provide a curable resin composition having a high viscosity dependence on the shear rate, thereby providing a method for producing a structure having excellent workability using the curable resin composition. That is.

Therefore, the present inventor has made it an issue to improve the temperature dependence of the viscosity of the curable resin composition. The resin composition in which the particle components such as the polymer fine particles (B) according to the embodiment of the present invention are dispersed in the liquid matrix resin such as the epoxy resin (A) is formed between the particle components (hereinafter, also between the particles). It is known that structural viscosity associated with a weak interaction (referred to as) is likely to occur. In order to improve the shear rate dependence of the viscosity of the resin composition, the present inventor has set an original problem of obtaining a resin composition having a large structural viscosity in a low shear rate range, and conducted a diligent study. It was. In the process, the present inventor has independently found that the structural viscosity of the resin composition increases in the low shear rate range by enhancing the interaction between the polymer fine particles (B).

As a result of further diligent studies based on such new findings, the present inventor found that in a curable resin composition containing an epoxy resin, the shear rate dependence of the viscosity of the curable resin composition was (i) polymer fine particles and fumed. It was independently found that it changes depending on the combined use with silica and the structure of (ii) polymer fine particles. Based on this new finding, the present inventor has diligently studied polymer fine particles and fumed silica, and as a result, completed the present invention.

It is known that the larger the measured value called Yield Stress (also referred to as yield stress), the more the curable resin composition can be suppressed from scattering and deformation in the washing shower step (for example, Patent Document 3).

Further, in the production of a structure, the curable resin composition is (1) applied to one of the adherends after being heated (also referred to as heating coating), and then (2) one of them. Before or at the same time that the adherend and the other adherend are bonded together at room temperature, they can be thinly stretched from the thickness at the time of application. Here, the present inventor has independently found that the following problems (i) and (ii) occur when the viscosity of the curable resin composition is highly temperature-dependent: (i) curable resin composition. If the viscosity of the material during warm coating is set low, the viscosity of the curable resin composition during warm coating may be too low and the applied curable resin composition may drip; and (ii) curability. When the viscosity of the resin composition during warm coating is set high, the viscosity of the curable resin composition after coating is significantly increased due to the decrease in temperature in a room temperature environment. It may be difficult to stretch an object thinly. As a result of diligent studies based on these problems, the present inventor has improved workability in the production of structures using the curable resin composition by reducing the temperature dependence of the viscosity of the curable resin composition. I found it uniquely to get.

Therefore, a preferred embodiment of the present invention provides a curable resin composition having a high Yield Stress and / or a small temperature dependence of viscosity in addition to a high viscosity shear rate dependence. With the goal.

[2. Structure manufacturing method]
In the method for producing a structure according to an embodiment of the present invention, a curable resin composition is applied to a first adherend, and the second adherend is bonded to the first adherend. It includes a step, a cleaning step of cleaning the bonded body obtained in the bonding step, and a curing step of curing the curable resin composition. The curable resin composition comprises 1 part by mass to 100 parts by mass of polymer fine particles (B) and 1 part by mass of fumed silica (C) with respect to 100 parts by mass of the epoxy resin (A) and the epoxy resin (A). Contains to 30 parts by mass. The polymer fine particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body and containing a hydroxy group. "Method for manufacturing a structure according to an embodiment of the present invention", "Epoxy resin (A)", "Polymer fine particles (B)" and "Fumed silica (C)" are described below as "Method for manufacturing the present invention", respectively. , "(A) component", "(B) component" and "(C) component".

The curable resin composition used in this production method has a high viscosity dependence on the shear rate. That is, the curable resin composition used in this production method has a lower viscosity in the high shear rate range and a higher viscosity in the low shear rate range than the conventional curable resin composition. Therefore, it can be said that the curable resin composition used in this production method has excellent shower resistance. Further, the curable resin composition used in the present production method may have an advantage that the temperature dependence of the viscosity is small. That is, the curable resin composition used in this production method has a higher viscosity at the time of coating (which can be said to be the viscosity at the time of heating and the viscosity at the high temperature) as compared with the conventional curable resin composition, and In some cases, the viscosity when working in a room temperature environment (which can be said to be the viscosity at low temperature) is low. Since this production method uses a curable resin composition having the above-mentioned advantages, it has an advantage of excellent workability.

(2-1. Curable resin composition)
Hereinafter, the curable resin composition used in this production method will be described in detail.

The curable resin composition according to the embodiment of the present invention comprises 1 part by mass to 100 parts by mass of the polymer fine particles (B) with respect to 100 parts by mass of the epoxy resin (A) and the epoxy resin (A). It contains 1 part by mass to 30 parts by mass of fumed silica (C). The polymer fine particles (B) include a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body and containing a hydroxy group. The "curable resin composition according to one embodiment of the present invention" may be hereinafter referred to as "the present curable resin composition".

Since the present curable resin composition has the above-mentioned structure, the viscosity is highly dependent on the shear rate. Therefore, by using the present curable resin composition, it is possible to provide a method for producing a structure having excellent workability. In the present specification, the shear rate dependence of the viscosity is evaluated by the ratio of the viscosity when the shear rate is 5s ^-1 to the viscosity when the shear rate is 50s ^-1 . A high shear rate dependence of the viscosity, the viscosity / shear rate ^{50s -1} at a ratio (shear rate ^{5s -1} and the viscosity at a viscosity and shear rate ^{50s -1} at a shear rate of ^{5s -1} It means that the viscosity at the time of) is large. The method for measuring the viscosity will be described in detail in Examples.

The reason why the viscosity of this curable resin composition is highly dependent on the shear rate is not clear, but it is estimated as follows. The polymer fine particles (B) according to the embodiment of the present invention have a hydroxy group at the graft portion. In addition, the present curable resin composition contains fumed silica (C). Humed silica (C) has a hydroxy group derived from a silanol group or the like on its surface. As a result, due to the hydrogen bonds between the hydroxy groups, between the polymer fine particles (B), between the polymer fine particles (B) and the fumed silica (C), and / or between the fumed silica (C). It is estimated that the action will be higher. It is presumed that when the interaction between the particles is enhanced, the particles are less likely to be separated from each other in the low shear rate region, and as a result, the structural viscosity is maintained high in the low shear rate region and the shear rate dependence of the viscosity becomes high.

Since the present curable resin composition has the above-mentioned structure, it may have an advantage that the temperature dependence of the viscosity is small. By using a curable resin composition having a small temperature dependence of viscosity, it is possible to provide a method for producing a structure having more excellent workability.

The reason why the temperature dependence of the viscosity of this curable resin composition is small is not clear, but it is estimated as follows. That is, it is presumed that if the interaction between the particles is enhanced, the particles are less likely to be separated from each other even at a high temperature, and as a result, the structural viscosity is maintained even at a high temperature and the temperature dependence of the viscosity is reduced.

(Epoxy resin (A))
The present curable resin composition contains an epoxy resin (A) as a main component.

As the epoxy resin (A), various hard epoxy resins can be used except for the rubber-modified epoxy resin and the urethane-modified epoxy resin described later. 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, glycidyl amine type epoxy resin, and novolac type epoxy resin. , Bisphenol A propylene oxide adduct glycidyl ether type epoxy resin, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, flame-retardant epoxy resin such as tetrabromo bisphenol A glycidyl ether, p-oxybenzo Glycidyl acid ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, various alicyclic epoxy resins, N, N-diglycidyl aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocia Nurate, divinylbenzene dioxide, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, glycidyl ether of divalent or higher polyvalent aliphatic alcohol such as glycerin , Chelate-modified epoxy resin, hidden-in type epoxy resin, epoxidized products of unsaturated polymers such as petroleum resin, aminoglycidyl ether resin containing aminoglycidyl, and bisphenol A (or F) or polybasic acids and the like in these above-mentioned epoxy resins. Epoxy compounds obtained by the addition reaction of the above are exemplified. The epoxy resin (A) is not limited to these, and a generally used epoxy resin can be used.

The "hard epoxy resin" is intended to be an epoxy resin having a specific glass transition temperature (Tg), and examples thereof include an epoxy resin having a Tg of 50 ° C. or higher.

More specific examples of the polyalkylene glycol diglycidyl ether include polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether. More specific examples of the glycol diglycidyl ether include neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether and the like. Be done. More specific examples of the aliphatic polybasic acid diglycidyl ester include dimer acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, and maleic acid diglycidyl ester. More specifically, the glycidyl ether of the divalent or higher polyvalent aliphatic alcohol includes trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil-modified polyglycidyl ether, propoxylated glycerin triglycidyl ether, and sorbitol. Examples include polyglycidyl ether. Examples of the epoxy compound obtained by adding a polybasic acid or the like to an epoxy resin include a dimer of a tall oil fatty acid (dimeric acid) and a bisphenol A type epoxy as described in WO2010-098950. Examples include an addition reaction product with a resin. One type of these epoxy resins may be used alone, or two or more types may be used in combination.

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

The chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound (chelate ligand) containing a chelate functional group. When a chelate-modified epoxy resin is added to the curable resin composition and used as an adhesive, the adhesiveness to the surface of a metal substrate contaminated with an oily substance can be improved. The chelate functional group is a functional group of a compound having a plurality of coordination positions capable of coordinating to a metal ion in the molecule, and is, for example, a phosphorus-containing acid group (for example, -PO (OH) ₂ ) or a carboxylic acid group (-). CO ₂ H), sulfur-containing acid groups (eg, -SO ₃ H), amino groups and hydroxyl groups (particularly, hydroxyl groups adjacent to each other in the aromatic ring) and the like. Examples of the chelating ligand include ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether, and the like. Examples of commercially available chelate-modified epoxy resins include ADEKA ADEKA Resin EP-49-10N.

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

In the present specification, the "usage amount" of a certain component can be said to be the "addition amount" of the component, and can also be said to be the "content" of the component in the curable resin composition.

Among these epoxy resins, those having at least two epoxy groups in one molecule have high reactivity in curing of the obtained curable resin composition, and the obtained cured product easily forms a three-dimensional network. It is preferable from the point of view.

Among the above-mentioned epoxy resins, the bisphenol A type epoxy resin and the bisphenol F type epoxy resin can (a) obtain a cured product having high elasticity and excellent heat resistance and adhesiveness, and (b) be relatively inexpensive. Therefore, bisphenol A type epoxy resin is particularly preferable.

Further, among the various epoxy resins described above, an epoxy resin having an epoxy equivalent of less than 220 is preferable because it has a small temperature dependence of viscosity and a high elastic modulus and heat resistance of the obtained cured product. Among the above-mentioned epoxy resins, an epoxy resin having an epoxy equivalent of 90 or more and less than 210 is more preferable, and an epoxy resin having an epoxy equivalent of 150 or more and less than 200 is further preferable.

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

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 to 100% by mass of the component (A) in a range of preferably 40% by mass or less, more preferably 20% by mass or less. Is preferable. According to the above configuration, the obtained adhesive layer has an advantage of being excellent in impact resistance.

(Polymer fine particles (B))
The curable resin composition according to one embodiment of the present invention can provide an adhesive layer having excellent toughness and impact peeling adhesiveness due to the toughness improving effect of the component (B).

From the balance between the shear rate dependence of the viscosity of the obtained curable resin composition and the ease of handling, and the effect of improving the toughness of the obtained adhesive layer, the component (B) is 1 mass by mass with respect to 100 parts by mass of the component (A). 3 parts to 100 parts by mass is preferable, 3 parts by mass to 70 parts by mass is more preferable, 5 parts by mass to 50 parts by mass is further preferable, and 10 parts by mass to 40 parts by mass is particularly preferable.

The volume average particle diameter (Mv) of the polymer fine particles (B) is not particularly limited, but in consideration of industrial productivity, 10 nm to 2000 nm is preferable, 10 nm to 1000 nm is preferable, 30 nm to 600 nm is more preferable, and 50 nm to 400 nm is preferable. More preferably, 100 nm to 200 nm is particularly preferable. According to the above configuration, there is also an advantage that a highly stable curable resin composition having a desired viscosity can be obtained. In the present specification, the "volume average particle size (Mv) of the polymer fine particles (B)" is intended to be the volume average particle size of the primary particles of the polymer fine particles (B) unless otherwise specified. The volume average particle size (Mv) of the polymer fine particles (B) is a dynamic light scattering type particle size distribution measuring device (for example, Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.)) using an aqueous latex containing the polymer fine particles (B) as a sample. Can be measured using. The method for measuring the body volume average particle diameter of the polymer fine particles (B) will be described in detail in the following Examples. The volume average particle diameter of the polymer fine particles (B) is determined by cutting the adhesive layer of the structure, imaging the cut surface of the adhesive layer using an electron microscope, or the like, and then using the obtained imaging data (imaging image). It can also be measured.

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

Since the above-mentioned specific particle size distribution can be easily realized, it is preferable that two or more maximum values exist in the number distribution of the volume average particle size of the component (B). It is more preferable that there are two or three maximum values in the number distribution of the volume average particle diameter of the component (B), and two maximum values are present, because the labor during manufacturing is small and the cost is low. Is more preferable. The component (B) particularly contains 10 to 90% by mass of polymer fine particles having a volume average particle diameter 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 diameter of 150 nm or more and 2000 nm or less. Is preferable.

The component (B) is preferably dispersed in the state of primary particles in the curable resin composition or the adhesive layer. In one embodiment of the present invention, "the polymer fine particles (B) are dispersed in the curable resin composition or the adhesive layer in the form of primary particles" means that in the curable resin composition or the adhesive layer, This means that the polymer fine particles (B) are dispersed substantially independently (without contact). The dispersed state of the polymer fine particles (B) in the curable resin composition or the adhesive layer is, for example, the volume average particle diameter (Mv) / number average particle diameter (Mn) of the polymer fine particles (B) (hereinafter, “Mv / Mn”. It may be confirmed by measuring).

The Mv / Mn of the polymer fine particles (B) is the volume average particle diameter (Mv) of the polymer fine particles (B) using a dynamic light scattering type particle size distribution measuring device (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). ) And the number average particle size (Mn) are measured respectively, and Mv can be obtained by dividing by Mn. For the Mv / Mn of the polymer fine particles (B) in the curable resin composition, for example, a part of the curable resin composition is dissolved in a solvent such as methyl ethyl ketone, and the obtained mixture (dissolved product) is subjected to dynamic light. It can be measured by using it in a scattering type particle size distribution measuring device or the like. The Mv / Mn of the polymer fine particles (B) in the adhesive layer is obtained, for example, after cutting the adhesive layer of the structure and imaging the cut surface of the adhesive layer using an electron microscope or the like. ) Can be used for measurement.

The value of the volume average particle diameter (Mv) / number average particle diameter (Mn) of the polymer fine particles (B) is not particularly limited, but is preferably 3 or less, more preferably 2.5 or less, and further 2 or less. It is preferable, and 1.5 or less is particularly preferable. When the volume average particle size (Mv) / number average particle size (Mn) of the polymer fine particles (B) is 3 or less, the polymer fine particles (B) are good in the curable resin composition or the adhesive layer, that is, the primary particles. It is considered that they are dispersed in the state of. The curable resin composition in which the Mv / Mn of the polymer fine particles (B) is 3 or less, that is, the curable resin composition in which the polymer fine particles (B) have good dispersibility, has physical properties such as impact resistance and adhesiveness. An excellent adhesive layer can be provided. The adhesive layer in which the Mv / Mn of the polymer fine particles (B) is 3 or less, that is, the adhesive layer in which the polymer fine particles (B) have good dispersibility is excellent in physical properties such as impact resistance and adhesiveness.

