Adhesive composition

Abstract

The present invention provides an adhesive composition that can simultaneously achieve sufficient tensile shear bonding strength, a high modulus of elasticity, and excellent stress relaxation performance. [Solution] In one embodiment, an adhesive composition containing resin particles (1) and a base resin, wherein the resin particles (1) are resin particles obtained by polymerizing a monomer containing at least one selected from a monofunctional (meth)acrylate monomer (A) having an alkyl group having 10 to 30 carbon atoms and a polyfunctional (meth)acrylate monomer (B) having polyethylene glycol groups with a degree of polymerization of 9 to 14. In another embodiment, an adhesive composition containing resin particles (2) and a base resin, wherein the resin particles (2) are resin particles having a non-porous shell portion and a hollow portion surrounded by the shell portion, wherein the shell portion is a resin particle obtained by polymerizing a monomer containing at least one selected from a monofunctional vinyl monomer and a polyfunctional vinyl monomer.

Description

Technical Field

[0001] The present invention relates to an adhesive composition.

Background Art

[0002] Conventionally, adhesive compositions containing epoxy resins, second-generation acrylic resins, etc. have been used for adhesives used in electronic materials such as semiconductors and adhesives used in structural members of automobiles. For adhesives used in electronic materials, stress relaxation properties that can absorb the difference in the coefficient of thermal expansion between the semiconductor chip and the wiring board and reduce the warping of the semiconductor chip caused by thermal stress are required. For adhesives used in structural members of automobiles, in the adhesion of dissimilar materials such as metal and CFRP, it is required to absorb the difference in the coefficient of thermal expansion and suppress the decrease in structural strength caused by thermal stress.

[0003]

[0004]

[0005] In Patent Document 1, in a one-component curable adhesive composition containing an epoxy resin, a technique for imparting stress relaxation performance by dissolving a polymer material having a low glass transition point or adding a soft resin filler has been reported. However, the adhesive obtained from the adhesive composition described in Patent Document 1 has a problem that the tensile shear adhesive strength decreases due to a large decrease in the elastic modulus.

[0005]

[0006]

[0007] In Patent Document 2, an electrical insulating resin composition used for an insulating layer such as a multilayer printed wiring board is described, and a technique for improving the adhesive performance by adding organic particles has been reported. However, in the adhesive obtained from the electrically insulating resin composition described in Patent Document 2 The text does not mention stress relaxation performance or elastic modulus. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Special Publication No. 2018-518554 [Patent Document 2] Japanese Patent Publication No. 2006-8750 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The objective of this invention is to achieve a balance between sufficient tensile shear adhesive strength, high elastic modulus, and excellent stress relaxation performance. The objective is to provide an adhesive composition that can be expressed in this way. [Means for solving the problem]

[0010] [1] The adhesive composition according to the embodiment of the present invention contains resin particles (1) and a base resin. An adhesive composition wherein the resin particles (1) have an alkyl group having 10 to 30 carbon atoms. Monofunctional (meth)acrylate monomer (A) and polyethylene with a degree of polymerization of 9 to 14 Selected from the group consisting of polyfunctional (meth)acrylate monomers (B) having a glycol group. These are resin particles obtained by polymerizing monomers containing at least one of the specified substances. [2] The adhesive composition according to the embodiment of the present invention contains resin particles (2) and a base resin. An adhesive composition wherein the resin particles (2) are composed of a non-porous shell portion and the shell portion Resin particles having an enclosed hollow portion, wherein the shell portion is made of a monofunctional vinyl monomer and and polymerizing a monomer containing at least one selected from the group consisting of polyfunctional vinyl monomers is obtained. [3] In the adhesive composition according to [1] or [2] above, the base resin is an epoxy resin, phenol resin, resorcinol resin, acrylic resin, silicone resin, melamine resin system, urea resin, urethane resin, polyimide resin, and , a polyester resin, and may be an embodiment in which at least one selected from the group consisting of is used. [Advantages of the Invention]

[0011] According to an embodiment of the present invention, an adhesive composition capable of achieving both sufficient tensile shear adhesion strength, high elastic modulus, and excellent stress relaxation performance can be provided. [Brief Description of the Drawings]

[0012] [Figure 1] It is a cross-sectional photograph of the resin particles (B) produced in Production Example 2. [Figure 2] It is a cross-sectional photograph of the resin particles (C) produced in Production Example 3. [Modes for Carrying Out the Invention]

[0013] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments .

[0014] In this specification, when there is an expression of "(meth)acryl", it means "acryl and / or methacryl", and when there is an expression of "(meth)acrylate", it means "acrylate and / or methacrylate". When there is an expression of "(meth)acryloyl", it means "acryloyl and / or methacryloyl".

[0015] <<<Resin particles (1)>>> The resin particles (1) are monofunctional (meth)acrylic having alkyl groups with 10 to 30 carbon atoms. Polyethylene glycol group having a polymer monomer (A) and a degree of polymerization of 9 to 14 It contains at least one selected from the group consisting of (meth)acrylate monomers (B). These are resin particles obtained by polymerizing monomers. They have alkyl groups with 10 to 30 carbon atoms. The monofunctional (meth)acrylate monomer (A) may be just one type, or two or more types. The above is also acceptable. A polyfunctional (meth) polyethylene glycol group having a degree of polymerization of 9 to 14. The acrylate monomer (B) may be one type or two or more types. stomach.

[0016] The average particle size of the resin particles (1) is preferably 0.1 μm to 50 μm, and more preferably The particle size is 0.5 μm to 30 μm, and more preferably 1 μm to 15 μm. (1) If the average particle size is within the above range, sufficient tensile shear adhesive strength and high elastic modulus and excellent This provides an adhesive composition that can simultaneously exhibit excellent stress relaxation performance. If the average particle size of (1) is too small and falls outside the above range, the resin particles in the adhesive composition The dispersibility of (1) may become extremely poor, potentially leading to a deterioration in adhesive performance. If the average particle size is too large and falls outside the above range, the surface of the adhesive will become uneven, resulting in a less uniform surface. It may become difficult to obtain a suitable adhesive surface, and when a load is applied to the adhesive area, individual Each resin particle (1) is subjected to a load, and if the average particle size is too large, the load on each individual particle will be greater. Because particles tend to concentrate in one area, this could potentially lead to a deterioration in adhesive performance.

[0017] <<A monofunctional (meth)acrylate monomer having an alkyl group with 10 to 30 carbon atoms> )≫ Monofunctional (meth)acrylate monomers having alkyl groups with 10 to 30 carbon atoms (A The alkyl group in ) is the alkyl group of the ester portion, and has 10 to 30 carbon atoms. It is a chain alkyl group. Below are monofunctional (meth) alkyl groups having 10 to 30 carbon atoms. The acrylate monomer (A) is referred to as "long-chain monofunctional (meth)acrylate monomer (A)". It is sometimes referred to as such.

[0018] Alkyl groups may be linear or branched.

[0019] The number of carbon atoms in the alkyl group is preferably 10 to 26, more preferably 10 to 24. More preferably 11 to 20, and particularly preferably 12 to 18. If the number of carbon atoms is within the above range, then a long-chain alkyl of an appropriate length will be present in the resin particle (1). The base reduces excessive concentration of crosslink density, lowering the brittleness of the resin particles (1) (when subjected to external force). (Preventing excessive brittleness that causes it to break before it can take shape) while improving flexibility. This can be achieved. And by incorporating such resin particles (1) into the adhesive composition, It can achieve sufficient tensile shear bonding strength, a high modulus of elasticity, and excellent stress relaxation performance simultaneously.

[0020] The long-chain monofunctional (meth)acrylate monomer (A) is not particularly limited, for example, Decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth) acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, 2 - Decyltetradecanyl (meth)acrylate, pentadecyl (meth)acrylate, Xadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate (T)Acrylate, Nonadecyl(meth)acrylate, 1-Methylnonyl(meth)acrylate 1-ethyldecyl(meth)acrylate, 1,2-dimethyloctyl(meth)acrylate acrylate, 1,2-diethylhexyl (meth)acrylate, eicosyl (meth)acrylate Examples include rilates and behenyl (meth)acrylates. Among these, the effects of the present invention In terms of being able to express more, lauryl (meth)acrylate and tridecyl (meth)acrylate Hexadecyl (meth)acrylate, stearyl (meth)acrylate, eicosyl Methacrylate is preferred.

[0021] Long-chain monofunctional (meth) components in the total monomer used to obtain resin particles (1) by polymerization reaction The preferred content of acrylate monomer (A) is, in proportion to 100 parts by mass of the total monomer... More precisely, it is 20 to 85 parts by mass, and more preferably 30 to 80 parts by mass. More preferably 40 to 75 parts by mass, and particularly preferably 50 to 70 parts by mass This is the component. If the above content ratio is within the above range, it will further prevent a decrease in the brittleness of the resin particles (1). This allows for further improvement of softness. If the above content is too low and falls outside the above range, This may reduce the flexibility of the resin particles (1). If the value is too high, the brittleness of the resin particles (1) may decrease.

