KR102198770B1 - Energy beam-curable adhesive - Google Patents

Abstract

Provides a curable adhesive with excellent heat and cooling resistance. An energy ray-curable adhesive containing (A) 100 parts by mass of (meth)acrylate, (B) 25 to 150 parts by mass of polyolefin particles, (C) an inorganic filler, and (D) a photoradical polymerization initiator. (A) (meth)acrylate may contain (A1) monofunctional (meth)acrylate and (A2) polyfunctional (meth)acrylate. (B) The polyolefin particles may contain polyethylene particles and/or polypropylene particles.

Description

Energy beam-curable adhesive

The present invention relates to an energy ray-curable adhesive. For example, the present invention relates to an energy ray-curable adhesive having excellent curability, adhesiveness, low curing shrinkage, low adhesive deformation, and excellent cold and heat cycle resistance, and a cured product and a joint using the same.

In the field of optoelectronics, as devices become more high-performance, there are increasing cases of bonding between various different materials as adherends such as glass, metal, ceramic, plastic, and engineering plastic.

In particular, engineering plastics represented by polycarbonate, polyphenyl sulfide, and liquid crystal polymers, which are plastics having excellent heat resistance, low thermal expansion, and moldability from the viewpoint of device weight reduction, have been used instead of metal materials. However, since engineering plastics generally lack adhesiveness, an adhesive exhibiting high adhesion to engineering plastics has been required.

Furthermore, there is a demand for an adhesive having high adhesive strength and good heat resistance and moisture resistance even between various different materials as described above. In the adhesion between various different materials, since the influence of the internal stress caused by curing shrinkage of the adhesive or the like on various adherends cannot be neglected, it is required to have less adhesive deformation due to low curing shrinkage. Further, in the cold-heat cycle test, which is repeatedly exposed to a low-temperature atmosphere and a high-temperature atmosphere, there has been a problem in that a significant stress is applied to the adhesive due to the difference in the linear expansion coefficient of the adherend, so that peeling or whitening is likely to occur. There is a demand for the development of an adhesive having excellent resistance to the cooling and heating cycle, that is, the cooling and heating cycle resistance.

Among these technologies, adhesives in the field have been shifted from thermosetting epoxy adhesives to ultraviolet curing acrylic adhesives or epoxy adhesives in consideration of mass production.

For example, Patent Documents 1 to 3 have excellent adhesion to various adherends, heat resistance, and moisture resistance, and furthermore, diene-based or hydrogenated having a specific molecular weight, characterized in that there is little adhesion deformation due to low curing and shrinkage properties. An energy ray-curable resin composition containing a diene-based (meth)acrylate, a (meth)acrylate of a specific structure, a photopolymerization initiator and an antioxidant is disclosed.

In addition, for example, in Patent Documents 1 and 4 to 6, an energy ray-curable resin composition is described.

Patent Document 1: International Publication No. 2006/129678 Patent Document 2: Japanese Laid-Open Patent No. 2007-77321 Patent Document 3: Japanese Laid-Open Patent No. 2008-101106 Patent Document 4: Japanese Laid-Open Patent No. 2007-9131 Patent Document 5: Japanese Laid-Open Patent No. 2010-95627 Patent Document 6: Japanese Laid-Open Patent No. 2007-77321 Patent Document 7: Japanese Laid-Open Patent No. 2010-143153

However, these prior art documents have not been able to satisfy the recently required cold and heat cycle resistance in adhesion of different types of adherends. In addition, Patent Documents 4 to 5 do not describe making the amount of polyolefin particles more than 20 parts by mass. In addition, Patent Documents 1 and 6 do not describe a combination of polyolefin particles. Patent Document 7 does not describe what is used as an adhesive.

The present invention has been made in view of the circumstances of these prior art documents. An object of the present invention is to provide an energy ray-curable resin composition having a high adhesive strength to various adherends such as glass, metal, and plastic, particularly engineering plastics. It is an object of the present invention to provide an energy ray-curable resin composition having low curing shrinkage, excellent heat-cooling resistance and excellent storage stability in adhesion of different types of adherends.

According to one aspect of the present invention, the following is provided.

(1) (A) 100 parts by mass of (meth)acrylate, (B) 25 to 150 parts by mass of polyolefin particles, (C) an inorganic filler, (D) an energy ray-curable adhesive containing a photoradical polymerization initiator.