Further, the polymer fine particles (B) are stably dispersed over a long period of time under normal conditions without agglomeration, separation, or precipitation in the continuous layer. , Also referred to as "stable dispersion" of the polymer fine particles (B). Examples of the "continuous layer" include a curable composition and an adhesive layer. It is preferable that the distribution of the polymer fine particles (B) in the continuous layer does not change substantially. Further, even when the continuous layer (for example, a curable resin composition) is heated within a non-hazardous range to reduce the viscosity of the continuous layer and stirred, the polymer fine particles (B) in the continuous layer are "stable". It is preferable that the "dispersion" is maintained.

As the component (B), one type may be used alone, or two or more types may be used in combination.

(Elastic body)
The elastic body preferably contains at least one selected from the group consisting of natural rubber, diene rubber, (meth) acrylate rubber and polysiloxane rubber elastic, and preferably diene rubber and (meth) acrylate rubber. It is more preferable to contain at least one selected from the group consisting of polysiloxane rubber-based elastic bodies. The elastic body can also be rephrased as rubber particles. As used herein, the term (meth) acrylate means acrylate and / or methacrylate. The polysiloxane rubber-based elastic body may also be referred to as an organosiloxane-based rubber.

Curability obtained because (a) the effect of improving toughness and impact resistance peeling adhesiveness in the obtained adhesive layer is high, and (b) the affinity with the matrix resin (for example, epoxy resin (A)) is low. The elastic body preferably contains a diene rubber, and more preferably a diene rubber, because the resin composition is unlikely to increase in viscosity with time due to swelling of the elastic body. When the elastic body contains a diene-based rubber, the obtained curable resin composition can also provide an adhesive layer having excellent toughness and impact resistance.

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

Examples of the diene-based monomer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2-chloro-1,3-butadiene and the like. Only one type of these diene-based monomers may be used, or two or more types may be used in combination.

Examples of vinyl-based monomers other than the diene-based monomer copolymerizable with the diene-based monomer (hereinafter, also referred to as vinyl-based monomer A) include (i) styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene. Vinyl monomers; (ii) Vinyl carboxylic acids such as acrylic acid and methacrylic acid; (iii) Vinyl cyanes such as acrylonitrile and methacrylate; (iv) Vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; (V) Vinyl acetate; Alkens such as ethylene, propylene, butylene, and isobutylene; (vi) Polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene, and the like. As the vinyl-based monomer A described above, only one type may be used, or two or more types may be used in combination. Among the vinyl-based monomers A described above, styrene is particularly preferable.

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

Since a wide range of polymer designs can be performed by combining various monomers, the elastic body preferably contains (meth) acrylate-based rubber, and more preferably (meth) acrylate-based rubber. Hereinafter, a case where the elastic body contains (meth) acrylate-based rubber (case B) will be described.

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

Examples of the (meth) acrylate-based monomer include (i) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth). Alkyl (meth) acrylates such as acrylates, stearyl (meth) acrylates and behenyl (meth) acrylates; aromatic ring-containing (meth) acrylates such as (ii) phenoxyethyl (meth) acrylates and benzyl (meth) acrylates; (iii) ) Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; glycidyl (meth) acrylate such as (iv) glycidyl (meth) acrylate and glycidylalkyl (meth) acrylate. Classes; (v) alkoxyalkyl (meth) acrylates; (vi) allylalkyl (meth) acrylates such as allyl (meth) acrylates and allylalkyl (meth) acrylates; (vi) monoethylene glycol di (meth) acrylates, Examples thereof include polyfunctional (meth) acrylates such as triethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate. One of these (meth) acrylate-based monomers may be used alone, or two or more thereof may be used in combination. Among these (meth) acrylate-based monomers, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable.

As a vinyl-based monomer other than the (meth) acrylate-based monomer copolymerizable with the (meth) acrylate-based monomer (hereinafter, also referred to as a vinyl-based monomer other than the (meth) acrylate-based monomer), in the vinyl-based monomer A. The listed monomers can be mentioned. As the vinyl-based monomer other than the (meth) acrylate-based monomer, one type may be used alone, or two or more types may be used in combination. Among vinyl-based monomers other than the (meth) acrylate-based monomer, styrene is particularly preferable.

When trying to improve the impact resistance of the adhesive layer at a low temperature without lowering the heat resistance of the obtained adhesive layer, the elastic body preferably contains a polysiloxane rubber-based elastic body, and the polysiloxane rubber-based elastic body is preferable. It is more preferable to be a body. Hereinafter, a case where the elastic body includes a polysiloxane rubber-based elastic body (Case C) will be described.

The polysiloxane rubber-based elastic body is composed of alkyl or aryl disubstituted silyloxy units such as (a) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy. Polysiloxane-based polymer to be prepared, and (b) polysiloxane-based polymer composed of alkyl or aryl1-substituted silyloxy units such as organohydrogensilyloxy in which a part of alkyl in the side chain is substituted with a hydrogen atom. , Can be mentioned. Only one kind of these polysiloxane-based polymers may be used, or two or more kinds thereof may be used in combination. Among these polysiloxane-based polymers, (a) the obtained curable resin composition can provide an adhesive layer having excellent heat resistance, so that dimethylsilyloxy units, methylphenylsilyloxy units, and / or dimethyl A polymer composed of silyloxy-diphenylsilyloxy units is preferable, and (b) a polymer composed of dimethylsilyloxy units is most preferable because it is easily available and economical.

In Case C, the polymer fine particles (B) preferably contain 80% by mass or more of the polysiloxane rubber-based elastic body, and 90% by mass or more of the elastic body contained in the polymer fine particles (B). It is more preferable to do so. According to the above configuration, the obtained curable resin composition can provide an adhesive layer having excellent heat resistance.

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

(Cross-linked structure of elastic body)
Since the dispersion stability of the polymer fine particles (B) in the curable resin composition can be maintained, it is preferable that a crosslinked structure is introduced into the elastic body. As a method for introducing the 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 an elastic body, a method of mixing a polyfunctional monomer and / or a crosslinkable monomer such as a mercapto group-containing compound with a monomer that can form an elastic body and then polymerizing the material can be mentioned. In the present specification, producing a polymer such as an elastic body is also referred to as polymerizing a polymer.

In addition, as a method for introducing a crosslinked structure into a polysiloxane rubber-based elastic body, the following methods can also be mentioned: (a) When polymerizing a polysiloxane rubber-based elastic body, a polyfunctional alkoxysilane compound is used. A method of partially using it together with other materials, (b) introducing a reactive group such as a vinyl-reactive group or a mercapto group into a polysiloxane rubber-based elastic body, and then adding a vinyl-polymerizable monomer or an organic peroxide. In the method of causing a radical reaction, or (c) when polymerizing a polysiloxane rubber-based elastic body, a crosslinkable monomer such as a polyfunctional monomer and / or a mercapto group-containing compound is mixed with other materials and then polymerized. How to do, etc.

It can be said that the polyfunctional monomer has two or more radically polymerizable reactive groups in the same molecule. The radically polymerizable reactive group is preferably a carbon-carbon double bond. Examples of the polyfunctional monomer include allylalkyl (meth) acrylates such as allyl (meth) acrylate and allylalkyl (meth) acrylate, and ethylenically unsaturated double bonds such as allyloxyalkyl (meth) acrylates. (Meta) acrylate having the above is exemplified. Examples of the monomer having two (meth) acrylic groups include ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and cyclohexanedimethanol di (meth). Examples thereof include meta) acrylates and polyethylene glycol di (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, and polyethylene glycol (600) di (meth) acrylate. Is exemplified. Further, as a monomer having three (meth) acrylic groups, alkoxylated trimethylolpropane tri (meth) acrylates, glycerol propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl). Examples thereof include isocyanurate tri (meth) acrylate. Examples of the alkoxylated trimethylolpropane tri (meth) acrylate include trimethylolpropane tri (meth) acrylate and trimethylolpropane triethoxytri (meth) acrylate. Further, examples of the monomer having four (meth) acrylic groups include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. Further, as a monomer having five (meth) acrylic groups, dipentaerythritol penta (meth) acrylate and the like are exemplified. Further, as a monomer having six (meth) acrylic groups, ditrimethylolpropane hexa (meth) acrylate and the like are exemplified. Examples of the polyfunctional monomer 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 preferable as the polyfunctional monomer.

Examples of the mercapto group-containing compound include alkyl group-substituted mercaptan, allyl group-substituted mercaptan, aryl group-substituted mercaptan, hydroxy group-substituted mercaptan, alkoxy group-substituted mercaptan, cyano group-substituted mercaptan, amino group-substituted mercaptan, silyl group-substituted mercaptan, and acid group-substituted mercaptan. Examples thereof include mercaptans, halo group-substituted mercaptans and acyl group-substituted mercaptans. As the alkyl group-substituted mercaptan, an alkyl group-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkyl group-substituted mercaptan having 1 to 10 carbon atoms is more preferable. As the aryl group-substituted mercaptan, a phenyl group-substituted mercaptan is preferable. As the alkoxy group-substituted mercaptan, an alkoxy group-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkoxy group-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 polymer fine particles (B) preferably has rubber properties in order to increase the toughness of the obtained adhesive layer. The elastic material is preferably one that can swell in a suitable solvent but is substantially insoluble. The elastic body is preferably insoluble in the epoxy resin (A) used.

The gel content of the elastic body is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, because the obtained adhesive layer has excellent toughness. It is particularly preferable that it 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 the polymer fine particles (B) is obtained, and then a powder of the polymer fine particles (B) is obtained from the aqueous latex. The method for obtaining the powder of the polymer fine particles (B) from the aqueous latex is not particularly limited, but for example, (i) the polymer fine particles (B) in the aqueous latex are aggregated, and (ii) the obtained aggregate is dehydrated. Then, (iii) further, a method of obtaining the powder of the polymer fine particles (B) by drying the agglomerates can be mentioned. Next, 0.5 g of the polymer fine particle (B) powder is immersed in 100 g of toluene. The resulting mixture is then allowed to stand at 23 ° C. for 24 hours. Then, the obtained mixture is separated into a toluene-soluble component (toluene-soluble component) and a toluene-insoluble component (toluene-insoluble component). The mass of the obtained toluene-soluble component and the toluene-insoluble component is measured, and the gel content is calculated from the following formula.
Gel content (%) = (mass of toluene insoluble) / {(mass of toluene insoluble) + (mass of toluene soluble)} x 100
(Glass transition temperature of elastic body)
The glass transition temperature of the elastic body (hereinafter, may be simply referred to as “Tg”) is preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and more preferably −20 ° C. or lower in order to increase the toughness of the obtained adhesive layer. It is more preferably 40 ° C. or lower, and particularly preferably −60 ° C. or lower.

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

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

Here, when a homopolymer obtained by polymerizing only one type of monomer is obtained, a group of monomers that provide a homopolymer having a Tg larger than 0 ° C. is referred to as a monomer group a. Further, when a homopolymer formed by polymerizing only one type of monomer, a group of monomers that provide a homopolymer having a Tg of less than 0 ° C. is referred to as a monomer group b. As a polymer capable of forming an elastic body having a Tg larger than 0 ° C. and capable of suppressing a decrease in rigidity of the obtained adhesive layer,
The constituent units derived from at least one monomer selected from the monomer group a are derived from 50 to 100% by mass (more preferably 65 to 99% by mass), and from at least one monomer selected from the monomer group b. Examples thereof include a polymer composed of 0 to 50% by mass (more preferably 1 to 35% by mass) of the constituent units.

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

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

Examples of the monomer group b include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. As the monomer to be selected from these monomer group b, only one kind may be used, or two or more kinds may be used in combination. Among the monomer group b, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.

(Volume average particle size of elastic body)
The volume average particle size of the elastic body is preferably 0.03 to 2.00 μm, more preferably 0.05 to 1.00 μm, further preferably 0.10 to 0.80 μm, and particularly 0.10 to 0.50 μm. preferable. When the volume average particle size of the elastic body is (a) 0.03 μm or more, an elastic body having a desired volume average particle size can be stably obtained, and (b) when it is 2.00 μm or less, it is obtained. The heat resistance and impact resistance of the adhesive layer to be formed are improved. 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 type particle size distribution measuring device or the like. The method for measuring the volume average particle size of the elastic body will be described in detail in the following examples.

(Ratio of elastic body (ratio))
The ratio of the elastic body in the polymer fine particles (B) is preferably 40 to 97% by mass, more preferably 60 to 95% by mass, and further 70 to 93% by mass, assuming that the entire polymer fine particles (B) are 100% by mass. It is preferable, and 80 to 90% by mass is particularly preferable. When the ratio of the elastic body is (a) 40% by mass or more, there is no possibility that the toughness improving effect of the adhesive layer of the obtained curable resin composition is lowered, and (b) 97% by mass or less. Since the polymer fine particles (B) do not easily aggregate, the curable resin composition does not have a high viscosity, and as a result, the obtained curable resin composition can be easy to handle.

(Modification example of elastic body)
In one embodiment of the present invention, the elastic body is one selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and a polysiloxane rubber-based elastic body, and has a structural unit having 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, each having a structural unit having a different composition.

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 referred to as elastic body ₁ , elastic body ₂ , ..., And elastic body _n . Here, n is an integer of 2 or more. The elastic body may contain a mixture obtained by mixing the elastic body ₁ , the elastic body ₂ , ..., And the elastic body _n , which are separately polymerized. The elastic body may contain a polymer obtained by sequentially polymerizing the elastic body ₁ , the elastic body ₂ , ..., And the elastic body _n , respectively. Such polymerization of a plurality of polymers (elastic bodies) in order is also referred to as multistage polymerization. A polymer obtained by multi-stage polymerization of a plurality of types of elastic bodies is also referred to as a multi-stage polymerization elastic body. The method for producing the multi-stage polymerized elastic body will be described in detail later.

A multi-stage 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 or may cover at least a portion of the elastic body _n-1, or the whole of the elastic body _n-1 coating. In the multi-stage polymer elastic body, sometimes some of the elastic body _n has entered the inside of the elastic body _n-1.

In the multi-stage polymerized 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 the elastic body ₁ , the elastic body ₂ , and the elastic body ₃ , the elastic body ₁ is the innermost layer, the layer of the elastic body ₂ exists outside the elastic body ₁ , and the elastic body is further formed. An embodiment in which the layer of the elastic body ₃ exists as the outermost layer in the elastic body outside the layer ₂ is also an aspect of the present invention. As described above, a multi-stage polymerized elastic body in which each of the plurality of elastic bodies has a layered structure can be said to be a multi-layer elastic body. That is, in one embodiment of the present invention, the elastic body may include a mixture of a plurality of types of elastic bodies, a multi-stage polymerized elastic body and / or a multilayer elastic body.