[0022] Long-chain monofunctional (meth)acrylate-based monomers in all monomer units constituting the resin particles (1) The content ratio of monomer units derived from MA(A) is, per 100 parts by mass of total monomer units, The amount is 20 to 85 parts by mass, and more preferably 30 to 80 parts by mass. More preferably 40 to 75 parts by mass, and particularly preferably 50 to 70 parts by mass This is in parts. If the above content ratio is within the above range, it will further prevent a decrease in the brittleness of the resin particles (1). It is possible to further improve softness while preventing spoilage. If the above content is too low and falls outside the above range... If this occurs, the flexibility of the resin particles (1) may decrease. If the level is too high, the brittleness of the resin particles (1) may decrease.

[0023] Polyfunctional (meth)acrylate system having polyethylene glycol groups with a degree of polymerization of 9 to 14 Monomer (B)≫ Polyfunctional (meth)acrylate system having polyethylene glycol groups with a degree of polymerization of 9 to 14 Monomer (B) has repeating units of polyethylene glycol groups and vinyl groups in the molecule It is a crosslinkable monomer with both ends. Below are polyethylene glycols with a degree of polymerization of 9 to 14. A polyfunctional (meth)acrylate monomer (B) having an EO group is defined as "a polyfunctional ( It is sometimes referred to as "meth)acrylate monomer (B)".

[0024] Polyfunctional (meth)acrylate monomer (B) having an EO group enhances the effects of the present invention. Preferably, in terms of being able to express, CH2=C(CH3)-COO-(CH2CH2O) n -CO-C(CH3)=CH2 It is represented by the chemical formula, where n is an integer between 9 and 14.

[0025] A polyfunctional (meth)acrylate monomer (B) having an EO group is represented by the above chemical formula. If n is an integer between 9 and 14, then in the polymer resin particles (1), the crosslinking density is excessive. By mitigating the concentration, the brittleness of the resin particles (1) is prevented while improving their flexibility. This can be achieved. By incorporating such resin particles (1) into the adhesive composition, it is possible to achieve sufficient It can achieve a combination of high tensile shear adhesive strength, high elastic modulus, and excellent stress relaxation performance.

[0026] The polyfunctional (meth)acrylate monomer (B) having an EO group is not particularly limited. For example, pentaethylene glycol di(meth)acrylate, hexaethylene glycol Di(meth)acrylate, heptethylene glycol di(meth)acrylate, oc Ethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate Relate, Decaethylene glycol di(meth)acrylate, Tetradecaethylene glycol Di(meth)acrylate, pentadecaethylene glycol di(meth)acrylate It can be listed.

[0027] A polymer containing an EO group in the total monomer used to obtain resin particles (1) by polymerization reaction The content of functional (meth)acrylate monomer (B) is as follows: Preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. It is more preferably 13 to 30 parts by mass, and particularly preferably 15 parts by mass The amount is 25 parts by mass. If the above content ratio is within the above range, the brittleness of the resin particles (1) will decrease. This allows for better prevention while further improving softness. If the concentration is too low, the flexibility of the resin particles (1) may decrease. The above content ratio is within the above range. If the value deviates too much from this range, the brittleness of the resin particles (1) may decrease.

[0028] Polyfunctional (meth)acrylic having an EO group in all monomer units constituting the resin particle (1) The content ratio of monomer units derived from tetramethyl monomer (B) is per 100 parts by mass of all monomer units. In contrast, the amount is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. It is part, more preferably 13 to 30 parts by mass, and particularly preferably 15 parts by mass. The amount is approximately 25 parts by mass. If the above content ratio is within the above range, the brittleness of the resin particles (1) will decrease. This can further prevent this while improving softness. If the content is too low, the flexibility of the resin particles (1) may decrease. If the temperature is too high outside the bounds, the brittleness of the resin particles (1) may decrease.

[0029] ≪Polyfunctional (meth)acrylate monomer (C)≫ As a monomer used to obtain resin particles (1) by polymerization reaction, resin particles (1) From the standpoint of preventing a decrease in brittleness, improving softness, and improving oil resistance, polyfunctional (meth)acrylic resin is used. A methyl-based monomer (C) may also be used. A polyfunctional (meth)acrylate monomer (C) is, Polyethylene glycol with a degree of polymerization of 9-14, without groups, and polyfunctional (meth) having EO groups. Different from acrylate monomer (B). Polyfunctional (meth)acrylate monomer (C) ) may be one type or two or more types.

[0030] The polyfunctional (meth)acrylate monomer (C) preferably has multiple polymerizations within the molecule. It has sexually unsaturated bonds and multiple (meth)acryloyl groups within the molecule. Polyfunctional (meth )The acrylate monomer (C) is preferably a polyfunctional (meth)acrylate monomer -(C) polymerizes with other monomers or other monomers to form a crosslinked structure. This results in resin particles (1) This can improve softness while preventing a decrease in brittleness, and further improve oil resistance. obtain.

[0031] The polyfunctional (meth)acrylate monomer (C) is not particularly limited, for example, E Teylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Triethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate ) Acrylate, pentadecaethylene glycol di(meth)acrylate, pentaconta Hectaethylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate Rate, allyl (meth)acrylate, trimethylolpropane, tri(meth)acrylate Pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa (Meth)acrylates are one example. Among these, those that can better exhibit the effects of the present invention In terms of points, ethylene glycol di(meth)acrylate (ethylene glycol dimethacrylate (T), allyl (meth)acrylate (allyl methacrylate) and other difunctional (meth) acrylates A monomer is preferred.

[0032] Polyfunctional (meth)a in the total monomer used to obtain resin particles (1) by polymerization reaction The content of acrylate monomer (C) is preferably in the amount of 100 parts by mass of the total monomer. The amount is 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 The amount is less than or equal to parts by mass, particularly preferably 20 parts by mass or less, and most preferably 15 parts by mass or less. Below. If the above content ratio is within the above range, the reduction in the brittleness of the resin particles (1) will be further prevented. This allows for further improvement of flexibility and, moreover, further improvement of oil resistance.

[0033] Polyfunctional (meth)acrylate monomers in all monomer units constituting resin particles (1) (C) The content ratio of monomer units derived from (C) is preferably 100 parts by mass of total monomer units. The amount is 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 3 The amount is 0 parts by mass or less, particularly preferably 20 parts by mass or less, and most preferably 15 parts by mass. The following applies: If the above content ratio is within the above range, it will further prevent a decrease in the brittleness of the resin particles (1). It is possible to further improve flexibility while preventing further deterioration, and also to further improve oil resistance.

[0034] The polyfunctional (meth)acrylate monomer (C) can further enhance the effects of the present invention. In particular, the monomer used to obtain resin particles (1) by polymerization reaction is a long-chain monofunctional ( It is preferable to use this when it contains a meth)acrylate monomer (A).

[0035] The monomer used to obtain resin particles (1) by polymerization reaction is a long-chain monofunctional (meth) monomer. If a acrylate monomer (A) is included, resin particles (1) are obtained by polymerization reaction. The proportion of polyfunctional (meth)acrylate monomers (C) in the total monomers used is: Preferably 50 parts by mass or less per 100 parts by mass of total monomer, more preferably 2 The amount is 4 to 40 parts by mass, more preferably 4 to 30 parts by mass, and particularly preferred The amount is 6 to 20 parts by mass, most preferably 8 to 15 parts by mass. If the proportion is within the above range, it will further prevent a decrease in the brittleness of the resin particles (1) while maintaining flexibility. This can be improved, and furthermore, oil resistance can be further enhanced.

[0036] The monomer units that make up the resin particle (1) are long-chain monofunctional (meth)acrylic If monomer units derived from a monomethyl monomer (A) are included, the total amount of the resin particles (1) The content of monomer units derived from polyfunctional (meth)acrylate monomers (C) within monomer units The proportion is preferably 50 parts by mass or less per 100 parts by mass of total monomer units. Preferably 2 to 40 parts by mass, and even more preferably 4 to 30 parts by mass. Particularly preferably 6 to 20 parts by mass, and most preferably 8 to 15 parts by mass Therefore, if the above content ratio is within the above range, it will further prevent a decrease in the brittleness of the resin particles (1). Furthermore, it is possible to further improve flexibility and, moreover, oil resistance.

[0037] <<Other monomers (D)>> As a monomer used to obtain resin particles (1) by polymerization reaction, the effects of the present invention Any other suitable monomer (D) may be used, provided that it does not impair the original monomer. ) may be one type or two or more types.

[0038] Other monomers (D) include, for example, monofunctional molecules having alkyl groups with 1 to 8 carbon atoms. Examples include meth)acrylate monomers. Alkyl alkyl groups may be linear or branched. You may do so.

[0039] Monofunctional (meth)acrylate monomers having an alkyl group with 1 to 8 carbon atoms include: For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate ) Acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate Isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate ) Acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl ( Meth)acrylate, isooctyl(meth)acrylate, cyclopentyl(meth)acrylate Examples include relates and cyclohexyl (meth)acrylates. Among these, the present invention... In terms of being able to better express the effect, monofunctional (meth) alkyl groups having 1 to 4 carbon atoms A acrylate monomer is preferred, and more preferably methyl (meth)acrylate, n- It is butyl (meth)acrylate.