(2) The (A) (meth)acrylate is an energy ray-curable adhesive containing (A1) a monofunctional (meth)acrylate and (A2) a polyfunctional (meth)acrylate.

(3) The energy ray-curable adhesive wherein (A2) the polyfunctional (meth)acrylate is an oligomer having two or more (meth)acryloyl groups in the molecule.

(4) The (A2) main chain skeleton of the oligomer having two or more (meth)acryloyl groups in the molecule is one selected from the group consisting of polybutadiene, polyisoprene, hydrogenated products of polybutadiene, and hydrogenated products of polyisoprene The above energy ray curable adhesive.

(5) The (A1) monofunctional (meth)acrylate is (a-1) a monofunctional (meth)acrylate having an alicyclic hydrocarbon group, (a-2) a hydroxyl group-containing monofunctional (meth)acrylate, and (a -3) Energy ray-curable adhesive containing a monofunctional (meth)acrylate having a carboxyl group or a phosphate ester group.

(6) The (a-1) monofunctional (meth)acrylate having an alicyclic hydrocarbon group is (a-11) a monofunctional (meth)acrylate having a saturated alicyclic hydrocarbon group and (a-22) an unsaturated alicyclic Energy ray-curable adhesive containing monofunctional (meth)acrylate having a formula hydrocarbon group.

(7) The energy ray-curable adhesive in which the (B) polyolefin particles are polyethylene particles and/or polypropylene particles.

(8) The energy ray-curable adhesive having a density of (B) polyolefin particles of 0.85 to 0.95 g/cm 3 and an average particle diameter of 5 to 30 μm.

(9) The energy ray-curable adhesive of the (C) inorganic filler having a density of 2.00 to 3.00 g/cm 3 and an average particle diameter of 0.001 to 40 μm.

(10) The energy ray-curable adhesive in which the (C) inorganic filler is at least one selected from the group consisting of fused silica, spherical silica, fumed silica, finely divided silica, quartz, quartz glass, and glass filler.

(11) A cured product obtained by curing the energy ray-curable adhesive.

(12) An adhesive for energy ray-curable heterogeneous materials comprising the energy ray-curable adhesive.

(13) Energy ray-curable adhesive for engineering plastics comprising the energy ray-curable resin composition.

(14) A bonded body using the energy ray-curable adhesive.

(15) A method of bonding two or more adherends using the energy ray-curable adhesive.

The energy ray-curable adhesive of the present invention can be cured by, for example, irradiation with energy rays, and has low curing shrinkage at the time of curing and exhibits high elongation, so it has the effect of excellent cold heat cycle resistance and storage stability. .

<Explanation of terms>

In this specification, the energy ray-curable resin composition means a resin composition that can be cured by irradiating energy rays. Here, the energy ray means an energy ray represented by ultraviolet rays and visible rays.

One embodiment of the present invention is a novel adhesive containing an energy ray-curable resin composition of a specific composition. Hereinafter, an energy ray-curable resin composition used in an embodiment of the present invention will be described.

The energy ray-curable resin composition used in one embodiment of the present invention includes (A) 100 parts by mass of (meth)acrylate, (B) 25 to 150 parts by mass of polyolefin particles, (C) inorganic filler, (D) photoradical polymerization. The initiator is an essential component. (A) (meth)acrylate preferably contains (A1) monofunctional (meth)acrylate and (A2) polyfunctional (meth)acrylate as essential components.

(A1) Monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in the molecule.

(A1) Monofunctional (meth)acrylate is preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, out of 100 parts by mass in total of the component (A) when the balance of workability, adhesion, and low curing shrinkage is considered. It is preferable, and 30-50 mass parts is most preferable. If it is 10 mass parts or more, the viscosity of the obtained resin composition becomes too high, and there is no problem in workability in a manufacturing process or practical use, and if it is 80 mass parts or less, excellent adhesiveness and low hardening shrinkage can be obtained. In addition, the above value may be, for example, 10, 20, 30, 40, 50, 60, 70, or 80 parts by mass, and may be within the range of any two of these values.