(Graft part)
In the present specification, a polymer graft-bonded to an elastic body is referred to as a graft portion. The graft portion can play various roles. The "various roles" include, for example, improving the compatibility between the components (a) and (B) and the component (A), and (b) dispersibility of the polymer fine particles (B) in the epoxy resin (A). It is improved, and (c) it is possible to disperse the polymer fine particles (B) in the state of primary particles in the present curable resin composition or its adhesive layer.

The graft portion of the component (B) contains a hydroxy group. With this configuration, the obtained curable resin composition has a high viscosity dependence on the shear rate, and as a result, it is possible to provide a method for producing a structure having excellent workability. Further, by including the component (B) containing a hydroxy group in the graft portion in combination with the fumed silica (C) described later, the obtained curable resin composition has a higher viscosity dependence on the shear rate. As a result, it is possible to provide a method for manufacturing a structure having better workability. Since the graft portion of the component (B) contains a hydroxy group, the obtained curable resin composition also has an advantage that it can provide an adhesive layer having excellent impact-resistant peeling adhesiveness.

The content of the hydroxy group contained in the graft portion of the component (B) is not particularly limited. The content of the hydroxy group in the graft portion of the component (B) is preferably 0.01 mmol / g or more, more preferably 0.1 mmol / g or more, based on the total mass of the graft portion. It is more preferably 2 mmol / g or more, and particularly preferably 0.4 mmol / g or more. The greater the content of the hydroxy group contained in the graft portion of the component (B), the higher the dependence of the viscosity of the obtained curable resin composition on the shear rate, and in the adhesive layer provided by the obtained curable resin composition. Impact resistance Peeling Adhesiveness is good. The graft portion of the component (B) is preferably 5.0 mmol / g or less, more preferably 4.0 mmol / g or less, and 2.5 mmol / g or less, based on the total mass of the graft portion. It is more preferable, and it is particularly preferable that it is 1.5 mmol / g or less. The smaller the content of the hydroxy group contained in the graft portion of the component (B), the smaller the change in viscosity of the obtained curable resin composition during storage, and the easier the handleability of the curable resin composition becomes.

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

Specific examples of the monomer having a hydroxy group include (i) hydroxy linear alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. (In particular, hydroxy linear C1-6 alkyl (meth) acrylate); (ii) caprolactone-modified hydroxy (meth) acrylate; (iii) methyl α- (hydroxymethyl) acrylate, α- (hydroxymethyl) ethyl acrylate, etc. Hydroxy branched alkyl (meth) acrylate; (iv) mono (meth) acrylate of polyester diol (particularly saturated polyester diol) obtained from divalent carboxylic acid (such as phthalic acid) and dihydric alcohol (such as propylene glycol). Examples thereof include hydroxyl group-containing (meth) acrylates.

The graft portion preferably contains 0.2% by mass to 70.0% by mass, and 2.0% by mass to 50.0% by mass, of a structural unit derived from the hydroxy group-containing monomer in 100% by mass of the graft portion. More preferably, it is more preferably 4.0% by mass to 40.0% by mass, and particularly preferably 10.0% by mass to 30.0% by mass. When 0.2% by mass or more of the structural unit derived from the hydroxy group-containing monomer is contained in 100% by mass of the graft portion, (a) the viscosity dependence of the viscosity in the obtained curable resin composition becomes high, and the obtained curing The impact-resistant peeling adhesiveness of the adhesive layer provided by the sex resin composition is good, and (b) the obtained curable resin composition can provide an adhesive layer having sufficient impact resistance. When the constituent unit derived from the hydroxy group-containing monomer is contained in an amount of 70.0% by mass or less in 100% by mass of the graft portion, the obtained curable resin composition can provide an adhesive layer having sufficient impact resistance. Moreover, it has an advantage that the storage stability of the curable resin composition is improved.

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

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

Since the compatibility and dispersibility of the component (B) in the curable resin composition are good, the graft portion is a group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and a (meth) acrylate monomer as a constituent unit. 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 the aromatic vinyl monomer include vinylbenzenes such as styrene, α-methylstyrene, p-methylstyrene and 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 obtained curable resin composition and the impact strength of the adhesive layer obtained by curing are good. Therefore, 0.5 mmol / g to 15.0 mmol / g is preferable, 1.0 mmol / g to 13.0 mmol / g is more preferable, and 1.5 mmol / g to 11.0 mmol / g is more preferable. .0 mmol / g to 11.0 mmol / g is more preferable, 2.0 mmol / g to 10.0 mmol / g is more preferable, 2.5 mmol / g to 9.0 mmol / g is more preferable, and 3.0 mol / g to 3.0 mol / g. 9.0 mol / g is more preferred, 5.0 mmol / g to 10.0 mmol / g is even more preferred, 5.5 mmol / g to 9.5 mmol / g is even more preferred, 7.0 mmol / g to 9.0 mmol / g. g is particularly preferable. When the content of the cyano group with respect to the total mass of the graft portion of the component (B) is (a) 0.5 mmol / g or more, there is an advantage that the temperature dependence of the viscosity of the obtained curable resin composition becomes small. When (b) is 15.0 mmol / g or less, there is no possibility that the amount of the cyano group-containing monomer remaining in the polymer fine particles (B) will increase, and as a result, there is an advantage that the safety is high.

Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

Specific examples of the (meth) acrylate monomer include (a) methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid alkyl ester such as butyl (meth) acrylate; and (b) hydroxyethyl (meth). Examples thereof include (meth) acrylic acid hydroxyalkyl esters such as acrylates and hydroxybutyl (meth) acrylates.

As the above-mentioned one or more kinds of monomers selected from the group consisting of aromatic vinyl monomer, vinyl cyan monomer and (meth) acrylate monomer, only one kind may be used, or two or more kinds may be used in combination. May be good.

As the constituent unit, the graft portion includes a structural unit derived from an aromatic vinyl monomer, a structural unit derived from a vinyl cyan monomer, and a structural unit derived from a (meth) acrylate monomer, in a total of 100% by mass of all the structural units. It is preferably contained in an amount of 10 to 95% by mass, more preferably 30 to 92% by mass, further preferably 50 to 90% by mass, particularly preferably 60 to 87% by mass, and 70 to 85% by mass. Is the most preferable.

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

The graft portion is preferably a polymer having an epoxy group. The content of the epoxy group with respect to the total mass of the graft portion is preferably 0.1 mmol / g to 5.0 mmol / g, more preferably 0.2 to 5.0 mmol / g, and more preferably 0.3 to 5.0 mmol / g. Preferably, 0.4 to 5.0 mmol / g is more preferable, 0.4 to 3.5 mmol / g is further preferable, 0.4 to 3.0 mmol / g is further preferable, and 0.4 to 2.5 mmol / g is more preferable. g is particularly preferable. The content of the epoxy group with respect to the total mass of the graft portion may be 0.2 mmol / g to 3.5 mmol / g, or may be 0.3 mmol / g to 3.0 mmol / g. According to this configuration, the resulting curable resin composition has the advantages of excellent viscosity temperature dependence and storage stability.

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

Specific examples of the monomer 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.

As the above-mentioned reactive group-containing monomer, only one type may be used, or two or more types may be used in combination.

The graft portion preferably contains 0.5 to 90% by mass of a structural unit derived from the reactive group-containing monomer, more preferably 1 to 50% by mass, and 2 to 35% by mass in 100% by mass of the graft portion. % Is more preferable, and 3 to 20% by mass is particularly preferable. When the graft portion contains (a) 0.5% by mass or more of the structural unit derived from the reactive group-containing monomer in 100% by mass of the graft portion, the obtained curable resin composition has sufficient resistance. An adhesive layer having impact resistance can be provided, and (b) when 90% by mass or less is contained, the obtained curable resin composition can provide an adhesive layer having sufficient impact resistance. Moreover, it has an 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) the curable resin composition can prevent the polymer fine particles (B) from swelling in the curable resin composition. Since the viscosity is low, the curable resin composition tends to be easy to handle, and (c) the dispersibility of the polymer fine particles (B) in the epoxy resin (A) is improved.

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the obtained curable resin composition has an advantage that it can provide an adhesive layer excellent in toughness improving effect and impact peeling adhesiveness improving effect.

Examples of the polyfunctional monomer that can be used for the polymerization of the graft portion include the same monomer as the above-mentioned polyfunctional monomer. Among these polyfunctional monomers, the polyfunctional monomers that can be preferably used for the polymerization of the graft portion include allyl methacrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate. , Cyclohexanedimethanol di (meth) acrylate, triallyl isocyanurate and polyethylene glycol di (meth) acrylate, with allyl methacrylate and triallyl isocyanurate being more preferred. Only one kind of these polyfunctional monomers may be used, or two or more kinds thereof may be used in combination.

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

The graft portion has a structural unit of 0% by mass to 50% by mass (more preferably 1% by mass to 50% by mass) derived from an aromatic vinyl monomer (particularly styrene) in 100% by mass of all the structural units as a structural unit. , More preferably 2% by mass to 48% by mass), a structural unit derived from a vinyl cyan monomer (particularly acrylonitrile) 0% by mass to 50% by mass (more preferably 0% by mass to 30% by mass, still more preferably 10% by mass). ~ 25% by mass), structural unit derived from (meth) acrylate monomer (particularly methyl methacrylate) 0% by mass to 90% by mass (more preferably 5% by mass to 85% by mass, still more preferably 20% by mass to 80% by mass). ), And 5% by mass to 90% by mass (more preferably 10% by mass to 50% by mass, still more preferably 15% by mass to 30% by mass) of structural units derived from a monomer having an epoxy group (particularly glycidyl methacrylate). Contains 100% by mass in total. According to this structure, a curable resin composition having a small temperature dependence of viscosity can be obtained.

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

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

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

In the present specification, the ratio of the polymer graft-bonded to the elastic body, that is, the graft portion, among the polymers produced in the polymerization of the graft portion is referred to as the graft ratio. The graft ratio can be said to be a value represented by (mass of graft portion) / {(mass of graft 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 further 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 of calculating the graft ratio is as follows. First, an aqueous latex containing the polymer fine particles (B) is obtained, and then a powder of the polymer fine particles (B) is obtained from the aqueous latex. As a method for obtaining the powder of the polymer fine particles (B) from the aqueous latex, the method described in the section (Gel content of elastic body) can be used. Next, 2 g of the polymer fine particle (B) powder is immersed in 100 g of methyl ethyl ketone (hereinafter, may be referred to as MEK). The resulting mixture is then allowed to stand at 23 ° C. for 24 hours. Then, the obtained mixture is separated, and then the obtained mixture is separated into a MEK-soluble component (MEK-soluble component) and a MEK-insoluble component (MEK-insoluble component). Further, the MEK-soluble component is mixed with methanol to separate the methanol-insoluble component from the MEK-soluble component. Then, the mass of the obtained MEK insoluble matter and the methanol insoluble matter is measured, and the graft ratio is calculated by obtaining the ratio of the MEK insoluble matter to the total amount of the MEK insoluble matter and the methanol insoluble matter. Specifically, the graft ratio is calculated by the following formula.
Graft ratio (%) = (mass of MEK insoluble matter) / {(mass of MEK insoluble matter) + (mass of methanol insoluble matter)} x 100
(Modification example of graft part)
In one embodiment of the present invention, the graft portion may consist of only one type of graft portion having a structural unit having 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 structural unit having a different composition.

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 referred to as a graft portion ₁ , a graft portion ₂ , ..., A graft portion _n (n is an integer of 2 or more). The graft portion may contain a mixture obtained by mixing the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n, which are polymerized separately, respectively. The graft portion may contain a polymer obtained by multi-stage polymerization of the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n . A polymer obtained by multi-stage polymerization of a plurality of types of graft portions is also referred to as a multi-stage polymerization graft portion. The method for producing the multi-stage polymerization graft portion will be described in detail later.

When the graft portion is composed of a plurality of types of graft portions, all of the plurality of types of graft portions do not have to be graft-bonded to the elastic body. At least a part of the graft portion of at least one kind may be graft-bonded to the elastic body, and the graft portion of the other species (several other kinds) is the graft portion graft-bonded to the elastic body. It may be graft-bonded to. When the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers (non-graft polymers) that have the same configuration as the plurality of types of graft portions and are not graft-bonded to an elastic body. ) May have.

A multi-stage polymerization graft portion including the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n will be described. In the multi-stage polymerization grafts, the graft section _n may either be coated onto at least a portion of the graft portion _n-1, or may cover the entire graft portion _n-1. In the multi-stage polymerization grafting unit, a portion of the graft portion _n sometimes has entered the inside of the graft portion _n-1.

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

When the elastic body and the graft portion are polymerized in this order in the production of the polymer fine particles (B), at least a part of the graft portion can cover at least a part of the elastic body in the obtained polymer fine particles (B). The fact that the elastic body and the graft portion are polymerized in this order can be said to mean that the elastic body and the graft portion are polymerized in multiple stages. The polymer fine particles (B) obtained by multi-stage polymerization of the elastic body and the graft portion can be said to be a multi-stage polymer.

When the polymer fine particles (B) are multi-stage polymers, the graft portion can cover at least a part of the elastic body or can cover the entire elastic body. When the polymer fine particles (B) are multi-stage polymers, a part of the graft portion 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 a core layer) and the layer of the graft portion is present as the outermost layer (also referred to as a shell layer) outside the elastic body is also one aspect of the present invention. A structure in which the elastic body is the core layer and the graft portion is the shell layer can be said to be a core-shell structure. As described above, the polymer fine particles (B) in which the elastic body and the graft portion have a layered structure (core-shell structure) can be said to be a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (B) may be a multi-stage polymer and / or a multilayer polymer or a core-shell polymer. However, as long as the graft portion is graft-bonded to the elastic body, the polymer fine particles (B) are not limited to the above configuration.

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

(Surface crosslinked polymer)
The polymer fine 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, in the production of (a) the polymer fine particles (B), the blocking resistance can be improved, and (b) the dispersibility of the polymer fine particles (B) in the epoxy resin (A) becomes better. .. The reasons for these are not particularly limited, but can be presumed as follows: By coating at least a part of the elastic body with the surface crosslinked polymer, the exposure of the elastic body portion of the polymer fine particles (B) is reduced. As a result, the elastic bodies are less likely to stick to each other, so that the dispersibility of the polymer fine particles (B) is improved.

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

It is preferable that the polymer fine particles (B) do not contain a surface crosslinked polymer because the obtained adhesive layer is excellent in toughness and impact resistance peeling adhesiveness.

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

Examples of the polyfunctional monomer that can be used for the polymerization of the surface crosslinked polymer include the same monomers as the above-mentioned polyfunctional monomer. Among these polyfunctional monomers, the polyfunctional monomers that can be preferably used for the polymerization of surface crosslinked polymers include allyl methacrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth). ) Acrylate, cyclohexanedimethanol di (meth) acrylate, triallyl isocyanurate and polyethylene glycol di (meth) acrylate are mentioned, with allyl methacrylate and triallyl isocyanurate being more preferred. Only one kind of these polyfunctional monomers may be used, or two or more kinds thereof may be used in combination.