[0040] Other monomers (D) in the total monomers used to obtain resin particles (1) by polymerization reaction The content ratio of ) is such that the effects of the present invention can be more fully expressed, relative to 100 parts by mass of the total monomer. Preferably, it is 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably The amount is 85 parts by mass or less.

[0041] Monomer units derived from other monomers (D) in all monomer units constituting the resin particle (1) The content ratio is such that the effects of the present invention can be more fully expressed, relative to 100 parts by mass of total monomer. Preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably Or it is 85 parts by mass or less.

[0042] The monomer used to obtain resin particles (1) by polymerization reaction is a long-chain monofunctional (meth) monomer. When a acrylate monomer (A) is included, the effects of the present invention can be more fully expressed. Other monomers (D) in the total monomers used to obtain lipid particles (1) by polymerization reaction The content ratio is preferably 80 parts by mass or less per 100 parts by mass of total monomer, and Preferably 1 to 60 parts by mass, and more preferably 5 to 50 parts by mass. Particularly preferably 10 to 45 parts by mass, and most preferably 15 to 40 parts by mass It is a department.

[0043] The monomer units constituting the resin particles (1) are long-chain monofunctional (meth)acrylate monomers. (A) When monomer units derived from the present invention are included, the effects of the present invention can be more fully expressed, in resin Content of monomer units derived from other monomers (D) in all monomer units constituting particle (1) The ratio is preferably 80 parts by mass or less, and more preferably, per 100 parts by mass of the total monomer. More preferably 1 to 60 parts by mass, and more preferably 5 to 50 parts by mass, Preferably 10 to 45 parts by mass, most preferably 15 to 40 parts by mass. be.

[0044] The monomer used to obtain resin particles (1) by polymerization reaction is polyfunctional, having an EO group. When (meth)acrylate monomer (B) is included, the effects of the present invention can be more strongly exhibited. In this respect, other monomers in the total monomer used to obtain resin particles (1) by polymerization reaction The content of (D) is preferably 95 parts by mass or less per 100 parts by mass of the total monomer. Yes, more preferably 50 to 95 parts by mass, and even more preferably 60 to 9 parts by mass. It is 0 parts by mass, particularly preferably 70 to 87 parts by mass, and most preferably 75 parts by mass. It is approximately 85 parts by mass.

[0045] The monomer units constituting the resin particles (1) are polyfunctional (meth)acrylates having an EO group. When monomer units derived from system monomer (B) are included, the effects of the present invention can be more effectively exhibited. At a given point, the monomers derived from other monomers (D) in the total monomer units constituting the resin particle (1) The unit content is preferably 95 parts by mass or less per 100 parts by mass of total monomer. More preferably 50 to 95 parts by mass, and even more preferably 60 to 90 parts by mass. This is in parts, particularly preferably 70 to 87 parts by mass, and most preferably 75 parts by mass. It is approximately 85 parts by mass.

[0046] ≪≪Method for producing resin particles (1)≫≫ Resin particles (1) are polymerized in a polymerization medium (aqueous medium or It can be manufactured by polymerization using an organic medium. Such a manufacturing method is described in this invention. Any appropriate method may be adopted, as long as it does not impair the effect of the light.

[0047] The aqueous medium is not particularly limited and can be, for example, water, water-soluble organic media (methanol, ethanol). Lower alcohols such as ethanol and isopropyl alcohol (alcohols with 5 or fewer carbon atoms) Examples include a mixed medium of water and a water-soluble organic medium, with an aqueous medium containing water being preferred. Organic medium Examples include toluene, benzene, and ethyl acetate, but are not particularly limited. In terms of better demonstrating the effects of the invention, an aqueous medium is preferred as the polymerization medium.

[0048] Typically, resin particles (1) are formed by composing a polymerization initiator in an aqueous medium using raw material monomers. It is preferable to manufacture by suspension polymerization. Suspension polymerization involves the polymerization of raw materials in an aqueous medium (aqueous phase). A suspension is prepared by dispersing droplets of an oily mixture (oil phase) containing a polymer and a polymerization initiator. It is preferable to polymerize the raw material monomers in a suspension.

[0049] The amount of aqueous medium used is preferably 100 parts by mass per 100 parts by mass of raw material monomer. The amount is 2000 parts by mass, more preferably 200 to 1000 parts by mass. Aqueous medium By adjusting the amount used within the above range, the dispersion stability of monomers and other elements in the reaction solution can be improved. This improves properties and suppresses the formation of aggregates of resin particles (1) during polymerization. It is possible.

[0050] A dispersion stabilizer may be included in the aqueous medium. The dispersion stabilizer may be of one type. There may be two or more types.

[0051] Examples of dispersion stabilizers include calcium phosphate, magnesium phosphate, and aluminum phosphate. nium, zinc phosphate and other phosphates, calcium pyrophosphate, magnesium pyrophosphate, Pyrophosphates such as aluminum pyrophosphate and zinc pyrophosphate; calcium carbonate, magnesium carbonate Magnesium, magnesium oxide, colloidal silica, calcium hydroxide, magnesium hydroxide Aluminum, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, Poorly water-soluble inorganic compounds such as roydal silica; polyvinylpyrrolidone, partially saponified polyvinyl Alcohol, polyacrylic acid, carboxymethylcellulose, methylcellulose, etc. Examples include water-soluble polymers. Among these, those that decompose in acid and dissolve in water (e.g.) For example, calcium carbonate, tricalcium phosphate, magnesium hydroxide, magnesium pyrophosphate Using calcium pyrophosphate allows for easy removal of the dispersion stabilizer after the polymerization process. This is preferable because it makes it possible to do so.

[0052] The amount of dispersion stabilizer used should be such that it ensures the fluidity of the suspension while controlling the oily mixture in the suspension. In terms of improving droplet dispersibility, preferably 0. The amount is 1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass.

[0053] The polymerization initiator is not particularly limited as long as it can initiate the polymerization of the raw material monomers. i. As polymerization initiators, radical polymerization initiators are preferred, and thermal radical polymerization initiators are more Preferred. Examples of polymerization initiators include persulfates (e.g., ammonium persulfate, persulfate). Examples include potassium acid, sodium persulfate, hydrogen peroxide, organic peroxides, and azo compounds. The polymerization initiator may be one type or two or more types.

[0054] Examples of organic peroxides include cumene hydroperoxide and di-tert-butyl. Lauroyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide - Oxide, Dimethylbis(tert-butylperoxy)hexane, Dimethylbis( tert-butylperoxy)hexine-3, bis(tert-butylperoxyisop Ropyr benzene, bis(tert-butylperoxy)trimethylcyclohexane, Tyl-bis(tert-butylperoxy)valerate, 2-ethylhexaneperoxy Tert-butyl acid, dibenzoyl peroxide, paramenthane hydroperoxide One example is tert-butyl peroxybenzoate.

[0055] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'- Azobis(2-methylbutyronitrile), 2,2'-Azobis(2-isopropylbutyronitrile) Nitrile), 2,2'-azobis(2,3-dimethylbutyronitrile), 2,2'-azo Bis(2,4-dimethylbutyronitrile), 2,2'-azobis(2-methylcapronite) 2,2'-Azobis(2,3,3-trimethylbutyronitrile), 2,2'-A Zobis(2,4,4-trimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) (Cylvaleronitrile), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile) Tolyl), 2,2'-azobis(4-ethoxy-2,4-dimethylvaleronitrile), 2 ,2'-Azobis(4-n-butoxy-2,4-dimethylvaleronitrile), 1,1'- Azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyrate Examples include rotrinitrile and 4,4'-azobis(4-cyanopentanoic acid).

[0056] The amount of polymerization initiator used is important in that it allows for the smooth initiation of polymerization of the raw material monomers. Preferably, the amount is 0.1 to 3 parts by mass per 100 parts by mass of the material monomer, and more preferably... Or, it is between 0.2 parts by mass and 1.0 parts by mass.

[0057] To further stabilize the suspension (reaction solution) during suspension polymerization, an interfacial agent is added to the aqueous medium. It may contain a surfactant. The surfactant may be one type or two or more types. stomach.

[0058] Examples of surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. Examples include surfactants and amphoteric surfactants. As surfactants, they react with the raw material monomers. It is preferable to use a reactive surfactant that has properties. When a reactive surfactant is used, A surfactant can be left on the surface of the resin particles (1), and such resin particles (1) can be uniformly dispersed in the adhesive composition without agglomerating.

[0059] Examples of anionic surfactants include sodium oleate and potassium castor oil soap. Fatty acid soaps; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate Ster salts; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; Alkylnaphthalene sulfonates; Alkanesulfonates; Dialkyl sulfosuccinates Alkyl phosphate salts; Naphthalene sulfonic acid formalin condensate; Polyoxyethylene Lenalkylphenyl ether sulfate salts; polyoxyethylene sulfonated phenyl Ether phosphate; polyoxyethylene alkyl sulfate salts; phosphate ester surfactants Examples include fertilizers and phosphite-based surfactants.