(A1) Monofunctional (meth)acrylate is (a-1) monofunctional (meth)acrylate having an alicyclic hydrocarbon group, (a-2) monofunctional (meth)acrylate containing a hydroxyl group, (a-3) carboxyl group Or it is preferable to make monofunctional (meth)acrylate which has a phosphoric acid ester group essential. (A-1) The monofunctional (meth)acrylate having an alicyclic hydrocarbon group used in the embodiment of the present invention refers to a monofunctional (meth)acrylate having an alicyclic hydrocarbon group through an ester bond.

(a-1) Examples of the alicyclic hydrocarbon group of the monofunctional (meth)acrylate having an alicyclic hydrocarbon group include a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group. Examples of the unsaturated hydrocarbon group include an unsaturated hydrocarbon group having a carbon-carbon double bond or a carbon-carbon triple bond. The alicyclic hydrocarbon group preferably has 6 to 20 carbon atoms.

Monofunctional (meth)acrylates having a saturated alicyclic hydrocarbon group include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, Bonyl (meth)acrylate, bonyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tricyclodecanyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (meth) Acrylate, 1-adamantanyl (meth)acrylate, and the like. Among these, isobornyl (meth)acrylate is preferable. Examples of the monofunctional (meth)acrylate having an unsaturated alicyclic hydrocarbon group include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate. . Among these, dicyclopentenyloxyethyl (meth)acrylate is preferable.

(a-1) Among the monofunctional (meth)acrylates having an alicyclic hydrocarbon group, (a-11) monofunctional (meth)acrylates having a saturated alicyclic hydrocarbon group and (a -22) It is preferable to contain a monofunctional (meth)acrylate having an unsaturated alicyclic hydrocarbon group. When (a-11) and (a-22) are used together, the content ratio of (a-11) and (a-22) is (a-11) and (a-22) in 100 parts by mass in total. -11): (a-22) is preferably 30 to 80 parts by mass: 70 to 20 parts by mass, more preferably 45 to 65 parts by mass: 55 to 35 parts by mass. In addition, (a-11): (a-11) in (a-22) may be, for example, 30, 40, 45, 50, 55, 60, 70, or 80 parts by mass, and any two of these values It may be within the range of. In addition, (a-11): (a-22) to (a-22) may be, for example, 70, 65, 60, 50, 40, 35, 30, or 20 parts by mass, and any two of these values It may be within the range of.

As the (a-2) hydroxyl group-containing monofunctional (meth)acrylate used in one embodiment of the present invention, a monofunctional (meth)acrylate monomer having a hydroxyl group in the molecule is preferable. As a hydroxyl group-containing monofunctional (meth)acrylate monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( Meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalate, glycerol mono(meth)acrylate, 1,6 -Hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, 1,4-butanediol mono(meth)acrylate, etc. are mentioned. Among these, 2-hydroxyethyl (meth)acrylate is preferable.

(A-3) Monofunctional (meth)acrylates having a carboxyl group or phosphoric acid ester group used in the embodiment of the present invention include (meth)acryloyloxyethyl acid phosphate, (meth)acryloyloxyethyl polyethylene glycol acid Phosphate, (meth)acrylic acid, ω-carboxy-polycaprolactone mono (meth)acrylate, phthalic acid monohydroxyethyl (meth)acrylate, (meth)acrylic acid dimer, β-(meth)acryloyloxyethyl hydrogen Succinate, 2-(meth)acryloyloxyethyl succinic acid, etc. are mentioned. Among these, a monofunctional (meth)acrylate having a carboxyl group is preferable. Among the monofunctional (meth)acrylates having a carboxyl group, 2-(meth)acryloyloxyethylsuccinic acid is preferable.

(a-1) monofunctional (meth)acrylate having an alicyclic hydrocarbon group, (a-2) monofunctional (meth)acrylate containing a hydroxyl group, (a-3) monofunctional (meth)acryl having a carboxyl group or a phosphate ester group The content ratio of the rate is 100 parts by mass of the total 100 parts by mass of the (A1) component, especially the (a-1) component, the (a-2) component, and the (a-3) component in terms of curability, adhesiveness, and low shrinkage. 50 to 70 parts by mass of (a-1) component, 25 to 45 parts by mass of component (a-2), and 1 to 15 parts by mass of component (a-3) are preferred, and 55 to 65 parts by mass of component (a-1) , (a-2) component 30-40 mass parts, (a-3) component 3-10 mass parts are more preferable. In addition, even if the (a-1) component is, for example, 50, 55, 60, 65 or 70 parts by mass among 100 parts by mass of the total of the component (a-1), the component (a-2) and the component (a-3) And any two of these values may be in the range. In addition, the component (a-2) may be, for example, 25, 30, 35, 40, or 45 parts by mass, and may be in the range of any two values of these. In addition, the component (a-3) may be, for example, 1, 3, 5, 10, 12, or 15 parts by mass, and may be within the range of any two of these values.