The polymer fine particles (B) may contain a surface crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or the surface crosslinked polymer polymerized together with the rubber-containing graft copolymer. May include. The polymer fine 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 may cover at least a portion of the elastic body.

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

A case (case D) in which the polymer fine particles (B) are multi-stage polymers 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 crosslinked polymer can cover part of the elastic body or the entire elastic body. In case D, a part of the surface crosslinked polymer may have entered the inside of the elastic body. In case D, the graft portion can cover a part of the surface crosslinked polymer or can cover the whole surface crosslinked polymer. In case D, a part of the graft portion may enter the inside of 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 on the outside of the elastic body, and the grafted layer is the outermost layer (shell layer) on the outside of the surface crosslinked polymer. The existing aspect is also one aspect of the present invention.

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

The polymer fine particles (B) can be produced by a known method, for example, a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. Specifically, the polymerization of the elastic body in the polymer fine particles (B), the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer are known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization and the like. It can be manufactured by the method of. Among these, in particular, the composition design of the polymer fine particles (B) is easy, the industrial production is easy, and the aqueous latex of the polymer fine particles (B) that can be suitably used for producing the present curable resin composition is easy. As a method for producing the polymer fine particles (B), emulsion polymerization is preferable. Hereinafter, a method for producing an elastic body, a graft portion, and a surface crosslinked polymer having an arbitrary configuration, which can be contained in the polymer fine particles (B), will be described.

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

Consider the case where the elastic body contains a polysiloxane rubber-based elastic body. In this case, the elastic body can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like, and as the production method, for example, the method described in WO2006 / 070664 can be used. ..

A method for manufacturing an elastic body will be described when the elastic body is composed of a plurality of types of elastic bodies (for example, elastic body ₁ , elastic body ₂ , ..., Elastic body _n ). In this case, the elastic body ₁ , the elastic body ₂ , ..., The elastic body _n are separately polymerized by the above-mentioned method and then mixed to produce an elastic body having a plurality of types of elastic bodies. May be good. Alternatively, the elastic body ₁ , the elastic body ₂ , ..., And the elastic body _n may be polymerized in multiple stages in this order to produce an elastic body having a plurality of types of elastic bodies.

The multi-stage polymerization of an elastic body will be specifically described. For example, (1) as an elastic body ₁ by polymerizing the elastic member _1; (2) then obtain an elastic body ₂ polymerized by a two-stage elastic member _{1 + 2} in the presence of the elastic member _1; (3) then elastically body _{1 +} obtain ₂ in the presence of the elastic body ₃ polymerized to a three-stage elastic member _{1 + 2 + 3;} (4) below, after the same manner, in the presence of ₊ elastic body _{1 + 2 + · · · (n-1)} The elastic body _n is polymerized to obtain a multi-stage polymerized elastic body _{1 + 2 + ... + N.}

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

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

A method for manufacturing the graft portion will be described when the graft portion is composed of a plurality of types of graft portions (for example, the graft portion ₁ , the graft portion ₂ , ..., The graft portion _n ). In this case, the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n are separately polymerized by the above-mentioned method and then mixed to produce a graft portion having a plurality of types of graft portions. May be good. Alternatively, the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n may be polymerized in multiple stages in this order to produce a graft portion having a plurality of types of graft portions.

The multi-stage polymerization of the graft portion will be specifically described. For example, (1) obtaining a graft portion ₁ by polymerizing a graft portion _1; (2) then obtain grafts ₂ polymerized by two-stage graft section _{1 + 2} in the presence of the graft portion _1; (3) then grafted part _{1 + 2} of obtaining by polymerizing a graft portion ₃ 3-stage graft section _{1 + 2 + 3} in the presence; (4) below, after the same manner, in the presence of the graft section _{1 + 2 + · · · + (n-1)} The graft portion _n is polymerized to obtain a multi-stage polymerization 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 the plurality of types of graft portions and then graft-polymerizing the graft portions onto an elastic body. In the presence of an elastic body, a plurality of types of polymers constituting a plurality of types of graft portions may be sequentially graft-polymerized with respect to the elastic body to produce polymer fine particles (B).

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

The surface crosslinked polymer is a method of polymerizing after adding a monomer used for forming the surface crosslinked polymer to an aqueous latex containing a polymerized elastic material at a time or by continuously adding a fixed amount at a time. May be obtained. Such polymerization can be said to be the polymerization of the surface crosslinked polymer performed in one step. The polymerization of the surface crosslinked polymer may be carried out in two or more stages. That is, it is also possible to adopt a method in which the polymerization is carried out after adding the aqueous latex containing the polymerized elastic body to the reactor in which the monomer used for forming the surface crosslinked polymer is charged in advance.

(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. One type of these emulsifiers may be used alone, or two or more types may be used in combination. The emulsifier can also be said to be a dispersant.

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

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

A redox-type initiator can also be used in the production of the polymer fine particles (B). The redox-type initiators include (a) peroxides such as organic peroxides and inorganic peroxides, (b) reducing agents such as sodium formaldehyde sulfoxylate and glucose as required, and optionally. It is an initiator in which a transition metal salt such as iron (II) sulfate, a chelating agent such as disodium ethylenediamine tetraacetate as required, and a phosphorus-containing compound such as sodium pyrophosphate as necessary are used in combination. Examples of the organic peroxide include t-butyl peroxyisopropyl carbonate, paramentan hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and t-hexyl. Examples include peroxide. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

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

When a polyfunctional monomer is used for the polymerization of an elastic body, a graft part or a surface crosslinked polymer for the purpose of introducing a crosslinked structure into an elastic body, a graft part or a surface crosslinked polymer, a known chain transfer agent is used. It can be used in a range of quantities. By using a chain transfer agent, the molecular weight and / or degree of cross-linking of the obtained elastic body, graft portion or surface cross-linked polymer can be easily adjusted.

In addition to the above-mentioned components, a surfactant can be further used in the production of the polymer fine particles (B). The types and amounts of the surfactants used are in the known range.

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

(Humeed silica (C))
Since the present curable resin composition contains fumed silica (C), the viscosity depends on the shear rate, and as a result, a method for producing a structure having excellent workability can be provided. Further, by containing the fumed silica (C) in combination with the above-mentioned component (B), the obtained curable resin composition has a higher viscosity dependence on the shear rate, and as a result, is more excellent in workability. A method for manufacturing a structure can be provided.

Fumed silica is also called dry silica. The fumed silica includes hydrophilic fumed silica having no surface treatment and hydrophobic fumed silica produced by chemically treating the silanol group portion of the hydrophilic fumed silica with silane and / or siloxane. Can be mentioned. As the fumed silica (C), hydrophilic fumed silica is preferable because (a) excellent workability, and (b) excellent dispersibility in the components (A), and the obtained curable resin composition is obtained. Hydrophobic fumed silica is preferable because it has excellent storage stability.

Fumed silica (C) is produced by (a) Aerosil method produced by decomposition of silicon halide, and (b) Arc that heats and reduces silica sand and then oxidizes it with air to obtain silicic acid. Laws, etc. can be mentioned, but there are no particular restrictions. As a method for producing fumed silica (C), the Aerosil method is preferable from the viewpoint of availability.

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

In the present curable resin composition, the content of the component (C) with respect to 100 parts by mass of the component (A) is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 7 parts by mass. More than 10 parts by mass is more preferable. The content of the component (C) with respect to 100 parts by mass of the component (A) may be 12 parts by mass or more, 15 parts by mass or more, 17 parts by mass or more, or 20 parts by mass. It may be the above. The greater the content of the component (C) with respect to 100 parts by mass of the component (A), the higher the dependence of the viscosity of the obtained curable resin composition on the shear rate, and a method for producing a structure using the curable resin composition. Has excellent workability. In the present curable resin composition, the content of the component (C) with respect to 100 parts by mass of the component (A) is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 13 parts by mass. It is more preferably parts or less, and particularly preferably 10 parts by mass or less. The content of the component (C) with respect to 100 parts by mass of the component (A) may be 8 parts by mass or less, or 5 parts by mass or less. The smaller the content of the component (C) with respect to 100 parts by mass of the component (A), the more the obtained curable resin composition has an advantage of being excellent in storage stability.

(Blocked urethane (D))
The present curable resin composition may or may not contain blocked urethane (D). In the present specification, "blocked urethane (D)" is also referred to as "component (D)".

First, the case where the blocked urethane (D) is not included will be described. The present inventor has compared the case where the present curable resin composition containing the above-mentioned components (A), (B) and (C) further contains the component (D) with the case where the component (D) is not contained. Therefore, it has been independently found that the viscosity dependence of the viscosity of the curable resin composition is low. In the present curable resin composition, the larger the content of the component (D) in the curable resin composition, the lower the dependence of the viscosity of the curable resin composition on the shear rate.

In this curable resin composition, the reason for the decrease in the shear rate dependence of the viscosity of the curable resin composition due to the inclusion of the component (D) is not clear, but it is estimated as follows.

As described above, the formation of hydrogen bonds between the hydroxy groups contained in the graft portion of the polymer fine particles (B) between the polymer fine particles (B) enhances the interaction between the polymer fine particles (B), resulting in curability. It is considered that the viscosity of the resin composition depends on the shear rate. Here, the blocked urethane (D) may contain a large amount of urethane bond, urea bond and / or ether bond, for example, in the main clavicle. These urethane bonds, urea bonds and ether bonds can be hydrogen bonded to hydroxy groups. Therefore, when the curable resin composition containing the component (A), the component (B) and the component (C) further contains the component (D), the formation of hydrogen bonds between the polymer fine particles (B) is caused by the component (D). It is presumed to be inhibited by the hydroxy group inside. This weakens the interaction between the polymer microparticles (B). As a result, when the curable resin composition containing the component (A), the component (B) and the component (C) further contains the component (D), the curable resin is compared with the case where the component (D) is not contained. It is presumed that the shear rate dependence of the viscosity of the composition becomes low.

From the above, in order to obtain a curable resin composition having a high viscosity dependence on the shear rate, it is preferable that the curable resin composition does not substantially contain blocked urethane (D). In the present specification, "substantially free of blocked urethane (D)" means that the curable resin composition does not contain blocked urethane (D) at all, or (A). ) It is intended to contain less than 1 part by mass of blocked urethane (D) with respect to 100 parts by mass of the component.

Next, an embodiment including blocked urethane (D) will be described. The blocked urethane (D) has the effect of improving the toughness of the cured product (adhesive layer) of the curable resin composition. Therefore, in order to obtain an adhesive layer having excellent toughness and extensibility, the curable resin composition preferably contains blocked urethane (D).

Even when the present curable resin composition contains blocked urethane (D), the inorganic filler (E) described later is contained in an amount of 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (A). Moreover, by setting the value (X) represented by the formula (1) to 25 or more, the shear rate dependence of the viscosity of the curable resin composition due to the interaction between the component (D) and the hydroxy group Can be suppressed.

Hereinafter, the mode of the blocked urethane (D) and the like will be described with respect to the case where the present curable resin composition contains the blocked urethane (D).

The ratio (W1 / W2) of the mass (W1) of the polymer fine particles (B) to the mass (W2) of the blocked urethane (D) is not particularly limited. The ratio (W1 / W2) of the mass (W1) of the polymer fine particles (B) to the mass (W2) of the blocked urethane (D) is preferably 0.1 to 10.0, preferably 0.2 to 7.0. More preferably, 1.5 to 7.0 is more preferable, 1.8 to 5.0 is further preferable, 2.0 to 4.0 is further preferable, and 2.5 to 3.5 is particularly preferable. The W1 / W2 may be 0.2 to 5.0, 0.3 to 4.0, 0.4 to 3.0, 0.5 to 2 It may be 0.0. When the W1 / W2 is within the above range, there is an advantage that the temperature dependence of the viscosity of the obtained curable resin composition can be made smaller. Further, when W1 / W2 is 1.5 or more, there is an advantage that the impact resistance peeling adhesiveness of the cured product obtained by curing the curable resin composition at a low temperature does not decrease.

Blocked urethane (D) is an elastomer type, and all or part of the terminal isocyanate groups of a compound containing a urethane group and / or a urea group and having an isocyanate group at the terminal has an active hydrogen group. It is a compound capped with various blocking agents. In particular, a compound in which all of the terminal isocyanate groups are capped with a blocking agent is preferable. Such a compound (ie, blocked urethane (D)) can be obtained, for example, by the following method: (i) An excess polyisocyanate compound is added to an organic polymer having an active hydrogen-containing group at the terminal. The reaction is carried out to obtain a polymer (urethane prepolymer) having a urethane group and / or a urea group in the main chain skeleton and an isocyanate group at the terminal; (ii) after the above (i) or the above (i). At the same time, it is obtained by allowing a blocking agent having an active hydrogen group to act on all or a part of the isocyanate groups of the urethane prepolymer, and capping all or a part of the isocyanate groups with the blocking agent.

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

The isocyanate group capped with the blocking agent is regenerated by heating, and the regenerated isocyanate group reacts with an active hydrogen-containing compound or the like in the composition to improve the toughness of the obtained cured product. The mass% of isocyanate groups regenerated by heating with respect to 100% by mass of blocked urethane (D) is defined as latent NCO%. It is considered that the reaction between the urethane prepolymer and the blocking agent proceeds almost quantitatively. Therefore, when a blocking agent having an equivalent amount or more of active hydrogen groups is reacted with the isocyanate group of the urethane prepolymer, the latent NCO% can be calculated by NCO titrating the urethane prepolymer before capping with the blocking agent. .. Further, when a blocking agent having an active hydrogen group less than the equivalent amount is reacted with the isocyanate group of the urethane prepolymer, the latent NCO% can be calculated by the amount of the reacted blocking agent.

In one embodiment of the present invention, the latent NCO% of the component (D) is not particularly limited, but is 0.1% from the viewpoint of the temperature dependence of the viscosity of the obtained curable resin composition and the toughness of the cured product. ~ 10.0% is preferable, 0.1% to 5.0% is more preferable, 0.1% to 4.0% is more preferable, and 0.1% to 3.5% is more preferable.

In one embodiment of the present invention, the latent NCO% of the blocked urethane (D) is more preferably 0.1% to 2.9%. When the latent NCO% of the component (D) is 0.1 to 2.9%, a curable resin composition having a small temperature dependence of viscosity can be obtained. When the latent NCO% of the component (D) is (a) 0.1% or more, there is no possibility that the toughness of the cured product obtained by curing the curable resin composition is deteriorated, and (b) 2.9. When it is less than%, the temperature dependence of the viscosity of the obtained curable resin composition tends to be small.

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

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

The latent NCO% can also be expressed using the unit "mmol / g". For latent NCO, the unit "mmol / g" means the molar amount (mmol) of isocyanate groups regenerated by heating with respect to 1 g of blocked urethane (D). For latent NCO, "%" and "mmol / g" are interchangeable.

The number average molecular weight of the blocked urethane (D) is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC), preferably 2000 to 40,000, more preferably 3000 to 30000, and particularly 4000 to 20000. preferable. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of blocked urethane (D) is preferably 1 to 4, more preferably 1.2 to 3, and particularly preferably 1.5 to 2.5.