[0060] As anionic reactive surfactants, commercially available ones can be used. Examples of nionic reactive surfactants include Aqualon (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ) KH-10, KH-1025, KH-05, HS-10, HS-1025, BC-0 515, BC-10, BC-1025, BC-20, BC-2020, AR-1025, AR-2025, etc.; S-120, S-180A, S-120, S-180A, S-120 from Kao Corporation's Latemul (registered trademark) -180, PD-104, etc.; SR- of Adekaria Soap (registered trademark) manufactured by ADEKA Corporation Examples include the 1025 and SE-10N.

[0061] Examples of cationic surfactants include laurylamine acetate and stearylamine. Alkylamine salts such as ammonium acetate; lauryltrimethylammonium chloride, etc. Quaternary ammonium salts are examples.

[0062] Examples of nonionic surfactants include (meth)acrylate sulfate ester-based surfactants. Sexual agents (commercially available products include, for example, RMA-564, RMA-568, R from Nippon Emulsifier Co., Ltd.) MA-1114, etc.) Polyoxyalkylene branched decyl ether, polyoxyethylene Tridecyl ether, polyoxyalkylene alkyl ether, polyoxyalkylate Lidecyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether Lyl ether, polyoxyalkylene alkyl ether, polyether polyol, poly Oxyethylene styrene-modified phenyl ether, polyoxyethylene naphthyl ether, Polyoxyethylene phenyl ether, polyoxyethylene polyoxypropylene glyco Polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether Polyoxyethylene glyceryl isostearate, polyoxyethylene alkyl ether Polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene Alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene blotter Examples include mac polymers.

[0063] Nonionic reactive surfactants can be commercially available. Examples of reactive surfactants include alkyl ether surfactants (commercially available products include For example, ADEKA's Adekaria soaps ER-10, ER-20, ER-30, ER-40, etc.; Kao Corporation's Latemul PD-420, PD-430, PD-450, etc. ); alkylphenyl ether-based surfactants or alkylphenyl ester-based surfactants (Commercially available products include, for example, Aqualon RN-10 and RN-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , RN-30, RN-50, AN-10, AN-20, AN-30, AN-5065, etc. ;ADEKA's Adekaria soaps NE-10, NE-20, NE-30 and NE Examples include -40, etc.

[0064] Examples of amphoteric surfactants include lauryldimethylamine oxide. Examples include mine oxide type; alkyl betaine type; and fatty acid amidopropyl betaine type. .

[0065] The amount of surfactant used is preferably 0.001 parts by mass per 100 parts by mass of raw material monomer. It is 0.005 parts by mass to 5 parts by mass, more preferably 0.005 parts by mass to 3 parts by mass, and even more preferably Or, it is between 0.01 parts by mass and 1 part by mass.

[0066] The oily mixture may contain an acidic organic modified phosphorus compound. The acid compound may be one type or two or more types. Acidic organic modified phosphorylation By incorporating a substance into an oily mixture, stable, fine oil droplets of the oily mixture are formed in the suspension. It can be made to happen.

[0067] Examples of acidic organic modified phosphate compounds include monophosphate and diphosphate. Examples include phosphate monoesters and phosphate diesters. Acidic organic modified phosphate compounds include , not particularly limited, but specifically, for example, lauryl phosphate, polyoxyethylene (1 ) Lauryl ether phosphate, dipolyoxyethylene (2) alkyl ether phosphate, dipo Polyoxyethylene (4) alkyl ether phosphate, dipolyoxyethylene (6) alkyl Ether phosphate, dipolyoxyethylene (8) alkyl ether phosphate, dipolyoxyethylene -Tel(4) nonylphenyl ether phosphate, caprolactone EO modified phosphate dimethacrylate (EO: ethylene oxide), 2-methacryloyloxyethyl acid phosphate Among these, lauryl is one that can better demonstrate the effects of the present invention. Calcium acid and caprolactone EO-modified phosphate dimethacrylate are preferred.

[0068] The content ratio of the acidic organic modified phosphate compound is preferably, per 100 parts by mass of the oily mixture. It is 10 parts by mass or less, more preferably 0.01 parts by mass to 5 parts by mass, and even more preferably Or, it is between 0.01 parts by mass and 3 parts by mass.

[0069] As for the method of preparing the suspension, any appropriate method can be adopted as long as it does not impair the effects of the present invention. Such methods can be used. For example, a method using a stirring device such as a homomixer can be used. It can be listed.

[0070] Any suitable conditions can be adopted for suspension polymerization, as long as they do not impair the effects of the present invention. This is possible. The polymerization temperature is preferably, for example, 10°C to 200°C, and more preferably The polymerization time is 20°C to 150°C, and more preferably 30°C to 120°C. For example, it is preferably 10 minutes to 24 hours, and more preferably 1 hour to 12 hours. More preferably, it is 2 to 10 hours.

[0071] After suspension polymerization is complete, washing, drying, crushing, classification, etc. may be performed as needed. For example, separating an aqueous medium from a reaction solution containing resin particles (1) obtained by suspension polymerization. The resin particles (1) are reduced to produce a cake containing resin particles (1). The method for separating and reducing the aqueous medium is not particularly limited, and includes, for example, suction filtration, centrifugation Separation and pressurized separation are examples. Next, for example, the cake is separated into an aqueous medium or organic medium as needed. After washing with a solvent, the resin particles (1) can be obtained by drying. The method of washing the cake is not particularly limited, for example, supplying the cake to a centrifugal separator and washing the cake with water A water-based medium is supplied to wash the resin particles (1), and the water-based medium after washing is removed by centrifugation. One possible method is to use a reactive surfactant in the aqueous medium of the cake. This eliminates the need for cleaning.

[0072] During the drying of the resin particles (1), in order to prevent the resin particles (1) from adhering to each other, An antiblocking agent may be applied to the surface of (1). This is not particularly limited, and includes, for example, silica nanoparticles, alumina nanoparticles, titania nanoparticles, zirconium Examples of inorganic powders include nia particles, ceria particles, iron oxide particles, and zinc oxide particles. .

[0073] The resin particles (1) may be crushed and classified as needed. The type of crusher used is not particularly limited, and for example, a mechanical crusher (e.g., blade Mills, super rotors) and air-jet grinders (for example, nano grinding mills (jet) Dry grinders such as Tomills, and wet grinders such as bead mills, ball mills, and hammer mills. These are some examples.

[0074] The method for classifying resin particles (1) is not particularly limited, and for example, wind classification and screen classification are available. One example is wind classification, which is a method of classification that utilizes airflow. This involves supplying resin particles (1) onto a screen and vibrating the screen, The resin particles (1) on the screen are divided into particles that pass through the mesh of the screen and particles that do not pass through. This refers to a method of classifying things into categories.

[0075] <<<Resin particles (2)>>> The resin particle (2) has a non-porous shell portion and a hollow portion surrounded by the shell portion. Resin particles, the shell portion of which is composed of monofunctional vinyl monomers and polyfunctional vinyl monomers. It is obtained by polymerizing a monomer containing at least one selected from the group consisting of the following.

[0076] The average particle size of the resin particles (2) is preferably 0.1 μm to 50 μm, and more preferably The particle size is 0.5 μm to 30 μm, and more preferably 1 μm to 15 μm. (2) If the average particle size is within the above range, sufficient tensile shear adhesive strength and high elastic modulus and excellent This provides an adhesive composition that can simultaneously exhibit excellent stress relaxation performance. (2) If the average particle size is too small and falls outside the above range, the resin particles in the adhesive composition (2) The dispersibility of the resin particles (2) may become extremely poor, potentially leading to a deterioration in adhesive performance. If the average particle size is too large and falls outside the above range, the surface of the adhesive will become uneven, resulting in a less uniform surface. It may become difficult to obtain a suitable adhesive surface, and when a load is applied to the adhesive area, individual Each resin particle (2) is subjected to a load, and if the average particle size is too large, the load on each individual particle will be greater. Because particles tend to concentrate in one area, this could potentially lead to a deterioration in adhesive performance.

[0077] ≪Shell section≫ The material constituting the shell is either monofunctional vinyl monomer or polyfunctional vinyl monomer. Obtained by polymerizing a monomer containing at least one selected from the group, the shell portion The material used to make up the shell is not particularly limited, as long as it can form a more enclosed hollow section. It may also contain inorganic components (for example, silica).