(A2) Polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in a molecule.

(A2) The polyfunctional (meth)acrylate is preferably an oligomer having two or more (meth)acryloyl groups in the molecule (A1).

As an oligomer having two or more (meth)acryloyl groups in the molecule (A2) used in one embodiment of the present invention, (meth)acrylic-modified polybutadiene having two or more (meth)acryloyl groups in the molecule, (meth )Acrylic modified polyisoprene, hydrogenated product of (meth)acrylic modified polybutadiene, hydrogenated product of (meth)acrylic modified polyisoprene, polyurethane (meth)acrylate oligomer, polyester (meth)acrylate oligomer, epoxy (meth) And acrylate oligomers and silicone-based (meth)acrylate oligomers.

Among these, the main chain skeleton of the oligomer having two or more (meth)acryloyl groups in the molecule from the viewpoint of excellent curability and compatibility is in the group consisting of polybutadiene, polyisoprene, hydrogenated product of polybutadiene, and hydrogenated product of polyisoprene. It is more preferable that it is at least 1 type selected, and it is most preferable that it is polybutadiene.

(A2) The molecular weight of the oligomer having two or more (meth)acryloyl groups in the molecule is preferably 500 to 20,000, more preferably 800 to 10,000, and most preferably 1,000 to 5,000. If the molecular weight is 500 or more, the hardness of the cured product obtained by irradiating the resin composition of one embodiment of the present invention with energy rays is not too low to make it difficult to form the adhesive layer. There is no problem in workability in practical use. Here, molecular weight means a number average molecular weight. (A2) A method of measuring the molecular weight of an oligomer having two or more (meth)acryloyl groups in the molecule is described in Examples. Further, the molecular weight may be, for example, 500, 800, 1,000, 3,000, 5,000, 10,000, 15,000, or 20,000, and may be within the range of any two of these values.

(A2) Examples of oligomers having two or more (meth)acryloyl groups in the molecule include oligomers having a polybutadiene structure and/or a hydrogenated polybutadiene structure in the molecule. Examples of oligomers having a polybutadiene structure in the molecule include both terminal (meth)acrylate-modified butadiene-based oligomers of the general formula (A). However, instead of the both-end (meth)acrylic-modified butadiene-based oligomer represented by the general formula (A), you may select the both-end (meth)acrylate-modified hydrogenated butadiene-based oligomer represented by the general formula (B). As an oligomer having a polybutadiene structure and/or a hydrogenated polybutadiene structure in a molecule, NISSO-PB TEAI-1000 (both acrylate-modified hydrogenated butadiene-based oligomers made by Nippon Soda) and NISSO-PB TE-2000 from Nippon Soda (Both terminal methacrylate-modified butadiene oligomers) and the like.

[Formula 1]

General formula (A)

(R in general formula (A) is a structural formula represented by general formula (X))

General formula (X)

(R' in the general formula (X) is H or CH ₃ )

[Formula 2]

General formula (B)

(R in general formula (B) is a structural formula represented by general formula (X))

When (A2) polyfunctional (meth)acrylate considers the balance of workability, adhesiveness, and low curing shrinkage, 20 to 90 parts by mass is preferable out of the total 100 parts by mass of the component (A), and more than 40 to 80 parts by mass It is preferred, and 50 to 70 parts by mass is most preferred. If it is 20 mass parts or more, excellent adhesiveness and low curing shrinkage can be obtained, and if it is 90 mass parts or less, the viscosity of the obtained resin composition becomes too high, and there is no problem in workability in a manufacturing process or practical use. In addition, (A2) component may be, for example, 20, 30, 40, 50, 60, 70, 80, or 90 parts by mass among the total 100 parts by mass of the (A) component, and even within the range of any two of these values. do. In one embodiment of the present invention, two or more may be, for example, 2, 3, 4, 5, or 10, and may be within the range of any two values.