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

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

(Organic polymer having an active hydrogen-containing group at the end)
The main chain skeleton constituting the organic polymer having an active hydrogen-containing group at the terminal includes a polyether polymer, a polyacrylic polymer, a polyester polymer, a polydiene polymer, and a saturated hydrocarbon polymer (polyolefin). ), Polythioether-based polymers and the like.

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

Examples of the organic polymer having an active hydrogen-containing group at the terminal include a polyether polymer having a hydroxyl group at the terminal (polyether polyol) and a polyether polymer having an amino group and / or an imino group at the terminal (polyether amine). ), Polyacrylic polyol, polyester polyol, diene-based polymer having a hydroxyl group at the terminal (polydiene polyol), saturated hydrocarbon-based polymer having a hydroxyl group at the terminal (polyolefin polyol), polythiol compound, polyamine compound and the like. Among these, the polyether polyol, the polyether amine, and the polyacrylic polyol have excellent compatibility with the component (A), the glass transition temperature of the organic polymer is relatively low, and the obtained adhesive layer is at a low temperature. It is preferable because it has excellent impact resistance. In particular, the polyether polyol and the polyether amine are more preferable because the viscosity of the obtained organic polymer is low and the workability is good, and the polyether polyol is particularly preferable.

As the organic polymer having an active hydrogen-containing group at the terminal, which is used when preparing the urethane prepolymer which is a precursor of blocked urethane (D), one type may be used alone or two or more types may be used in combination. You may.

The number average molecular weight of the organic polymer having an active hydrogen-containing group at the terminal is preferably 800 to 7000, more preferably 1500 to 5000, and particularly preferably 2000 to 4000, in terms of polystyrene-equivalent molecular weight measured by GPC.

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

R ¹ in the general formula (2) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the general formula (2) include -CH ₂ O-, -CH ₂ CH ₂ O-, -CH ₂ CH (CH ₃ ) O-, and -CH ₂ CH (C ₂ H _5). ) O-, -CH ₂ C (CH ₃ ) ₂ O-, -CH ₂ CH ₂ CH ₂ CH ₂ O- and the like. The main chain skeleton of the polyether polymer may consist of only one type of repeating unit or may consist of two or more types of repeating units. In particular, in a polyether polymer composed of a polymer containing polypropylene glycol as a main component, which has 50% by mass or more of repeating units of propylene oxide in 100% by mass of the organic polymer, the obtained cured product has a T-shaped peeling adhesive strength. It is preferable because it is excellent in. Further, polytetramethylene glycol (PTMG) obtained by ring-opening polymerization of tetrahydrofuran is preferable because the obtained cured product has excellent dynamic splitting resistance.

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

The blocked urethane (D) is preferably a compound in which a urethane prepolymer containing a polyalkylene glycol structure is capped with a blocking agent, and a compound in which a urethane prepolymer containing a polypropylene glycol structure is capped with a blocking agent. It is more preferable because the temperature-sensitive characteristics of the viscosity of the obtained curable resin composition are small.

"Small temperature sensitive characteristics of viscosity" means "small temperature dependence of viscosity".

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

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

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

(Polydiene polyol)
Examples of the polydiene polyol include polybutadiene polyol, polyisoprene polyol, and polychloroprene polyol. In particular, polybutadiene polyol is preferable.

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

(Polyisocyanate compound)
Specific examples of the polyisocyanate compound include (a) aromatic polyisocyanates such as toluene (toluene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; (b) isophorone diisocyanate, hexamethylene diisocyanate, hydrided toluene diisocyanate, and hydrogen. Examples thereof include aliphatic polyisocyanates such as diphenylmethane diisocyanate. Among these, aliphatic polyisocyanates are preferable from the viewpoint of heat resistance, and isophorone diisocyanates and hexamethylene diisocyanates are more preferable from the viewpoint of availability.

(Blocking agent having an active hydrogen group)
The blocking agent is, for example, a primary amine blocking agent, a secondary amine blocking agent, an oxime blocking agent, a lactam blocking agent, an active methylene blocking agent, an alcohol blocking agent, a mercaptan blocking agent, an amide. Examples thereof include system-based blocking agents, imide-based blocking agents, heterocyclic aromatic compound-based blocking agents, hydroxy-functional (meth) acrylate-based blocking agents, and phenol-based blocking agents. Among these, oxime-based blocking agents, lactam-based blocking agents, hydroxy-functional (meth) acrylate-based blocking agents and phenol-based blocking agents are preferable, and hydroxy-functional (meth) acrylate-based blocking agents and phenol-based blocking agents are more preferable. , Phenolic blocking agents are more preferred.

(Primary amine-based blocking agent)
Examples of the primary amine-based blocking agent include various compounds described in paragraph [0998] of the specification of WO2016-163491.

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

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

It is preferable that the blocking agent is bonded to the end of the polymer chain of the urethane prepolymer in such a manner that the end to which the blocking agent is bonded no longer has a reactive group. It can also be said that the polymer terminal obtained by binding the blocking agent to the end of the polymer chain of the urethane prepolymer preferably has no reactive group.

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

The blocked urethane (D) may contain a residue of a cross-linking agent, a residue of a chain extender, or both.

(Crosslinking agent)
The molecular weight of the cross-linking agent is preferably 750 or less, more preferably 50 to 500. The cross-linking agent is a polyol or polyamine compound having at least 3 hydroxyl groups, amino groups and / or imino groups per molecule. The cross-linking agent is useful for imparting branching to the blocked urethane (D) and increasing the functional value of the blocked urethane (D) (ie, the number of capped isocyanate groups per molecule).

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

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

(Content of blocked urethane (D))
When the present curable resin composition contains blocked urethane (D), the present curable resin composition further contains 1 part by mass to 100 parts by mass of the component (D) with respect to 100 parts by mass of the component (A). It is preferably contained in an amount of 2 to 50 parts by mass, more preferably 3 to 40 parts by mass, and particularly preferably 5 to 30 parts by mass. When the content of the component (D) is 1 part by mass or more of (a) with respect to 100 parts by mass of the component (A), the toughness of the obtained adhesive layer is good, and (b) 100 parts by mass or less. , The heat resistance and elastic modulus (rigidity) of the obtained adhesive layer are improved.

As the component (D), one type may be used alone, or two or more types may be used in combination.

(Inorganic filler (E))
The present curable resin composition may contain an inorganic filler (E). In the present specification, the above-mentioned fumed silica (C) is not included in the inorganic filler (E). The "inorganic filler (E)" may be hereinafter referred to as "component (E)".

When the present curable resin composition contains blocked urethane (D), it is preferable that the curable resin composition further contains an inorganic filler (E). Since the present curable resin composition contains the inorganic filler (E) in addition to the blocked urethane (D), the viscosity of the curable resin composition depends on the shear rate due to the inclusion of the component (D). The decline can be compensated for.

Examples of the inorganic filler (E) include silicic acid, silicate, reinforcing filler, calcium carbonate, magnesium carbonate, titanium oxide, ferric oxide, fine aluminum powder, zinc oxide, and active zinc oxide.

Examples of silicic acid and silicate include wet silica, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, and the like.

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

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

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

Examples of the surface treatment agent for the inorganic filler (E) include fatty acids and silane coupling agents.

The amount of the inorganic filler (E) used is preferably 1 to 200 parts by mass, more preferably 5 to 200 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 2 to 100 parts by mass with respect to 100 parts by mass of the component (A). 70 parts by mass is more preferable, 5 to 40 parts by mass is further preferable, and 7 to 20 parts by mass is particularly preferable.

One type of the inorganic filler (E) may be used alone, or two or more types may be used in combination.

(Calcium oxide)
When the curable resin composition contains calcium oxide as the inorganic filler (E), the calcium oxide removes water from the curable resin composition by reacting with water in the curable resin composition, and the presence of water is present. It can solve various physical problems caused by. Calcium oxide functions as, for example, an anti-bubble agent due to water removal, and can suppress a decrease in the adhesive strength of the obtained adhesive layer.

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 the surface-treated calcium oxide is used, the physical properties such as the adhesive strength of the obtained adhesive layer are improved as compared with the case where the surface-treated calcium oxide is used. The surface-treated calcium oxide can significantly improve the T-shaped peeling adhesiveness and the impact-resistant peeling adhesiveness of the obtained adhesive layer. The surface treatment agent that can be used for the surface treatment of calcium oxide is not particularly limited, but fatty acids are preferable.

When the curable resin composition contains calcium oxide as the inorganic filler (E), the content of calcium oxide in the curable resin composition is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Is preferable, 0.2 to 5 parts by mass is more preferable, 0.5 to 3 parts by mass is further preferable, and 1 to 2 parts by mass is particularly preferable. When the content of calcium oxide is (a) 0.1 parts by mass or more with respect to 100 parts by mass of the component (A), the water removing effect is sufficient, and (b) when it is 10 parts by mass or less, it is obtained. There is no risk of the strength of the adhesive layer being reduced.

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

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

The curable resin composition preferably has a value (X) represented by the following formula (1) of 25 or more:
Value (X) = {0.5 (V1) + 10 (V2) + (V3)} × 100 ... Equation (1)
(In the formula (1), the V1 represents the volume% of the polymer fine particles (B) in the curable resin composition, and the V2 is the fumed silica (C) in the curable resin composition. The volume% is shown, and V3 shows the volume% of the inorganic filler (E) in the curable resin composition).

The curable resin composition satisfying the above formula (1) has an advantage that the viscosity depends on the shear rate. The equation (1) will be specifically described. According to the present inventor, the contribution of fumed silica (C) to the improvement of the shear rate dependence of the viscosity of the curable resin composition is significantly larger than that of the polymer fine particles (B) and the inorganic filler (E). I found that on my own. The coefficient "+10" of the fumed silica (C) represents the magnitude of the contribution of such fumed silica (C).

The volume% of each component can be determined as follows: (1) The content of each component (compound) in the curable resin composition is divided by the specific gravity of each compound to obtain curability. The volume of each component in the resin composition is determined; (2) Next, the volume of each component obtained in (1) is divided by the total value of the volumes of all the components contained in the curable resin composition. Multiply the obtained value by 100. When the value (X) includes a numerical value after the decimal point, it is preferable that the integer value obtained by rounding off the first value after the decimal point is 25 or more.

In the present curable resin composition, the value (X) represented by the formula (1) is more preferably 26 or more, more preferably 27 or more, more preferably 30 or more, and 35. The above is more preferable, and 40 or more is particularly preferable.

The curable resin composition further comprises 1 part by mass to 100 parts by mass of blocked urethane (D) and 5 parts by mass to 200 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the epoxy resin (A). It is preferable that the value (X) represented by the above formula (1) is 25 or more. According to this structure, the obtained curable resin composition has an advantage that the viscosity has a higher shear rate dependence and can provide an adhesive layer having excellent toughness and extensibility.

(Epoxy resin curing agent (F))
In one embodiment of the present invention, the epoxy resin curing agent (F) can be used if necessary. The "epoxy resin curing agent (F)" may be hereinafter referred to as "component (F)".

A case where the present curable resin composition is temporarily used as a one-component composition (for example, a one-component curable resin composition) will be described. In this case, the type and amount of the component (F) should be selected so that the curable resin composition cures rapidly when the curable resin composition is heated to a temperature of 80 ° C. or higher, preferably 140 ° C. or higher. preferable. On the contrary, the component (F) and (G) described later so that the curable resin composition cures very slowly even if it cures at room temperature (about 22 ° C.) and at a temperature of at least 50 ° C. It is preferable to select the type and amount of ingredients.

As the component (F), a component that exhibits activity by heating (sometimes referred to as a latent epoxy curing agent) can be used. As such a latent epoxy curing agent, a nitrogen (N) -containing curing agent such as a specific amine-based curing agent (including an imine-based curing agent) can be used. Examples of the component (F) include boron trifluoride / amine complex, boron trifluoride / amine complex, dicyandiamide, melamine, diallyl melamine, guanamine (eg, acetguanamine and benzoguanamine), aminotriazole (eg, 3-amino-). 1,2,4-Triazole), hydrazide (eg, adipic acid dihydrazide, stearate dihydrazide, isophthalic acid dihydrazide, semicarbazide), cyanoacetamide, and aromatic polyamines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.) Can be mentioned. As the component (F), dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide, and 4,4'-diaminodiphenylsulfone are more preferably used, and dicyandiamide is particularly preferable, because they are excellent in adhesiveness.

Among the components (F) above, the latent epoxy curing agent is preferable because it enables the use of the present curable resin composition as a one-component curable resin composition.

Next, a case where the present curable resin composition is used as a two-component type or multi-component type composition will be described. In this case, amine-based curing agents (including imine-based curing agents) and / or mercaptan-based curing agents (sometimes referred to as room temperature curable curing agents) other than the above are active at a relatively low temperature of about room temperature (they are active at a relatively low temperature of about room temperature). F) It can be selected as a component.

Examples of the component (F) that exhibits activity at a relatively low temperature of about room temperature include amines such as polyamide amines, amine-terminated polyethers, amine-terminated rubbers, modified aliphatic polyamines, modified alicyclic polyamines, and polyamides. Examples include system curing agents and various compounds described in paragraph [0113] of the specification of WO2016-163491.

Amine-terminated polyethers containing a polyether main chain and having an average of 1 to 4 (preferably 1.5 to 3) amino groups and / or imino groups per molecule are also relatively at room temperature. It can be used as the component (F) that exhibits activity at low temperatures. Examples of commercially available amine-terminated polyethers include Huntsman's Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, and Jeffamine T-5000.

In addition, amine-terminated rubbers containing a conjugated diene polymer backbone and having an average of 1 to 4 (more preferably 1.5 to 3) amino and / or imino groups per molecule are also at room temperature. It can be used as the component (F) that exhibits activity at a relatively low temperature. Here, the main chain of 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 content of acrylonitrile monomer is 5 to 40% by mass (more preferably 10 to 35). Polybutadiene / acrylonitrile copolymers of% by weight, more preferably 15 to 30% by weight) are particularly preferred. Examples of commercially available amine-terminated rubber include Hyper 1300X16 ATBN manufactured by CVC.

Among the amine-based curing agents that show activity at a relatively low temperature of about room temperature, polyamide amines, amine-terminated polyethers, and amine-terminated rubbers are more preferable, and polyamide amines, amine-terminated polyethers, and amine-terminated rubbers. Is particularly preferable in combination with.

Further, among the components (F), acid anhydrides and phenols can also be used as the latent epoxy curing agent. Acid anhydrides and phenols require higher temperatures than amine-based curing agents, but have a long pot life, and the resulting adhesive layer has a balance of physical properties such as electrical properties, chemical properties, and mechanical properties. Becomes good. Examples of acid anhydrides include various compounds described in paragraph [0117] of the specification of WO2016-163491.

As the component (F), one type may be used alone, or two or more types may be used in combination.

The component (F) can be used in an amount sufficient to cure the curable resin composition. Typically, a sufficient amount of component (F) can be used to consume at least 80% of the epoxide groups present in the curable resin composition. Large excesses of component (F) that exceed the amount required to consume the epoxide group are usually not needed.