[0078] Examples of monofunctional vinyl monomers include methyl (meth)acrylate and ethyl (meth)acrylate. Carbon acrylates such as butyl (meth)acrylate and cetyl (meth)acrylate. Alkyl (meth)acrylic acid esters of numbers 1 to 16; styrene, α-methylstyrene, etc. Tyl vinylbenzene, vinyl toluene, o-chlorostyrene, m-chlorostyrene, p- Chlorostyrene, paramethylstyrene, ethylstyrene, i-propylstyrene, dimethicone Aromatic monofunctional compounds such as rustyrene, bromostyrene, vinyl biphenyl, and vinylnaphthalene. Monomers; dimethyl maleate, diethyl fumarate, dimethyl fumarate, diethyl f Dicarboxylic acid ester monomers such as maleates; maleic anhydride; N-vinylcarbazeo Examples include (meth)acrylonitrile. In terms of being able to better express the effects of the present invention, As functional vinyl monomers, aromatic monofunctional monomers are preferred, such as styrene and ethyl. Vinylbenzene is more preferred. The monofunctional vinyl monomer may be of only one type. There may be two or more types.

[0079] Examples of polyfunctional vinyl monomers include ethylene glycol di(meth)acrylate. Polyethylene glycol di(meth)acrylate, glycerin tri(meth)acrylate Polyfunctional (meth)acrylic acid esters such as methyl esters; N,N'-methylenebis(meth)acrylic acid Polyfunctional acrylamide derivatives such as amides and N,N'-ethylenebis(meth)acrylamide Body; polyfunctional allyl derivatives such as diallylamine and tetraallyloxyethane; divinylbene Examples include aromatic divinyl compounds such as zen, divinylnaphthalene, and diallyl phthalate. These polyfunctional vinyl monomers may be one type or two or more types. That's fine.

[0080] Polyfunctional vinyl monomers in the total monomers used to obtain the shell portion by polymerization reaction The proportion of this material is such that it forms a shell with sufficient strength, and is a monofunctional vinyl material. Preferably 20 parts by mass or more, and more preferably 20 parts by mass, per 100 parts by mass of mal. The amount is between 150 parts by mass and more preferably between 80 and 130 parts by mass.

[0081] Monomer units derived from polyfunctional vinyl monomers in all monomer units constituting the shell portion The proportion of monofunctional vinyl monomers is such that they form a shell with sufficient strength. Preferably 20 parts by mass or more, more preferably 20 parts by mass or more per 100 parts by mass The amount is 150 parts by mass, and more preferably 80 to 130 parts by mass.

[0082] ≪≪Method for producing resin particles (2)≫≫ Resin particles (2) consist of monofunctional vinyl monomer, polyfunctional vinyl monomer, and void-forming agent. A mixture containing a polymerization initiator is polymerized in an aqueous medium containing a suspension stabilizer in the presence of a dispersion aid. It can be manufactured by such a method. Such a manufacturing method does not impair the effects of the present invention. Within that scope, any appropriate method may be adopted.

[0083] As a void-forming agent, it promotes phase separation between the shell and void during polymerization. While there are no particular limitations, examples include non-reactive solvents and surfactants. ru.

[0084] Examples of non-reactive solvents include pentane, hexane, cyclohexane, heptane, and hydroxypropyl alcohol. Cane, hexadecane, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl keto Methyl isobutyl ketone, methyl chloride, methylene chloride, chloroform, carbon tetrachloride Examples include: The non-reactive solvent may be one type or two or more types. (e.g., resin particles) Since it is easy to remove from the hollow portion of child (2), the boiling point of the non-reactive solvent is 10 It is preferable that the temperature is below 0°C.

[0085] The amount of nonreactive solvent used is not particularly limited, but it is important to use an amount that can better demonstrate the effects of the present invention. Preferably, the amount is 40 to 250 parts by mass per 100 parts by weight of the total monomer. If the amount of the responsive solvent used falls too far outside the above range, the proportion of the hollow portion may decrease. This may prevent the effects of the present invention from being achieved. If the amount of non-reactive solvent used is within the above range... If too many particles are missing, the shell will not be formed properly, and the resin particles will not have sufficient physical strength. (2) may not be obtained.

[0086] While the surfactant is not particularly limited, it is important to note that it can better demonstrate the effects of the present invention. A comb-shaped polymer having a hydrophilic part and a hydrophobic part within its structure is preferred. Here, a comb-shaped polymer is a linear polymer. This refers to a polymer that has many tridental branching points where linear side chains are attached to the main chain. For example, the hydrophilic part. A polymer having a comb-like structure in which two or more hydrophobic parts are bonded to a main chain, or the reverse. Examples include polymers having a structure in which two or more hydrophilic parts are bonded in a comb-like manner to a main chain consisting of hydrophobic parts. Among these, a shape in which two or more hydrophobic parts are linked in a comb-like manner on a main chain consisting of hydrophilic parts. Polymers having this feature are preferable in that they can form a more stable suspension state. The bond between the main chain and the side chains The bonding form is not particularly limited, but it is usually a graft-based bonding form.

[0087] Specifically, comb-shaped polymers include, for example, those with 3 to 80 alkylene oxy side chains. It consists of two or more carbonyl-C3~C6 alkylene oxy chains containing a group, and is also an amide. Alternatively, it is bonded to the main chain by a salt crosslinking group, and the main chain is composed of poly(lower alkyleneimine) and free calcium Examples include polymers whose chains are derived from reaction products with polyesters containing vonic acid groups. Examples of alkylenes include ethylene, triethylene, and tetraethylene.

[0088] Examples of comb-type polymers include "Sol" from Lubrizol, a British company. Examples include commercially available comb-shaped polymers in the "Solsperse" series. For example, product numbers 11200, 13240, 13650, 13940, 2400 0SC, 24000GR, 26000, 28000, 32000, 32500, 3255 0, 32600, 33000, 34750, 35100, 35200, 36000, 36 600 and 37,500 are cited.

[0089] The weight-average molecular weight of the comb-type polymer is preferably 2,000 to 100,000, and more preferably The weight-average molecular weight is 20,000 to 30,000. These values ​​were measured using tography.

[0090] Comb-shaped polymers are selected from the group consisting of functional groups made of acidic groups and functional groups made of bases. It may have at least one of the following. There may be multiple acid groups and bases. The acid group is The acid may be present in such a way that it can give an acid value of 20-80. The base has a basicity of 1000-2000. It may exist in such a way that it can provide. When the acid value is less than 20, it is less likely to form single hollows, and multiple hollow grains are formed. It tends to produce offspring. If it exceeds 80, polymerization becomes unstable, and granular polymer cannot be obtained. There are cases where this is the case. Note that the acid value is based on JIS K 0070 and is calculated based on the amount contained in 1g of comb-type polymer. It can be measured as the number of mg of KOH required to neutralize the free carboxylic acid. (Base number is 100) If the value is less than 0, hollow formation may be difficult. If the value exceeds 2000, hollow formation may be difficult. This can sometimes be problematic. Note that the base number is the amount of basic components contained in 1g of comb-type polymer that neutralizes the base components. It can be measured as the amount of hydrochloric acid and the equivalent amount of potassium hydroxide required in milligrams.

[0091] The amount of comb-shaped polymer used is preferably 0.001 parts by mass per 100 parts by mass of the total monomer. It is 0.01 to 10 parts by mass, more preferably 0.01 to 4 parts by mass, and even more preferably The amount is between 0.01 parts by mass and 3 parts by weight. If the amount of comb-type polymer used is too small and falls outside this range, This may result in polymer particles that do not have a single void inside. If the amount exceeds the above range, the pore-forming effect (ease of pore formation) will not match the amount used. There is a risk that the desired result may not be obtained, or that the properties of the resulting resin particles (2) may be impaired.

[0092] Adhesive Composition The adhesive composition according to the embodiment of the present invention consists of resin particles (1) and resin particles (2). It contains at least one selected from the group and a base resin.

[0093] The resin particles (1) may be of only one type or of two or more types. ) may be of only one type or two or more types. The base resin may be of only one type. You may choose one, or two or more.

[0094] The base resins include epoxy resins, phenolic resins, resorcinol resins, and Acrylic resins, silicone resins, melamine resins, urea resins, urethane resins, At least one selected from the group consisting of polyimide resins and polyester resins. Among the various types, epoxy resins are preferred due to their superior mechanical, electrical, and chemical resistance properties. stomach.

[0095] The epoxy resin is not particularly limited; for example, bisphenol A type epoxy resin. Bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy Xylionic resin, a polyfunctional type containing many benzene rings, tetrakis(hydroxyphenyl) Tan-type or tris(hydroxyphenyl)methane-type epoxy resins, biphenyl-type epoxy resins Resins, triphenolmethane type epoxy resins, polybutadiene type epoxy resins (epoxy Polybutadiene, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin Examples include aminophenol-type epoxy resins and silicone epoxy resins.

[0096] The adhesive composition may contain a hardening agent. The hardening agent may be one type or two types. It may contain more than one type. The hardening agent can be appropriately selected depending on the type of base resin. Yes, it is possible. For example, when using epoxy resin as the base resin, the hardener could be, for instance, Phenolic resin curing agents, acid anhydride curing agents, amine curing agents, hydrazide compounds, Dicyandiamide can be used.