The energy ray-curable resin composition used in one embodiment of the present invention contains (B) polyolefin particles as an essential component.

As the polyolefin used for the (B) polyolefin particles used in the embodiment of the present invention, a copolymer of olefins such as polyethylene, polypropylene, and ethylene-propylene can be used. Among these, polyethylene and/or polypropylene are preferred. As the polyethylene, at least one of the group consisting of low density polyethylene, linear low density polyethylene, branched low density polyethylene, high density polyethylene, and ultra high molecular polyethylene is preferable.

(B) Polyolefin particles include low-density polyethylene particles (SK-PE-20L), polypropylene particles (PPW-5) manufactured by Seishin Corporation, ultra-high molecular polyethylene manufactured by Mitsui Chemicals (Miferon series, Hijax series), Sumitomo Chemical low-density polyethylene (Excelene GMH, Sumikasen EP), Nippon Seiro's low-density low molecular weight branched polyethylene (WEISSEN-0252C, WEISSEN-0453), Clariant's polyethylene and polypropylene (CERIDUST series), etc. I can.

(B) The molecular weight of the polyolefin constituting the polyolefin particles is preferably 50,000 or more and 10,000,000 or less, more preferably 100,000 or more and 5,000,000 or less, and more preferably 300,000 or more, as measured by the number average molecular weight (the viscosity average molecular weight of ultra-high molecular polyethylene). Most preferably, it is 2,000,000 or less. Within this molecular weight range, the viscosity of the obtained resin composition is too high, and there is no problem in workability when using the resin composition in the manufacturing process or in practical use, and the resin composition exhibits excellent adhesion and low curing shrinkage and excellent heat resistance. Cyclability can be obtained. Further, the molecular weight may be, for example, 50,000, 80,000, 100,000, 300,000, 1,000,000, 5,000,000, 8,000,000, or 10,000,000, and may be within the range of any two of these values.

(B) The molecular weight of the polyolefin particles can be measured by a known method such as gel permeation chromatography (GPC). As a measurement method, the following methods are mentioned, for example. As a column, "TSKgel GMHhr-H(20)HT" manufactured by Tosoh Corporation was used, the column temperature was set to 140°C, 1,2,4-trichlorobenzene was used as an eluent, and the measurement sample was 1.0 mg/ml. It was prepared at the concentration of and 0.3 ml was injected into the column to measure. The molecular weight calibration curve was calculated using a polystyrene sample whose molecular weight was already known, and the value was obtained as the molecular weight.

In the case of ultra-high molecular weight polyethylene having a molecular weight of more than 1 million, the molecular weight can be determined from the intrinsic viscosity [η] as a viscosity average molecular weight (Mv). Specifically, the intrinsic viscosity [η] is measured using tetralin at 130°C as a solvent, and the molecular weight can be obtained from the following equation.

[Η] = K × Mv ^a =4.60 × 10 ^-4 × M ^0.725 (wherein, K and a are constants, and Mv is a molecular weight.)

(B) The density (g/cm 3) of the polyolefin particles is a value measured by the density gradient tube method in accordance with JIS K 6760 (1995), preferably 0.85 g/cm 3 or more and 0.95 g/cm 3 or less, and 0.89 g/cm 3 It is more preferably 0.94 g/cm 3 or less. Within this density range, the viscosity of the obtained resin composition is too high, so that there is no problem in workability when the resin composition is used in the manufacturing process or in practical use, and the resin composition exhibits excellent adhesion and low curing shrinkage and excellent cold and heat resistance. Cyclability can be obtained.

(B) The average particle diameter of the polyolefin particles is a value measured by a known particle size distribution meter, and is preferably 5 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. Within this range of the average particle diameter, the viscosity of the obtained resin composition is too high to cause a problem in workability when the resin composition is used in the manufacturing process or in practical use, and the resin composition exhibits excellent adhesion and low curing shrinkage and excellent resistance to Cooling and heat cycling properties can be obtained. In the examples described later, a value measured with a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation) was employed. Moreover, the said average particle diameter may be 5, 10, 15, 20, 25, 30, 100, or 150 micrometers, for example, and may fall within the range of any two of these values.