The present curable resin composition preferably further contains 1 to 80 parts by mass of the epoxy curing agent (F) with respect to 100 parts by mass of the epoxy resin (A), and preferably contains 2 to 40 parts by mass. It is more preferable to contain 3 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass. When the content of the component (F) is 1 part by mass or more of (a) with respect to 100 parts by mass of the component (A), the curability of the present curable resin composition becomes good, and (b) 80 parts by mass. When the following, the curable resin composition has an advantage that the storage stability is good and it is easy to handle.

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

The component (G) is a catalyst for accelerating the reaction between the epoxy group and the epoxide-reactive group contained in the curing agent and other components of the curable resin composition.

Examples of the component (G) include (a) p-chlorophenyl-N, N-dimethylurea (trade name: Mouron), 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: Chlortroluron), 1,1-dimethylphenylurea Ureas such as (trade name: Dyhard); (b) in benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol, poly (p-vinylphenol) matrix Incorporated tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, triethylenediamine, N, N-dimethylpiperidine; (c) C1-C12 alkyleneimidazole, N-arylimidazole, 2-methyl Imidazoles such as imidazole, 2-ethyl-2-methylimidazole, N-butyl imidazole, 1-cyanoethyl-2-undecyl imidazolium trimellitate, addition product of epoxy resin and imidazole; (d) 6-caprolactam , And so on. The catalyst may be encapsulated or may be a potential catalyst that becomes active only when the temperature is raised.

The tertiary amines and imidazoles can be used in combination with the amine-based curing agent of the component (F) (for example, the component (F) that exhibits activity at a relatively low temperature of about room temperature) to increase the curing rate and the adhesive layer obtained. Physical properties and heat resistance can be improved.

As the component (G), one type may be used alone, or two or more types may be used in combination.

The present curable resin composition preferably further contains 0.1 to 10.0 parts by mass of the curing accelerator (G) with respect to 100 parts by mass of the epoxy resin (A), and 0.2 to 5. It is more preferably 0 parts by mass, further preferably 0.5 to 3.0 parts by mass, and particularly preferably 0.8 to 2.0 parts by mass. When the content of the component (G) is 0.1 part by mass or more of (a) with respect to 100 parts by mass of the component (A), the curability of the present curable resin composition becomes good, and (b) 10 When the amount is 0.0 parts by mass or less, the curable resin composition has an advantage that the storage stability is good and it is easy to handle.

(Other ingredients)
In one embodiment of the present invention, other compounding ingredients can be used, if necessary. Other ingredients include radical curable resins, monoepoxides, photopolymerization initiators, organic fillers, pigments, flame retardants, dispersants, defoaming agents, plasticizers, solvents, tackifiers, leveling agents, and thixo. Sex-imparting agents, antioxidants, light stabilizers, UV absorbers, silane coupling agents, titanate-based coupling agents, aluminate-based coupling agents, mold release agents, antistatic agents, lubricants, low shrinkage agents, azotype chemistry Examples thereof include a specific foaming agent and a swelling agent such as a thermostable microballoon, a fiber pulp such as an aramid-based pulp, and a thermoplastic resin.

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

The present curable resin composition may contain a rubber-modified epoxy resin and / or a urethane-modified epoxy resin as other compounding components. When the present curable resin composition contains a rubber-modified epoxy resin and / or a urethane-modified epoxy resin, the curable resin composition has performances such as toughness, impact resistance, shear adhesiveness and peeling adhesiveness. An even better adhesive layer can be provided. The rubber-modified epoxy resin and / or the urethane-modified epoxy resin can also be said to be a reinforcing agent.

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

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

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

(Viscosity shear rate dependence)
It is preferable that the viscosity of the present curable resin composition is highly dependent on the shear rate. The higher the shear rate dependence of the viscosity of the curable resin composition, the more excellent the shower resistance of the curable resin composition. Therefore, the higher the shear rate dependence of the viscosity of the curable resin composition, the more excellent the workability of the method for producing a structure using the curable resin composition. 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 5s ^-1 to the viscosity at a shear rate of 50s ^-1 . The "ratio of the viscosity at a shear rate of 5s ^-1 to the viscosity at a shear rate of 50s ^-1 " is sometimes referred to as a "shear velocity-dependent viscosity ratio (5s ^-1 / 50s ^-1 )". .. The larger the value of the shear rate-dependent viscosity ratio (5s ^-1 / 50s ^-1 ) of the curable resin composition, the higher the shear rate dependence of the viscosity of the curable resin composition.

The shear rate-dependent viscosity ratio (5s ^-1 / 50s ^-1 ) of the present curable resin composition is preferably larger than 1.7, more preferably 1.8 or more, more preferably 1.9 or more, and 2 9.0 or more is more preferable, 3.0 or more is more preferable, 4.0 or more is more preferable, 5.0 or more is further preferable, and 6.0 or more is particularly preferable.

(Temperature dependence of viscosity)
It is preferable that the temperature dependence of the viscosity of the present curable resin composition is small. The smaller the temperature dependence of the viscosity of the curable resin composition, the more excellent the workability of the method for producing a structure using the curable resin composition. The temperature dependence of the viscosity of the curable resin composition can be evaluated by the ratio of the viscosity at 60 ° C. to the viscosity at 25 ° C. The "ratio of the viscosity at 60 ° C. to the viscosity at 25 ° C." is sometimes referred to as the "temperature-dependent viscosity ratio (60 ° C./25 ° C.)". The larger the value of the temperature-dependent viscosity ratio (60 ° C./25 ° C.) of the curable resin composition, in other words, the closer it is to 1, the smaller the temperature dependence of the viscosity of the curable resin composition.

The temperature-dependent viscosity ratio (60 ° C./25 ° C.) of the present curable resin composition is preferably 0.03 or more, more preferably 0.05 or more, further preferably 0.07 or more, and particularly 0.10 or more. preferable.

The specific method for measuring the viscosity of the curable resin composition will be described in detail in the following examples.

(Yield Stress)
The shower resistance of the present curable resin composition can also be evaluated by Yield Stress. The Yield Stress of the present curable resin composition is preferably high. The higher the Yield Stress of the curable resin composition, the better the shower resistance of the curable resin composition. Therefore, the higher the Yield Stress of the curable resin composition, the more excellent the workability of the method for producing a structure using the curable resin composition. A specific method for measuring Yield Stress of the curable resin composition will be described in detail in the following Examples.

The Yield Stress of the present curable resin composition is preferably 3 or more, more preferably 5 or more, more preferably 10 or more, more preferably 30 or more, further preferably 50 or more, and particularly preferably 100 or more.

(Manufacturing method of curable resin composition)
The present curable resin composition contains a composition containing polymer fine particles (B) in a curable resin containing the component (A) as a main component, and preferably the polymer fine particles (B) are contained in the component (A). Contains a composition dispersed in the form of primary particles. The "composition in which the polymer fine particles (B) are dispersed in the component (A) in the form of primary particles" may be hereinafter referred to as "polymer fine particle composition".

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

Specific methods for producing the polymer fine particle composition include, in order, (1) an aqueous latex containing the polymer fine particles (B) (specifically, a reaction mixture after producing the polymer fine particles (B) by emulsification polymerization). The first step of mixing with an organic solvent having a solubility in water at 20 ° C. of 5% by mass or more and 40% by mass or less, and then mixing the obtained mixture with excess water to agglomerate the polymer fine particles (B). (2) After separating and recovering the agglomerated polymer fine particles (B) from the liquid phase, the polymer fine particles (B) are mixed with the organic solvent again to obtain an organic solvent solution in which the polymer fine particles (B) are dispersed. Examples thereof include a second step and a third step of (3) further mixing the obtained organic solvent solution with the component (A) and then distilling off the organic solvent from the mixture. The polymer fine particle composition is preferably prepared by this method.

The component (A) is preferably liquid at 23 ° C. because the third step is facilitated. "Component (A) is liquid at 23 ° C." means that the softening point of component (A) is 23 ° C. or lower, and component (A) exhibits fluidity at 23 ° C. Intended to be.

By further adding the component (C) to the polymer fine particle composition obtained through the above steps (first step to third step) and mixing the polymer fine particles (B), the polymer fine particles (B) are contained in the component (A). The present curable resin composition dispersed in the state of primary particles can be obtained. In the production of the present curable resin composition, the component (A) may be further added and mixed with the polymer fine particle composition if necessary. Further, in the production of the present curable resin composition, each component of the component (D), the component (E), and the other compounding components may be further added and mixed with the polymer fine particle composition, if necessary. ..

On the other hand, the polymer fine particles (B) are coagulated by a method such as salting out using an aqueous latex containing the polymer fine particles (B), and then the obtained coagulated product is dried to obtain powdery polymer fine particles (B). ) Can be obtained. The polymer fine particle composition is obtained by redispersing the powdery polymer fine particles (B) in the component (A) using a disperser having a high mechanical shearing force such as three paint rolls, a roll mill, and a kneader. It is also possible to manufacture. At this time, by applying a mechanical shearing force to the mixture of the component (A) and the component (B) at a high temperature, the component (B) can be efficiently dispersed in the component (A). The temperature at the time of dispersion (the temperature at which a shearing force is applied) is preferably 50 to 200 ° C., more preferably 70 to 170 ° C., further preferably 80 to 150 ° C., and particularly preferably 90 to 120 ° C. When the temperature at the time of dispersion is (a) 50 ° C. or higher, the component (B) can be sufficiently dispersed, and when (b) 200 ° C. or lower, the components (A) and (B) are sufficiently dispersed. There is no risk of thermal deterioration.

(Use of curable resin composition)
The curable resin composition can be used as a one-component curable resin composition. A one-component curable resin composition containing the above-mentioned curable resin composition can also be said to be an embodiment of the present invention. The one-component curable resin composition can be (i) pre-blended with all the ingredients and then sealed and stored without curing, and (ii) after applying the curable resin composition, heating and heating. / Or means a curable resin composition that is cured by light irradiation.

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

This curable composition is particularly beneficial when used as a one-component curable resin composition because it has excellent storage stability. Since the present curable resin composition is excellent in handleability, it is preferably a one-component curable resin composition.

This curable resin composition is useful as an adhesive. This curable resin composition is excellent in adhesive performance and flexibility not only at low temperature (about −20 ° C.) to room temperature (for example, 15 ° C. to 30 ° C.) but also at high temperature (about 80 ° C.). Therefore, the present curable resin composition can be more preferably used as a structural adhesive. An adhesive containing the above-mentioned curable resin composition or a structural adhesive can also be said to be an embodiment of the present invention.

(Subject)
Various structures can be manufactured by using the method for manufacturing a structure according to an embodiment of the present invention. In other words, various adherends can be adhered using the method for producing a structure according to an embodiment of the present invention. The "adhesive body" may also be referred to as a "board" or "adhesive board".

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

This curable resin composition has excellent adhesiveness. Therefore, the curable resin composition according to the embodiment of the present invention is sandwiched and bonded between a plurality of members including an aluminum base material, and then the curable resin composition is cured. A laminate formed by joining members is preferable because it exhibits high adhesive strength.

Since this curable resin composition has excellent toughness, it is suitable for joining different adherends having different linear expansion coefficients. In other words, it is preferable that the first adherend and the second adherend are different types of adherends having different coefficients of linear expansion.

The curable resin composition can also be used for joining aerospace components, especially exterior metal components.

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

(Adhesive layer)
When the adherends are adhered to each other using the present curable resin composition, an adhesive layer obtained by curing the curable resin composition is formed between the adherends. The adhesive layer can be said to be a cured product obtained by curing the curable resin composition. An adhesive layer or a cured product obtained by curing the above-mentioned curable resin composition can also be said to be an embodiment of the present invention.

The adhesive layer obtained by curing the present curable resin composition has (a) a beautiful surface, (b) high rigidity and high elastic modulus, and (c) toughness and adhesiveness (particularly impact-resistant peeling adhesion). It is excellent in sex).

In this curable resin composition, the polymer fine particles (B) are uniformly dispersed in the component (A) in the form of primary particles. Therefore, by curing the curable resin composition, an adhesive layer in which the polymer fine particles (B) are uniformly dispersed can be easily obtained. Further, in the present curable resin composition, the polymer fine particles (B) are difficult to swell, and the viscosity of the curable resin composition is low. Therefore, the adhesive layer can be obtained with good workability. In other words, by using the present curable resin composition, the adherend can be adhered with good workability, that is, a method for producing a structure with good workability can be provided.

When the curable resin composition is used as an adhesive for vehicles, the above-mentioned "difficulty in washing off the curable resin composition in the washing shower process" (hereinafter referred to as "difficulty in washing off"). It is effective to increase the viscosity of the curable resin composition in order to improve the above. This curable resin composition has an excellent "difficulty in being washed off" because the viscosity is highly dependent on the shear rate and tends to have a high viscosity. 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 coatable viscosity by heating the curable resin composition.

Further, this curable resin composition is a polymer having a crystal melting point near the coating temperature of the curable resin composition, as described in WO2005-118734, in order to improve "difficulty in being washed off". It is preferable that the compound is further contained. A curable resin composition further containing a polymer compound having a crystal melting point near the coating temperature of the curable resin composition is easy to coat because (a) the viscosity is low at the coating temperature, and (b) the temperature in the washing shower step. At (for example, a temperature lower than the coating temperature), the viscosity becomes high and the "difficulty of being washed off" is improved. In general, the coating temperature is higher than the flush shower temperature. Examples of the polymer compound having a crystal melting point near the coating temperature of the curable resin composition include various polyester resins such as crystalline or semi-crystalline polyester polyols.

Further, as another method for improving "difficulty in being washed off", the following methods can be mentioned as described in WO2006-093949: The curable resin composition is referred to as a two-component curable resin composition. Then, as the curing agent to be used, a small amount of a curing agent capable of curing at room temperature (room temperature curing curing agent) such as an amine-based curing agent having an amino group or an imino group is used, and there is a potential such as dicyandiamide which exhibits activity at a high temperature. This is a method in which a sex curing agent is used in combination with a room temperature curing curing agent. In this method, by using two or more kinds of curing agents having significantly different curing temperatures, partial curing proceeds immediately after application of the curable resin composition, and the viscosity becomes high at the time of the washing shower step, so that the curing property is curable. The "difficulty of being washed off" of the resin composition is improved.

(2-7. Manufacturing method of structure)
Hereinafter, specific aspects of the steps included in the method for manufacturing a structure according to an embodiment of the present invention will be described.

<Lasting process>
The bonding step is a step of applying the curable resin composition to the first adherend and then laminating the second adherend to the first adherend. At this time, the first adherend of the first adherend is sandwiched between the first adherend and the second adherend so that the curable resin composition applied to the first adherend is sandwiched between the first adherend and the second adherend. And stick together. Further, at this time, the curable resin composition sandwiched between the first adherend and the second adherend may protrude from the first adherend and / or the second adherend. .. Further, the curable resin composition may be applied to the second adherend, if necessary, in addition to the application to the first adherend.

This curable resin composition can be applied by any method.