[0097] Examples of phenolic resin curing agents include phenolic resins, which are known as curing agents for epoxy resins. A phenolic resin can be used. Examples of such phenolic resin curing agents include resol. Examples include type phenolic resins and novolac type phenolic resins, such as alkylresol. Phenolic resins, alkyl novolac type phenolic resins, aralkyl novolac type phenolic resins Examples include xylene resins, xylene resins, and allylphenol resins. Alkyl resol type resins In the case of phenol resins or alkylnovolac type phenol resins, the alkyl group is: Preferably, alkyl groups having 1 to 18 carbon atoms can be used, such as ethyl, propyl, and butyric alkyl groups. Alkyl compounds with 2 to 10 carbon atoms, such as 1, pentyl, hexyl, octyl, nonyl, and decyl. A base is preferred. The number-average molecular weight of the phenolic resin curing agent is preferably 220 to 1000. And more preferably, 220 to 500.

[0098] As an acid anhydride-based curing agent, for example, an acid anhydride known as a curing agent for epoxy resins can be used. It is possible. Examples of such acid anhydride-based curing agents include phthalic anhydride and anhydride. Maleic acid, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarbonate Examples include dianhydride of rubonate, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. .

[0099] Amine-based curing agents include aliphatic amines, aromatic amines, and imidazoles. Examples of fatty amines include diethylenetriamine, triethylenetetraamine, and tetra Laethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine, 2 -Aliphatic polyamines such as methylpentamethylenediamine; isophorone diamine, 1,3 -Bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbo Alicyclic polyamines such as runendiamines and 1,2-diaminocyclohexane; N-amino Ethylpiperazine, 1,4-bis(2-amino-2-methylpropyl)piperazine, etc. Examples include perazine-type polyamines. Aromatic amines include, for example, diaminodiph Phenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyl toluene Diamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxy Do-di-p-aminobenzoate is one example. Also, tris(dimethylaminomethyl) Enol, benzyldimethylamine, 1,8-diazabicyclo(5,4,0)undense Tertiary amines such as n-7 can also be used. Imidazoles include, for example, 2 -Ethyl-4-methylimidazole, 2-phenylimidazole, 2-methylimidazole 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole Lu, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Examples include . In addition, modified imidazole-based curing agents can also be used, and epoxy- Examples include imidazole adduct compounds and acrylate-imidazole adduct compounds. Examples of commercially available epoxy-imidazole adduct compounds include, Amicure PN-23, Amicure PN-40 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Nova Cure HX-3721 (manufactured by Asahi Kasei E-Materials Co., Ltd.), Fuji Cure FX-1000 (Fuji Examples include those manufactured by Shikasei Kogyo Co., Ltd. Also, acrylate-imidazole adduct compounds and One example of a commercially available product is the EH2021 (manufactured by ADEKA). ru.

[0100] The amount of hardener used is not particularly limited, but for example, the total amount of components in the adhesive composition may be 1 Preferably 0.1 to 10 parts by mass, and more preferably 0. It is 5 parts by mass to 5 parts by mass.

[0101] The total content ratio of resin particles (1) and resin particles (2) in the adhesive composition (resin particles If only (1) is used, the percentage of resin particles (1) is used; if only resin particles (2) is used, the percentage of resin particles ( 2) The content ratio of the adhesive composition is preferably 0 when the total amount of components of the adhesive composition is 100 parts by mass. It is 0.1 to 35 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably The amount is preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass. The amount is preferably 8 to 18 parts by mass. Total of resin particles (1) and resin particles (2) If the content ratio is within the above range, sufficient tensile shear adhesive strength, high modulus of elasticity, and excellent stress An adhesive composition can be provided that exhibits both relaxation properties and other properties. Resin particles (1) If the total content of the resin particles (2) falls too far outside the above range, the elastic modulus will decrease. There is a risk of deterioration or a decrease in stress relaxation performance. Resin particles (1) and resin particles (2) If the total content of these ingredients exceeds the above range, the viscosity of the adhesive composition before curing will increase. This can lead to a decrease in workability and a reduction in tensile shear adhesive strength.

[0102] The adhesive composition may contain any other suitable components as long as they do not impair the effects of the present invention. Other such components may be present. Examples include inorganic particles and coupling agents. It can be done.

[0103] Inorganic particles are added to adhesive compositions for purposes such as improving dimensional stability, reducing moisture absorption, and improving heat dissipation. This is possible. The inorganic particles may be of one type or two or more types. The inorganic particles are not particularly limited and include, for example, silica, alumina, aluminum nitride, carbon Calcium oxide, aluminum silicate, magnesium oxide, magnesium silicate, magnesium carbonate Nesium, barium sulfate, barium carbonate, calcium sulfate, aluminum hydroxide, calcium silicate Um, potassium titanate, titanium dioxide, zinc oxide, silicon carbide, silicon nitride, boron nitride Examples include: The shape of inorganic particles is not particularly limited, for example, spherical, flake-shaped, needle-shaped, etc. A regular shape is preferred, and from the standpoint of workability, a spherical shape is preferred. The average particle size of the inorganic particles is preferred. The particle size is 0.05 μm to 10 μm. The amount of inorganic particles used is 10 times the total amount of components in the adhesive composition. When set to 0 parts by mass, it is preferably 50 parts by mass or less, and more preferably 20 to 5 parts by mass. It is 0 parts by mass.

[0104] Coupling agents can be added to fillers for purposes such as improving their dispersibility. The coupling agent may be one type or two or more types. , not particularly limited, for example aminosilane, epoxysilane, mercaptosilane, alkyl Silane couplings such as lucilane, ureidosilane, vinylsilane, and sulfidosilane. Examples include coupling agents; titanate-based coupling agents; and aluminum-based coupling agents. The amount of pulling agent used is preferably such that the total amount of components in the adhesive composition is 100 parts by mass. The amount is 5 parts by mass or less, and more preferably 0.2 parts by mass to 5 parts by mass.

[0105] The adhesive composition may be manufactured by any suitable method, provided that the effects of the present invention are not impaired. Obtain. The adhesive composition is typically composed of resin particles (1) and resin particles (2) from the group... At least one selected from the above, a base resin, and other optional components are blended in a predetermined proportion. It can be manufactured by uniformly dispersing the blended ingredients and then removing the air bubbles contained in the composition. ru.

[0106] The means of uniformly dispersing the blended ingredients are not particularly limited, but for example, a rotary mill This includes stirring using a stirring device such as a mixer. Degassing may also be performed during stirring. The means of performing such degassing are not particularly limited, but for example, by using a centrifugal degasser One method involves performing degassing along with stirring.

[0107] To prevent a decrease in adhesive performance, the uniformly dispersed composition is degassed (removed of air bubbles). This is preferable. The means of degassing are not particularly limited, but for example, a centrifugal degasser may be used. Methods for degassing include using a vacuum oven or other means to degas under reduced pressure. ru.

[0108] When uniformly dispersing the blended ingredients or when degassing, the composition should be prepared to the extent that it does not harden. It may be heated. By heating in this way, the viscosity of the blended components is reduced, and dispersion and defoaming can be easily performed.

[0109] The adhesive composition typically cures by heating under predetermined conditions and exhibits adhesive performance. The heating conditions can be appropriately set referring to the starting region temperature and active region temperature of the curing agent to be used. During such heating, it is preferable not to rapidly heat up to the starting temperature region but to gradually heat up. By gradually heating in this way, the curing agent can act gently, whereby the crosslinking of the base resin can be more firmly constructed and good adhesive performance can be exhibited.

[0110] The adhesive composition according to an embodiment of the present invention can exhibit both sufficient tensile shear adhesive strength, a high elastic modulus, and excellent stress relaxation performance by including resin particles (1). Although not bound by a specific theory, the technical reason for this is considered to be that the long-chain crosslinked structure by the resin particles (1) maintains the high elastic modulus of the particles themselves, and the long-chain side chains reduce the resin density around the particles.

[0111] The adhesive composition according to an embodiment of the present invention can exhibit both sufficient tensile shear adhesive strength, a high elastic modulus, and excellent stress relaxation performance by including resin particles (2). Although not bound by a specific theory, the technical reason for this is considered to be that the crosslinked structure of the shell part by the resin particles (2) maintains the high elastic modulus of the particles themselves, and the stress is absorbed by the deformation of the airspace part.

[0112] The adhesive composition according to an embodiment of the present invention preferably has a lap shear adhesive strength described later of The pressure is 6.0 MPa or higher, more preferably 8.0 MPa or higher, and even more preferably 1 The pressure is 0.0 MPa or higher, and particularly preferably 10.7 Pa or higher. The upper limit is preferably The pressure is 16.5 MPa or less.

[0113] The adhesive composition according to the embodiment of the present invention has a storage modulus E' at 40°C, as described later. Preferably 0.50 GPa or higher, more preferably 0.80 GPa or higher, and further Preferably, it is 1.00 GPa or higher, and particularly preferably 1.12 GPa or higher. The limit is preferably 2.20 GPa or less.

[0114] The adhesive composition according to the embodiment of the present invention exhibits the following stress relaxation effect (R1-R0), The amount is 3.0% or less, more preferably 2.0% or less, and even more preferably 1%. The lower limit is, ideally, 0.7% or less, and particularly preferably 1.6% or less. The percentage is 0%. [Examples]

[0115] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. It is not meant to be used. Unless otherwise specified, "parts" refers to "parts by mass," and "%" refers to "mass." It means "%".