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

The viscosity of the curable resin composition is not particularly limited. The viscosity of the curable resin composition is preferably about 150 to 600 Pa · s at 45 ° C. in the (a) extruded bead method, and about 100 Pa · s at 45 ° C. in the (b) swirl coating method. (C) In the high volume coating method using a high speed flow device, about 20 to 400 Pa · s at 45 ° C. is preferable.

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

The first temperature may be room temperature. The first temperature is preferably higher than room temperature. In the present specification, "room temperature" is usually 5 ° C to 45 ° C, preferably 10 ° C to 40 ° C, more preferably 15 ° C to 34 ° C, and most preferably 20 ° C to 30 ° C. Is.

In the bonding step, the first temperature (the temperature of the curable resin composition when applied to the first adherend) is preferably, for example, 35 ° C to 80 ° C, preferably 40 ° C to 70 ° C. Is more preferable, and 45 ° C. to 60 ° C. is particularly preferable. When the first temperature is (a) 35 ° C. or higher, the viscosity of the composition is low, which has the advantage of facilitating the coating operation. When (b) 80 ° C. or lower, the epoxy resin (A) ) Will not start to react and the viscosity will increase, which has the advantage of facilitating the coating operation.

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

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

In the bonding step, the curable resin composition applied to the first adherend at the first thickness is before the first adherend and the second adherend are bonded together, or the first When the adherend of No. 1 and the second adherend are bonded together, they may be thinner than the first thickness and may be stretched. The thickness of the curable resin composition after being stretched is also referred to as a "second thickness".

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

In the bonding step, the specific method for stretching the curable resin composition applied to the first thickness to the second thickness is not particularly limited. As the method, for example, (i) a curable resin composition coated with the first thickness is applied with a spatula or the like before the first adherend and the second adherend are bonded together. , A method of stretching to a second thickness, and (ii) when the second adherend is attached to the first adherend coated with the curable resin composition, the curable resin composition is sandwiched between them. Examples thereof include a method in which the curable resin composition applied to the first thickness is spread and stretched by the two adherends to the second thickness by bringing these two adherends close to each other in the state.

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

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

The second temperature is, for example, preferably 0 ° C. to 34 ° C., more preferably 5 ° C. to 30 ° C., and particularly preferably 10 ° C. to 25 ° C. When the second temperature is (a) 0 ° C. or higher, the viscosity of the curable resin composition is lowered, so that there is an advantage that the work of stretching to the second thickness becomes easy, and (b) 34 ° C. or lower. If this is the case, there is no risk that the storage stability of the curable resin composition will deteriorate when it is stored for a long period of time.

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

<Washing process>
In the washing step, the bonded body obtained in the bonding step is washed.

The cleaning solution is not particularly limited. As the cleaning liquid, an aqueous solution containing water, an acid or an alkali can be preferably exemplified.

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

The cleaning method of the bonded body is not particularly limited, and examples thereof include a method of immersing the bonded body in the cleaning liquid and a method of spraying (showing) the cleaning liquid on the bonded body.

The pressure of the cleaning liquid when spraying the cleaning liquid onto the bonded body is not particularly limited. The pressure (water pressure) of the cleaning liquid may be 0.1 MPa to 1.0 MPa, 0.1 MPa to 0.5 MPa, or 0.2 MPa to 0.4 MPa. The higher the pressure of the cleaning liquid, the higher the cleaning effect (a) can be obtained, and (b) the risk of scattering and deformation of the applied curable resin composition increases. Therefore, the pressure of the cleaning liquid can be appropriately determined in consideration of the balance between the cleaning effect and the scattering and deformation of the curable resin composition. The present curable resin composition has the advantages that the viscosity has a high shear rate dependence and the Yield Stress value is high. Therefore, in the present production method, the cleaning liquid can be sprayed onto the adherend under higher pressure conditions as compared with the case where the conventional curable resin composition is used.

In the washing process, the object to be washed, that is, to be washed off is not particularly limited. Examples of the object to be washed off in the washing step include rust preventive oil previously applied to the raw material of the adherend.

<Curing process>
The curing step is a step of curing the curable resin composition sandwiched between the two bonded bodies. By the curing step, it is possible to obtain a structure in which the two adherends are bonded by the curable resin composition.

<Curing temperature>
In the curing step, the curing temperature of the present curable resin composition is not particularly limited. In the curing step, the curing temperature of the present curable resin composition is preferably 50 ° C. to 250 ° C., more preferably 80 ° C. to 220 ° C., and even more preferably 100 ° C. to 200 ° C. It is particularly preferably 130 ° C. to 180 ° C. The "curing temperature" can also be said to be the temperature exhibited by the heated curable resin composition in the curing step.

<Paint application process>
The present manufacturing method may further include a paint application step of applying the paint to the laminated body. The coating step can be carried out at any stage. The coating step is preferably carried out after the cleaning step and before the curing step. When the coating step is carried out after the cleaning step, it has the advantage of good coatability. When the coating liquid contains a curable resin and the coating step is performed before the curing step, the coating material can be cured at the same time as the curing of the curable resin composition.

The paint is not particularly limited, but examples thereof include the following: rust preventives, pigments, matting agents, gloss-imparting agents and antireflection agents.

(Structure)
The method for producing a structure according to an embodiment of the present invention can be used for producing various structures. It can be said that the structure obtained by the method for producing a structure according to an embodiment of the present invention contains at least two adherends and the present curable resin composition. The structure obtained by the method for producing a structure according to an embodiment of the present invention exhibits high adhesive strength.

The structures obtained by the method for manufacturing a structure according to an embodiment of the present invention include, for example, automobiles and vehicles (bullet trains, trains, etc.), aircraft, spacecraft, space stations, buildings, buildings, and wind farms. And so on.

One embodiment of the present invention may have the following configuration.

[1] Obtained in a bonding step of applying the curable resin composition to the first adherend and bonding the second adherend to the first adherend, and the bonding step. The curable resin composition comprises a cleaning step of cleaning the bonded body and a curing step of curing the curable resin composition, and the curable resin composition includes an epoxy resin (A) and 100 mass of the epoxy resin (A). 1 part to 100 parts by mass of the polymer fine particles (B) containing a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body and containing a hydroxy group. , And a method for producing a structure containing 1 part to 30 parts by mass of fumed silica (C).

[2] The production of the structure according to [1], wherein the curable resin composition substantially does not contain blocked urethane (D) with respect to 100 parts by mass of the epoxy resin (A). Method.

[3] The curable resin composition further comprises 1 part by mass to 100 parts by mass of the blocked urethane (D) and 5 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the epoxy resin (A). The method for producing a structure according to [1], which contains ~ 200 parts by mass and has a value (X) of 25 or more represented by the following formula (1):
Value (X) = {0.5 (V1) + 10 (V2) + (V3)} × 100 ... Equation (1)
(In the formula (1), the V1 represents the volume% of the polymer fine particles (B) in the curable resin composition, and the V2 is the fumed silica (C) in the curable resin composition. The volume% is shown, and V3 shows the volume% of the inorganic filler (E) in the curable resin composition).

[4] The method for producing a structure according to [3], wherein the inorganic filler (E) contains calcium carbonate.

[5] Any of [1] to [4], wherein the curable resin composition further contains 1 to 80 parts by mass of the epoxy curing agent (F) with respect to 100 parts by mass of the epoxy resin (A). The method for manufacturing a structure according to one.

[6] The curable resin composition further contains 0.1 to 10 parts by mass of the curing accelerator (G) with respect to 100 parts by mass of the epoxy resin (A) [1] to [5]. The method for manufacturing a structure according to any one of the above.

[7] The method for producing a structure according to any one of [1] to [6], wherein the elastic body is butadiene rubber and / or butadiene-styrene rubber.

[8] The graft portion is a polymer containing a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and a (meth) acrylate monomer as a structural unit. The method for producing a structure according to any one of [1] to [7].

[9] The method for producing a structure according to any one of [1] to [8], wherein the graft portion is a polymer having an epoxy group.

[10] The production of the structure according to any one of [1] to [9], wherein the blocked urethane (D) is a compound in which a urethane prepolymer containing a polyalkylene glycol structure is capped with a blocking agent. Method.

[11] In the bonding step, the temperature of the curable resin composition applied to the first adherend is 35 ° C to 80 ° C, any one of [1] to [10]. The method for manufacturing a structure according to.

[12] The method for producing a structure according to any one of [1] to [11], wherein in the curing step, the curing temperature of the curable resin composition is 50 ° C to 250 ° C.

Hereinafter, one embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. One embodiment of the present invention can be carried out by appropriately modifying the following examples to the extent that it can be adapted to the above-mentioned and the purposes described below. The embodiments in which the following examples are appropriately modified are included in the technical scope of the present invention. In the following Examples, Comparative Examples and Tables, "parts" and "%" mean parts by mass and% by mass, respectively.

(Evaluation methods)
First, the evaluation method of the curable resin composition produced by Examples and Comparative Examples will be described below.

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

[2] Measurement of Viscosity Using a rheometer, the viscosities of the curable resin compositions obtained in Examples and Comparative Examples at 50 ° C. were measured at shear rates of 5s ^-1 and 50s ^-1 . In the present specification, when the value of the ratio of the viscosity of 5s ^{-1 to} the viscosity of 50s ^-1 (viscosity ratio (5s ^-1 / 50s ^-1 )) is 1.9 or more, it is regarded as ◯ (good) and 1 When it was less than 0.9, it was evaluated as × (defective). The test results are shown in Tables 1-9.

Further, using a rheometer, the viscosities of the curable resin compositions obtained in Examples and Comparative Examples at a shear rate of 5s- ¹ were measured at 60 ° C. and 25 ° C. The larger the value of the ratio of the viscosity at 60 ° C. to the viscosity at 25 ° C. (closer to 1), the smaller the temperature dependence of the viscosity, and the better the workability. The test results are shown in Tables 5-8.

[3] Measurement of Yield Stress Using a rheometer, the yield stress (Yield Stress) of each curable resin composition obtained in Examples and Comparative Examples at 50 ° C. was measured. The test results are shown in Tables 5-8.

1. 1. Formation of elastic body Production Example 1-1; Preparation of polybutadiene rubber latex (R-1) In a pressure-resistant polymerizer having a volume of 100 L, 200 parts by mass of deionized water, 0.03 parts by mass of tripotassium phosphate, and dihydrogen phosphate. 0.25 parts by mass of potassium, 0.002 parts by mass of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by mass of ferrous sulfate heptahydrate (FE) and sodium dodecylbenzene sulfonate (SDS) 1 as an emulsifier .5 parts by mass was charged. 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 charged raw materials. Then, 100 parts by mass of butadiene (BD) was put into the pressure-resistant polymerizer, and the temperature inside the pressure-resistant polymerizer was raised to 45 ° C. After that, 0.015 parts by mass of paramentan hydroperoxide (PHP) was charged into the pressure-resistant polymerizer, and then 0.04 parts by mass of sodium formaldehyde sulfoxylate (SFS) was charged into the pressure-resistant polymerizer to carry out the polymerization. It started. Ten hours after the start of the polymerization, the polymerization was completed by devolatile under reduced pressure to remove the residual monomer that was not used in the polymerization. During the polymerization, each of PHP, EDTA and FE was added into the pressure resistant polymerizer in any amount and at any time. By the polymerization, a latex (R-1) containing an elastic body (polybutadiene rubber particles) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.10 μm.

Production Example 1-2; Preparation of Polybutadiene Rubber Latex (R-2) In a pressure-resistant polymerization machine having a volume of 100 L, the polybutadiene rubber latex (R-1) obtained in Production Example 1-1 was removed by 7 parts by mass in terms of solid content. 200 parts by mass of ionized water, 0.03 parts by mass of tripotassium phosphate, 0.002 parts by mass of EDTA, and 0.001 part by mass 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 charged raw materials. Then, 93 parts by mass of BD was put into the pressure-resistant polymerizer, and the temperature inside the pressure-resistant polymerizer was raised to 45 ° C. Then, 0.02 part by mass of PHP was put into the pressure-resistant polymerizer, and then 0.10 part by mass of SFS was put into the pressure-resistant polymerizer to start polymerization. Thirty hours after the start of the polymerization, the polymerization was completed by devolatile under reduced pressure to remove the residual monomer that was not used in the polymerization. During the polymerization, each of PHP, EDTA and FE was added into the pressure resistant polymerizer in any amount and at any time. By the polymerization, a latex (R-2) containing an elastic body (polybutadiene rubber particles) containing polybutadiene rubber as a main component was obtained. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 0.20 μm.

2. Preparation of polymer fine particles (formation of graft part)
Production Example 2-1; Preparation of Polymer Fine Particle Latex (L-1) A glass reactor contains 271 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (90 parts by mass of polybutadiene rubber particles). ) And 51 parts by mass of deionized water were added. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the raw material charged at 60 ° C. was stirred while performing the nitrogen substitution. Next, 0.004 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.2 parts by mass of SFS were added into the glass reactor. Then, a monomer for forming a graft portion (hereinafter, also referred to as a graft monomer) (6 parts by mass of methyl methacrylate (MMA), 2 parts by mass of glycidyl methacrylate (GMA) and 2 parts by mass of 4-hydroxybutyl acrylate (4HBA)). And 0.08 parts by mass of cumene hydroperoxide (CHP) were continuously added into a glass reactor over 120 minutes. After completion of the addition, 0.04 parts by mass of CHP was added into the glass reactor, and the mixture in the glass reactor was continuously stirred for 2 hours to complete the polymerization. By the above operation, an aqueous latex (L-1) containing the polymer fine particles (B) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 1.4 mmol / g.

Production Example 2-2; Preparation of Polymer Fine Latex (L-2) In Production Example 2-1 as graft monomers, <MMA 8 parts by mass, GMA 2 parts by mass and 4HBA 2 parts by mass> are replaced with <MMA 8 parts by mass and GMA 2 parts by mass. > Was used to obtain an aqueous latex (L-2) containing polymer fine particles by the same method as in Production Example 2-1. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 0 mmol / g.

Production Example 2-3; Preparation of Polymer Fine Particle Latex (L-3) The glass reactor contains 262 parts by mass of the polybutadiene rubber latex (R-2) prepared in Production Example 1-2 (87 parts by mass of polybutadiene rubber particles). ) And 57 parts by mass of deionized water were added. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the raw material charged at 60 ° C. was stirred while performing the nitrogen substitution. Next, 0.004 parts by mass of EDTA, 0.001 parts by mass of FE, and 0.13 parts by mass of SFS were added into the glass reactor. Then, a mixture of the graft monomer (3 parts by mass of MMA, 7 parts by mass of butyl acrylate (BA), 2 parts by mass of GMA and 1 part by mass of hydroxyethyl methacrylate (HEMA)) and 0.04 part by mass of cumenehydroperoxide (CHP) was added. It was continuously added to a glass reactor over 120 minutes. After completion of the addition, 0.04 parts by mass of CHP was added into the glass reactor, and the mixture in the glass reactor was continuously stirred for 2 hours to complete the polymerization. By the above operation, an aqueous latex (L-3) containing the polymer fine particles (B) was obtained. The polymerization conversion rate of the monomer component was 99% or more. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 0.59 mmol / g.

Production Example 2-4; Preparation of Polymer Fine Particle Latex (L-4) In Production Example 2-3, 3 parts by mass of MMA, 7 parts by mass of BA, 2 parts by mass of GMA and 1 part by mass of HEMA are used as graft monomers. , BA 7 parts by mass, GMA 2 parts by mass and 4HBA 1 part by mass> were obtained in the same manner as in Production Example 2-3 to obtain an aqueous latex (L-4) containing polymer fine particles (B). The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 0.53 mmol / g.

Production Example 2-5; Preparation of Polymer Fine Particle Latex (L-5) In Production Example 2-3, 10 parts by mass of MMA instead of <3 parts by mass of MMA, 7 parts by mass of BA, 2 parts by mass of GMA and 1 part by mass of HEMA> as graft monomers. , GMA 2 parts by mass and 4HBA 1 part by mass> were used to obtain an aqueous latex (L-5) containing the polymer fine particles (B) by the same method as in Production Example 2-3. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 0.53 mmol / g.

Production Example 2-6; Preparation of Polymer Fine Particle Latex (L-6) In Production Example 2-3, 7 parts by mass of MMA, 7 parts by mass of BA, 2 parts by mass of GMA and 1 part by mass of HEMA are used as graft monomers. , BA3 part by mass, GMA2 part by mass and 4HBA1 part by mass> were obtained, and an aqueous latex (L-6) containing polymer fine particles (B) was obtained by the same method as in Production Example 2-3. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 0.53 mmol / g.

Production Example 2-7; Preparation of Polymer Fine Particle Latex (L-7) In Production Example 2-3, 9 parts by mass of MMA instead of <3 parts by mass of MMA, 7 parts by mass of BA, 2 parts by mass of GMA and 1 part by mass of HEMA> as graft monomers. , GMA 2 parts by mass and 4HBA 2 parts by mass> were used to obtain an aqueous latex (L-7) containing the polymer fine particles (B) by the same method as in Production Example 2-3. The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 1.1 mmol / g.

Production Example 2-8; Preparation of Polymer Fine Particle Latex (L-8) In Production Example 2-3, 6 parts by mass of MMA instead of <3 parts by mass of MMA, 7 parts by mass of BA, 2 parts by mass of GMA and 1 part by mass of HEMA> as graft monomers. , BA3 parts by mass, GMA2 parts by mass and 4HBA2 parts by mass> were obtained in the same manner as in Production Example 2-3 to obtain an aqueous latex (L-8) containing polymer fine particles (B). The volume average particle size of the polymer fine particles contained in the obtained aqueous latex was 0.21 μm. The content of the hydroxy group with respect to the total mass of the graft portion in the obtained polymer fine particles was 1.1 mmol / g.

3. 3. Preparation of polymer fine particles (B) or dispersion (M) in which polymer fine particles are dispersed in a curable resin Production Example 3-1; Preparation of dispersion (M-1) 132 g of methyl ethyl ketone (MEK) in a 1 L mixing tank at 25 ° C. Was introduced. Next, while stirring 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 the raw materials in the mixing tank were uniformly mixed, 200 g of water was added into the mixing tank at a supply rate of 80 g / min while stirring the raw materials in the mixing tank. After the water supply was completed, the stirring was immediately stopped to obtain a slurry liquid consisting of an aggregate containing the polymer fine particles (B) and an aqueous phase containing a small amount of an organic solvent. The aggregate was buoyant. Next, 360 g of the aqueous phase was discharged from the discharge port at the bottom of the mixing tank so that the agglomerates containing a part of the aqueous phase remained in the mixing tank. 90 g of MEK was added to the obtained aggregate and these were uniformly mixed to obtain a dispersion in which the polymer fine particles (B) were uniformly dispersed in the MEK. To the obtained dispersion, 60 g of the epoxy resin (A-1) as the component (A) was added, and these were uniformly mixed. The epoxy resin (A-1) will be described in detail below. MEK was removed from the resulting mixture using a rotary evaporator. In this way, a dispersion (M-1) in which the polymer fine particles (B) were dispersed in the epoxy resin (A) was obtained. The epoxy resin (A) was 60% by weight and the polymer fine particles (B) were 40% by weight in 100% by weight of the dispersion (M-1).

Production Example 3-2; Preparation of dispersion (M-2) In Production Example 3-1 as an aqueous latex containing polymer fine particles, 132 g of (L-2) (equivalent to 40 g of polymer fine particles) instead of 132 g of (L-1). A dispersion (M-2) in which polymer fine particles were dispersed in the epoxy resin (A) was obtained by the same method as in Production Example 3-1 except that the above was used.

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

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

Production Example 3-5; Preparation of dispersion (M-5) In Production Example 3-1 as an aqueous latex containing polymer fine particles (B), 132 g of (L-5) (polymer fine particles) was used instead of 132 g of (L-1). A dispersion (M-5) in which the polymer fine particles (B) were dispersed in the epoxy resin (A) was obtained by the same method as in Production Example 3-1 except that (B) equivalent to 40 g) was used.

Production Example 3-6; Preparation of Dispersion (M-6) In Production Example 3-1 as an aqueous latex containing polymer fine particles (B), 132 g of (L-6) (polymer fine particles) was used instead of 132 g of (L-1). A dispersion (M-6) in which the polymer fine particles (B) were dispersed in the epoxy resin (A) was obtained by the same method as in Production Example 3-1 except that (B) equivalent to 40 g) was used.

Production Example 3-7; Preparation of dispersion (M-7) In Production Example 3-1 as the aqueous latex containing the polymer fine particles (B), 132 g (L-7) (polymer fine particles) instead of 132 g of (L-1). A dispersion (M-7) in which the polymer fine particles (B) were dispersed in the epoxy resin (A) was obtained by the same method as in Production Example 3-1 except that (B) equivalent to 40 g) was used.

Production Example 3-8; Preparation of Dispersion (M-8) In Production Example 3-1 as an aqueous latex containing polymer fine particles (B), 132 g of (L-8) (polymer fine particles) was used instead of 132 g of (L-1). A dispersion (M-8) in which the polymer fine particles (B) were dispersed in the epoxy resin (A) was obtained by the same method as in Production Example 3-1 except that (B) equivalent to 40 g) was used.

(Examples 1 to 36, Comparative Examples 1 to 12)
Each component was weighed according to the formulations (blending) shown in Tables 1 to 9 and mixed sufficiently to obtain a curable resin composition. Tables 1 to 9 show the viscosities of the obtained curable resin composition and the test results of Yield Stress. The value X in the curable resin composition was calculated from the amount of each component added in the table and the value of the specific gravity of each component described later.

The various compounding agents shown in Tables 1 to 9 were used.
<Epoxy resin (A)>
A-1: JER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin liquid at room temperature, epoxy equivalent: 184 to 194) [specific gravity: 1.16]
<Dispersion (M) in which polymer fine particles [specific gravity: 0.91] are dispersed in epoxy resins (A) and (A-1)> M-1 to M-8: Obtained in Production Examples 3-1 to 8 Dispersion <Fumed silica (C)>
CAB-O-SIL TS-720 (manufactured by CABOT, fumed silica surface-treated with polydimethylsiloxane) [specific gravity: 2.2]
<Blocked urethane (D)> [Specific gravity: 1.04]
C-1: QR-9466 (made by ADEKA, blocked urethane, latent NCO%: 3.0%, polystyrene-equivalent number average molecular weight by GPC: 7900)
C-2: Takenate B-7055 (Mitsui Chemicals, blocked urethane, latent NCO%: 2.0%, polystyrene-equivalent number average molecular weight by GPC: 12300)
C-3: Takenate B-7005 (Mitsui Chemicals, blocked urethane, latent NCO%: 2.7%, polystyrene-equivalent number average molecular weight by GPC: 7600)
C-4: Takenate B-7030 (Mitsui Chemicals, blocked urethane, latent NCO%: 3.4%, polystyrene-equivalent number average molecular weight by GPC: 6100)
<Inorganic filler (E)>
≪Heavy calcium carbonate≫
Shiraishi SB (made of Shiraishi calcium, surface-untreated heavy calcium carbonate, average particle size: 1.8 μm) [specific gravity: 2.7]
Ryton A (made of Shiraishi calcium, heavy calcium carbonate surface-treated with fatty acids, average particle size: 1.8 μm) [specific gravity: 2.7]
≪Calcium oxide≫
CML # 31 (manufactured by Omi Chemical Industry, calcium oxide surface-treated with fatty acids) [Specific gravity: 3.34]
<Epoxy resin curing agent (F)> [Specific gravity: 1.40]
Dyhard 100S (manufactured by AlzChem, dicyandiamide)
<Curing accelerator (G)> [Specific gravity: 1.12]
Dyhard UR300 (manufactured by AlzChem, 1,1-dimethyl-3-phenylurea)
<Other ingredients>
≪Carbon black≫
MONARCH 280 (manufactured by Cabot) [Specific gravity: 1.8]
≪Rubber-modified epoxy resin≫
Hyperx RA1340 (manufactured by CVC Thermoset Specialties) [Specific gravity: 1.08]

The amount (parts by mass) of the component (A) contained in the curable resin compositions of Tables 1 to 9 is the amount described in the columns of the components (a) and (A), that is, added as an epoxy resin (A). ) The amount of the component and the amount of the component (A) contained in the dispersion (M) described in the column of (b) component (A) + component (B) or the column of (A) component + polymer fine particles. It is the total amount.

From Tables 1, 2 and 5 to 9, the curable resin compositions of Examples 1 to 36 containing the components (A), (B) and (C) according to the embodiment of the present invention have shear rates. The dependent viscosity ratios (5s ^-1 / 50s ^-1 ) were all above good levels. Therefore, it can be seen that the present curable resin composition is excellent in workability because the viscosity has a large dependence on the shear rate.

It can be seen that the curable resin compositions of Example 1, Example 7, Example 11 and Example 36 which do not contain blocked urethane (D) have a large viscosity dependence on the shear rate and are excellent in workability.

The curable resin compositions of Examples 2 to 6, Examples 8 to 10 and Examples 12 to 35 containing the blocked urethane (D) depend on the shear rate of viscosity, particularly when the above formula (1) is satisfied. It can be seen that the property is large and the workability is excellent.

From Examples 31 to 36, it can be seen that the smaller the content of blocked urethane (D), the greater the dependence of viscosity on the shear rate and the better the workability.

Further, from Tables 5 to 8, the curable resin compositions of Examples 12 to 18, Examples 22 to 25 and Examples 29 to 30 have a high temperature-dependent viscosity ratio (60 ° C./25 ° C.) and workability. It turns out that it is excellent.

Further, from Tables 5 to 8, it can be seen that the curable resin compositions of Examples 12 to 18, Examples 22 to 25 and Examples 29 to 30 have high Yield Stress and excellent shower resistance.

A structure was produced using each of the curable resin compositions of Examples 1 to 36 and Comparative Examples 1 to 12. That is, (1) each of the curable resin compositions of Examples 1 to 36 and Comparative Examples 1 to 12 is applied to an aluminum base material (first adherend), and another aluminum base material (second adherend) is applied. The body) is bonded to an aluminum base material coated with each curable resin composition to carry out a bonding step, and then (2) the bonded body obtained in the bonding step is washed. The washing step was carried out, and (3) the curing step was carried out by curing the curable resin composition. The structure was manufactured by such a method. As a result, the production of the structure using the curable resin compositions of Examples 1 to 36 containing the components (A), (B) and (C) according to the embodiment of the present invention is workable. Was good. For the production of the structure using the curable resin compositions of Examples 1, 6, 7, 10, 11 and 33 to 36, the curable resin compositions of Examples 2 to 5, 8, 9, 31 and 32 were used. Workability was better than in the production of the structures used. Production of structures using the curable resin compositions of Examples 15, 16, 19-21, 23, 25-28 and 30 is the curability of Examples 12-14, 17, 18, 22, 24 and 29. The workability was better than that of the production of the structure using the resin composition.

According to one embodiment of the present invention, the curable resin composition has a small dependence on the shear rate of viscosity, and the method for producing a structure using the curable resin composition is excellent in workability. Therefore, the method for manufacturing a structure according to an embodiment of the present invention can be suitably used for bonding an iron plate, CFRP, an aluminum plate and concrete. One embodiment of the present invention can be suitably used in the fields of vehicles, aircraft, space, machinery, electricity, construction and civil engineering.

Claims (12)

1. A bonding step of applying the curable resin composition to the first adherend and laminating the second adherend to the first adherend.
   A cleaning step of cleaning the bonded body obtained in the bonding step, and
   A curing step of curing the curable resin composition is provided.
   The curable resin composition is
   Epoxy resin (A), and
   With respect to 100 parts by mass of the epoxy resin (A)
   Polymer fine particles (B) containing 1 part by mass to 100 parts by mass of a rubber-containing graft copolymer having an elastic body and a graft portion graft-bonded to the elastic body and containing a hydroxy group, and fumed silica. (C) A method for producing a structure, which comprises 1 part by mass to 30 parts by mass.
2. The method for producing a structure according to claim 1, wherein the curable resin composition does not substantially contain blocked urethane (D) with respect to 100 parts by mass of the epoxy resin (A).
3. The curable resin composition further comprises 1 part by mass to 100 parts by mass of blocked urethane (D) and 5 parts by mass to 200 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the epoxy resin (A). The method for producing a structure according to claim 1, wherein the value (X) represented by the following formula (1) is 25 or more.
   Value (X) = {0.5 (V1) + 10 (V2) + (V3)} × 100 ... Equation (1)
   (In the formula (1), the V1 represents the volume% of the polymer fine particles (B) in the curable resin composition, and the V2 is the fumed silica (C) in the curable resin composition. The volume% is shown, and V3 shows the volume% of the inorganic filler (E) in the curable resin composition).
4. The method for producing a structure according to claim 3, wherein the inorganic filler (E) contains calcium carbonate.
5. The curable resin composition according to any one of claims 1 to 4, further containing 1 to 80 parts by mass of the epoxy curing agent (F) with respect to 100 parts by mass of the epoxy resin (A). Structure manufacturing method.
6. Any one of claims 1 to 5, wherein the curable resin composition further contains 0.1 to 10 parts by mass of the curing accelerator (G) with respect to 100 parts by mass of the epoxy resin (A). The method for manufacturing a structure according to.
7. The method for producing a structure according to any one of claims 1 to 6, wherein the elastic body is butadiene rubber and / or butadiene-styrene rubber.
8. The graft portion is a polymer containing a structural unit derived from one or more monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer and a (meth) acrylate monomer as a structural unit. The method for producing a structure according to any one of 7 to 7.
9. The method for producing a structure according to any one of claims 1 to 8, wherein the graft portion is a polymer having an epoxy group.
10. The method for producing a structure according to any one of claims 1 to 9, wherein the blocked urethane (D) is a compound in which a urethane prepolymer containing a polyalkylene glycol structure is capped with a blocking agent.
11. The structure according to any one of claims 1 to 10, wherein the temperature of the curable resin composition applied to the first adherend in the bonding step is 35 ° C to 80 ° C. Manufacturing method.
12. The method for producing a structure according to any one of claims 1 to 11, wherein in the curing step, the curing temperature of the curable resin composition is 50 ° C to 250 ° C.