[0116] <Measurement of volume-average particle diameter> The volume-average particle size of the resin particles was measured using the Coulter method as follows. The volume-average particle size of the resin particles is Coulter Multisizer (registered trademark) 3 (Bet). The measurement was performed using a measuring device from Beckman Coulter, Inc. In accordance with the Multisizer(registered trademark)3 User Manual issued by Tar Co., Ltd. The measurement was performed using a calibrated aperture. The aperture used for the measurement was selected from the tree being measured. The appropriate size was selected depending on the size of the lipid particles. The assumed volume-average particle diameter of the resin particles to be measured is 1 For sizes between μm and 10 μm, select an aperture with a size of 50 μm and perform the measurement. If the assumed volume-average particle size of the resin particles is greater than 10 μm and less than or equal to 30 μm, then 100 μm. Select an aperture of the following size, and assume that the volume-average particle size of the resin particles is larger than 30 μm. For particles smaller than 90 μm, select an aperture with a size of 280 μm, and assume the resin particles If the volume-average particle diameter is greater than 90 μm and less than or equal to 150 μm, it has a size of 400 μm. We made appropriate adjustments, such as selecting the appropriate aperture. The volume-average particle size after measurement was equal to the expected volume-average particle size. If the measurement differed from the measured diameter, the aperture was changed to one of the appropriate size, and the measurement was repeated. . Current (aperture current) and Gain (gain) are set for the selected aperture. The settings were adjusted as needed depending on the size. For example, an aperture with a size of 50 μm was selected. In this case, the Current (aperture current) is set to -800 and the Gain is set to 4. And, if you select an aperture with a size of 100 μm, Current(Aperture The current is set to -1600, and the gain is set to 2, with 280μm and 400μm. If you select an aperture of size , the Current (aperture current) will be -3 The value was set to 200, and the Gain was set to 1. For the measurement sample, 0.1 g of particles were mixed with 10 ml of a 0.1% by mass nonionic surfactant aqueous solution. 1. Touch Mixer (Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and ultrasonic cleaner (Velvoclea Co., Ltd., "ULTRASONIC CLEA It was dispersed using "NER VS-150" to obtain a dispersion, which was then used. During the measurement, the inside of the beaker was gently stirred to prevent air bubbles from entering, and the measurement was terminated when 100,000 resin particles were measured. The volume average particle diameter of the particles was taken as the arithmetic mean in the volume-based particle size distribution of 100,000 particles.

[0117] <Cross-section Observation> The dried resin particles were mixed with a photocurable resin D-800 (manufactured by JEOL Ltd.), and cured by irradiating ultraviolet light. Thereafter, the cured product was cut with nippers, and the cross-section was smoothed using a cutter. The sample was coated using a sputtering apparatus "Auto Fine Coater JFC-1300" manufactured by JEOL Ltd. Subsequently, the cross-section of the sample was photographed using the secondary electron detector of a scanning electron microscope "SU1510" manufactured by Hitachi High-Technologies Corporation.

[0118] [Production Example 1]: Production of Resin Particles (A) Into a 2 L autoclave container equipped with a stirrer, a thermometer, and a cooling mechanism, 400 parts by mass of ion-exchanged water and 2.5 parts by mass of magnesium pyrophosphate as a dispersion stabilizer were supplied to prepare an aqueous phase. Next, 60 parts by mass of alkyl methacrylate having a tridecyl group (carbon number = 13) as an alkyl group (manufactured by EVONIK, trade name "VISIOMER Terra (registered trademark) C13.0-MA"), 10 parts by mass of n-butyl acrylate, 20 parts by mass of methyl methacrylate, 10 parts by mass of ethylene glycol dimethacrylate, 0.3 parts by mass of caprolactone EO-modified phosphoric acid dimethacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYAMER (registered trademark) PM-21") as a surfactant, and 2,2'-azobis(2-methylpropionitrile) as a polymerization initiator ​​​​​​​​4-Dimethylvaleronitrile (ABN-V): 0.5 parts by mass, Benzoyl peroxide An oil phase was prepared by uniformly mixing 0.2 parts by mass of d(BPO). The oil phase is supplied to the aqueous phase in the autoclave container, and a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., table) is used. Using an upper-type TK homomixer, the mixture is stirred at a rotation speed of 8000 rpm for 10 minutes. A dispersion was prepared by dispersing droplets of the oil phase in the aqueous phase. After replacing the inside of the autoclave container with nitrogen gas, the dispersion is heated to 55°C and kept for 2 hours. Hold, then continue stirring, and 2 hours after confirming the exothermic peak, add 100% of the dispersion. The mixture was heated to ℃ and held for 3 hours to carry out the polymerization reaction. Subsequently, the dispersion is cooled to obtain a slurry (reaction solution) containing resin particles. The obtained slurry was then decomposed by adding hydrochloric acid to decompose the magnesium pyrophosphate, and then dewatered by centrifugal dehydration. The resin particles were dehydrated and washed multiple times with water. The resulting resin particles were treated with an antiblocking agent. After supplying silica microparticles as a bonding agent, they are dried in a vacuum oven at 60°C, and resin particles (A) are formed. The obtained resin particles (A) had a volume-average particle size of 8.5 μm.

[0119] [Manufacturing Example 2]: Manufacturing of resin particles (B) In a 2L autoclave container equipped with a stirring device, thermometer, and cooling mechanism, 4 units of deionized water were placed. 80 parts by mass and 9.6 parts by mass of magnesium pyrophosphate as a dispersion stabilizer are supplied, and the aqueous phase I made it. Next, methyl methacrylate (MMA): 40 parts by mass, as a vinyl-based crosslinkable monomer Ethylene glycol dimethacrylate (EGDMA): 40 parts by mass, as a non-reactive solvent Cyclohexane (CH): 60 parts by mass and ethyl acetate (EA): 20 parts by mass, polymerization As an initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako) Junyakusha Co., Ltd., product name V-65): 0.8 parts by mass, lauryl phosphate as a dispersing agent: 0.0 84 parts by mass were uniformly mixed to prepare the oil phase. The oil phase is supplied to the aqueous phase in the autoclave container, and a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., table) is used. Using an upper-type TK homomixer, the mixture is stirred for 5 minutes at a rotation speed of 7000 rpm. A dispersion was prepared by dispersing droplets of the oil phase in the aqueous phase. After replacing the inside of the autoclave container with nitrogen gas, the dispersion is heated to 50°C and kept for 2 hours. Hold, then continue stirring, and 2 hours after confirming the exothermic peak, add 100% of the dispersion. The mixture was heated to ℃ and held for 3 hours to carry out the polymerization reaction. Subsequently, the dispersion is cooled to obtain a slurry (reaction solution) containing resin particles. The obtained slurry was then decomposed by adding hydrochloric acid to decompose the magnesium pyrophosphate, and then dewatered by centrifugal dehydration. The resin particles were dehydrated and washed multiple times with water. The resulting resin particles were treated with an antiblocking agent. After supplying silica microparticles as a bonding agent, they are dried in a vacuum oven at 100°C, and then resin particles (B The obtained resin particles (B) had a volume-average particle size of 9.8 μm. A cross-sectional photograph of the obtained resin particles (B) is shown in Figure 1. According to Figure 1, the resin particles (B) are... The hollow particle has a non-porous shell portion and a hollow portion surrounded by the shell portion. Confirmed.

[0120] [Manufacturing Example 3]: Manufacturing of resin particles (C) In a 2L autoclave container equipped with a stirring device, thermometer, and cooling mechanism, ion-exchanged water: 1 50 parts by mass, tricalcium phosphate as a dispersion stabilizer: 10 parts by mass, and as a surfactant By adding 0.02 parts by mass of sodium dodecylbenzenesulfonate, an aqueous phase is created. It was made. Next, styrene: 35 parts by mass and divinylbenzene as a crosslinkable styrene monomer: 5 5 parts by mass, having an alkylene oxide group as a hydrophilic (meth)acrylic monomer ( Meth)acrylic acid ester (manufactured by NOF Corporation, Bremmer 50PEP300): 10 parts by mass, weight Azobisvaleronitrile as a coagulation initiator: 0.4 parts by mass, a surfactant consisting of a comb-shaped polymer Agent (manufactured by Lubrizol, Solspers 26000, weight-average molecular weight 26000, acid value 5) An oil phase was prepared by mixing 1 part by mass of (0±4, basicity 1500±150). The oil phase is supplied to the aqueous phase in the autoclave container, and a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., table) is used. Using an upper-type TK homomixer, the mixture is stirred at a rotation speed of 8000 rpm for 10 minutes. A dispersion was prepared by dispersing droplets of the oil phase in the aqueous phase. After replacing the autoclave container with nitrogen gas, the dispersion was heated to 60°C for 12 hours. Hold the mixture, then continue stirring. After confirming the exothermic peak, 2 hours later, pour the dispersion into a 100ml container. The mixture was heated to 0°C and held for 3 hours to carry out the polymerization reaction. The resin particles were then dehydrated using a centrifugal dehydrator and washed multiple times with water. The resulting resin particles were then... After supplying silica microparticles to the child as an antiblocking agent, in a vacuum oven at 100°C The mixture was dried to obtain resin particles (C). The volume-average particle size of the obtained resin particles (C) was 8.3 μm. That was the case. Figure 2 shows a cross-sectional photograph of the obtained resin particles (C). As shown in Figure 2, the resin particles (C) are non It has been confirmed that it is a hollow particle having a porous shell portion and a hollow portion surrounded by the shell portion. I was able to confirm it.

[0121] [Manufacturing Example 4]: Manufacturing of resin particles (D) In a 2L autoclave container equipped with a stirring device, thermometer, and cooling mechanism, 4 units of deionized water were placed. 00 parts by mass, polyvinyl alcohol (saponification degree 85%) as a dispersion stabilizer: 8 parts by mass, interface 0.04 parts by mass of sodium lauryl sulfate was added as an activator to prepare the aqueous phase. Next, butyl acrylate: 80 parts by mass, tetradecaethylene glycol dimethacrylate Light Ester 14EG (manufactured by Kyoeisha Chemical Co., Ltd.): 20 parts by mass, as a polymerization initiator. An oil phase was prepared by uniformly mixing 0.3 parts by mass of benzoyl peroxide (BPO). . The oil phase is supplied to the aqueous phase in the autoclave container, and a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., table) is used. Using an upper-type TK homomixer, the mixture is stirred at a rotation speed of 5000 rpm for 10 minutes. A dispersion was prepared by dispersing droplets of the oil phase in the aqueous phase. After replacing the inside of the autoclave container with nitrogen gas, the dispersion is heated to 60°C and kept for 6 hours. Hold, then continue stirring, and 2 hours after confirming the exothermic peak, add 100% of the dispersion. The mixture was heated to ℃ and held for 3 hours to carry out the polymerization reaction. The resin particles were then dehydrated using a centrifugal dehydrator and washed multiple times with water. The resulting resin particles were then... After supplying silica microparticles to the child as an antiblocking agent, dry them in a vacuum oven at 60°C. Resin particles (D) were obtained by drying. The volume-average particle size of the obtained resin particles (D) was It was 7.8 μm.

[0122] [Examples 1-13, Comparative Examples 1-3] After weighing the resin particles and epoxy resin raw materials according to the mixing ratios listed in Table 1, stir and degas. Using a container (made by Shinky Co., Ltd., product name "Awatori Rentaro"), mix for 5 minutes, then degas for 2 minutes and mix again. The mixture was kneaded. Then, by vacuum drying at 80°C for 4 hours, the epoxy resin was processed. Compositions (1) to (13) and (C1) to (C3) were prepared. The resin particles include the resin particles (A) to (D) produced in manufacturing examples 1 to 4, and Nipol ( (Registered Trademark) DN601 (Carboxy-modified NBR, manufactured by Zeon Corporation), Paraloid EXL-2 314 (acrylic core-shell rubber, manufactured by DOW Corporation) was used. As a raw material for epoxy resin, the main component is bisphenol A type liquid epoxy resin (product Name: "EPICRON840" (manufactured by DIC Corporation), uses imidazole epoxy resin as a hardening agent. A lipid hardening agent (product name "2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.) was used. The obtained epoxy resin compositions (1) to (13) and (C1) to (C3) were superimposed. The bonding strength, stress relaxation rate, and storage modulus were measured by the following method. The results are shown in Table 1.

[0123] <Method for measuring overlapping adhesive strength> The overlapping adhesive strength was measured in accordance with JIS K6850:1999. The adhesive strength is based on Shimadzu Corporation's "Autograph AG-X plus 100kN". Universal testing machine, Shimadzu Corporation's "TRAPEZIUM-X" universal testing machine data processing is used. He went. The test specimen was made of cold-rolled steel coated with an epoxy resin composition, which had been degreased beforehand with ethanol. The edge (length 11.25 mm) of the board (length 100 mm, width 25 mm, thickness 1.6 mm) Place 0.06g on the 25mm wide section, and overlap the same section of a cold-rolled steel sheet of the same dimensions. After sandwiching it between lipsticks and letting it sit overnight, bake it in the oven at 100°C, 120°C, 140°C, and 160°C. The material was heated to 1°C and then 180°C for 1 hour each to cure it. After curing, the hardened material that had protruded from the cold-rolled steel sheet was removed. Test specimens were prepared by removing the monoxide. Five test specimens were prepared. The test specimens were placed under the standard atmosphere of Class 2, symbol "23 / 50" according to JIS K 7100:1999. After conditioning for 16 hours, the samples were used for measurement. The measurements were taken under the same environmental conditions, and the test speed was The rate of change was set to 1 mm / min, and the gripping distance was 112.5 mm. From the resulting graph, the slope was the maximum. The intersection of the resulting straight line and the stroke was defined as the origin of the elongation, and the fracture point test force (N) was automatically calculated. The overlapping adhesive strength was calculated from the obtained fracture strength using the following formula. Overlap bond strength (MPa) = Breaking point test force (N) ÷ Bonding area (mm²) 2 )

[0124] <Measurement of Storage Modulus E'> The viscoelasticity measurement device used was the "DMA 7100" manufactured by Hitachi High-Tech Science Co., Ltd. The test specimen was prepared by first shaping the epoxy resin composition into a test specimen (length 40 mm, width 10 mm, thickness After placing it in a silicone mold adjusted to 1 mm, and vacuum drying it again at 80°C for 1 hour, Heat at 100°C, 120°C, 140°C, 160°C, and 180°C for 1 hour each, then apply epoxy resin. The test was prepared by curing a lipid composition. Three test specimens were used. The conditions were as follows: Measurement mode: Tensile control mode Test specimen size: 40L x 10W x approximately 1.0T (mm) Atmosphere: Nitrogen atmosphere Frequency: 1Hz Heating rate: 5°C / min Measurement temperature: 30~250℃ Chuck spacing: 20mm Distortion amplitude: 5μm Minimum tension: 50mN Tension: Gain: 1.2 Initial force amplitude: 50 mN The analysis is performed using the analysis software included with the device, and the value of the storage modulus E' at a predetermined temperature is read. .

[0125] <Measurement of stress relaxation rate> The stress relaxation test was conducted using the "Autograph AG-X pl" measuring instrument manufactured by Shimadzu Corporation. "us 100kN" Universal Testing Machine, Shimadzu Corporation "TRAPEZIUM-X" Universal This was done using test machine data processing. The test specimen was prepared by first shaping the epoxy resin composition into a test specimen (length 80 mm, width 10 mm, thickness After placing it in a silicone mold adjusted to 4mm, and vacuum drying it again at 80°C for 1 hour, Heat at 100°C, 120°C, 140°C, 160°C, and 180°C for 1 hour each, then apply epoxy resin. The test was prepared by curing a lipid composition. Five test specimens were used. The test specimens were placed under the standard atmosphere of Class 2, symbol "23 / 50" according to JIS K 7100:1999. After conditioning for 16 hours, the samples were used for measurement. The measurements were taken under the same environmental conditions, and the test speed was The flow rate was set to 2 mm / min. The radius of the pressure wedge and the tip of the support point was set to 5R, and the distance between the support points was I set it to 64mm. After the test begins, the movement of the pressurized wedge is stopped when it has moved 1.5 mm, and then... I held it there for 5 minutes. The stress relaxation rate R was calculated using the following formula. R(%) = (σ0 - σ5) / σ0 × 100 Here, σ0 is the bending resistance of the test specimen when the displacement of the pressurized wedge is 1.5 mm. The force is expressed, and σ5 is the value obtained 5 minutes after the amount of movement of the pressurized wedge reaches 1.5 mm. This shows the bending stress of the test specimen. Note that the stress relaxation effect described in Table 1 is calculated based on the stress relaxation rate R1 (test results for each example and comparative example). (Stress relaxation rate of the test specimen) and stress relaxation rate R0 (test specimen without added resin particles (blank)) The stress relaxation rate is the difference (R1-R0) between the stress relaxation rate of the specimen (blank) of Comparative Example 1 and the stress relaxation rate of the specimen (blank). ru.

[0126] [Table 1] [Industrial applicability]

[0127] Adhesive compositions according to embodiments of the present invention, for adhesive applications in electrical and electronics, mechanical manufacturing, automobiles, etc. It can be suitably used for the following purposes.

Claims

1. An adhesive composition containing resin particles (2) and a base resin, The resin particle (2) is a resin particle having a non-porous shell portion and a hollow portion surrounded by the shell portion. The shell portion is obtained by polymerizing a monomer that includes at least one selected from the group consisting of monofunctional vinyl monomers and polyfunctional vinyl monomers. Adhesive composition.

2. The adhesive composition according to claim 1, wherein the base resin is at least one selected from the group consisting of epoxy resins, phenolic resins, resorcinol resins, acrylic resins, silicone resins, melamine resins, urea resins, urethane resins, polyimide resins, and polyester resins.

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