(B) As the polyolefin particle, a chemically modified surface can be used for the purpose of improving the affinity with (A) (meth)acrylate. Examples of the surface modification include a hydroxyl group modification, a carbonyl modification, a maleic anhydride modification, and the like, but can be used without being limited thereto.

(B) The amount of polyolefin particles used is preferably 25 to 150 parts by mass, more preferably 28 to 70 parts by mass, and most preferably 30 to 45 parts by mass based on 100 parts by mass of (A). In this range, the viscosity of the obtained resin composition does not increase, and excellent adhesion and heat-cooling cycle resistance can be obtained. In addition, the component (B) may be, for example, 25, 28, 30, 35, 45, 70, 100, 115, 120, or 150 parts by mass per 100 parts by mass of (A), the range of any two values It may be mine.

In one embodiment of the present invention, for the purpose of further imparting rigidity and low curing and shrinkage properties, an inorganic filler is used as an essential component as the component (C).

(C) As inorganic fillers, glass fillers such as quartz, quartz glass, glass frit, silica powders such as fused silica, spherical silica, fumed silica, and finely divided silica, or spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, etc. Oxides, boron nitride, silicon nitride, nitrides such as aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals or alloys such as copper, silver, iron, aluminum, nickel, titanium Carbon-based fillers such as oil, diamond, and carbon. One type or two or more types of inorganic fillers can be used. Among the inorganic fillers, at least one selected from the group consisting of fused silica, spherical silica, fumed silica, finely divided silica, quartz, quartz glass, and glass fillers is preferred from the viewpoint of being readily available and excellent in packing properties and stability.

(C) As inorganic fillers, fused silica (FB series) and finely divided silica (SFP series, UFP series) manufactured by Denki Chemical Industries, glass fillers manufactured by Nippon Frit (CF series), silica (Tokuseal series) manufactured by Tokuyama, Tatsumori's crystalline quartz (Crystallite series, Heurex series), Fuji Sicilia's hydrophilic silica (Syricia series), Nippon Silica's hydrophilic silica (Nippel series), Evonik's fumed silica (Aerozyl series) And the like.

(C) The density (g/cm 3) of the inorganic filler is a value measured by a density gradient tube method in accordance with JIS K 6760 (1995), and is preferably 2.00 g/cm 3 or more and 3.00 g/cm 3 or less, and 2.10 g/cm 3 or more 2.60 g/cm 3 or less is more preferable, and 2.10 g/cm 3 or more and 2.45 g/cm 3 or less are most preferable. Within this density range, the viscosity of the obtained resin composition is too high, so that there is no problem in workability when the resin composition is used in the manufacturing process or in practical use, and the resin composition exhibits excellent adhesion and low curing shrinkage and excellent cold and heat resistance. Cyclability can be obtained. In addition, the density may be, for example, 2.00, 2.10, 2.20, 2.30, 2.40, 2.45, 2.50, 2.60, 2.70 or 3.00 cm 3, and may be within the range of any two of these values.

(C) The average particle diameter of the inorganic filler is a value measured by a known particle size distribution meter, preferably 0.001 μm or more and 40 μm or less, more preferably 0.005 μm or more and 25 μm or less, and most preferably 0.1 μm or more and 23 μm or less. Within this range of the average particle diameter, the viscosity of the obtained resin composition is too high to cause a problem in workability when the resin composition is used in the manufacturing process or in practical use, and the resin composition exhibits excellent adhesion and low curing shrinkage and excellent resistance to Cooling and heat cycling properties can be obtained. In the examples described later, a value measured with a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation) was employed. Further, the average particle diameter may be, for example, 0.001, 0.005, 0.1, 0.7, 1, 5, 15, 20, 25, or 40 μm, and may be within the range of any two of these values.

(C) The amount of the inorganic filler used is preferably 10 to 150 parts by mass, more preferably 60 to 120 parts by mass, based on 100 parts by mass of (A). If it is in these ranges, the curability does not deteriorate, and the adhesiveness or high-temperature elastic modulus does not decrease. In addition, (C) component may be, for example, 10, 30, 45, 60, 80, 100, 105, 110, 120, or 150 parts by mass per 100 parts by mass of (A), and the range of any two values It may be mine.

In the resin composition obtained by using the (B) polyolefin particles and the (C) inorganic filler, even after a long period of time, the polyolefin particles do not float and separate, and the inorganic filler does not separate and settle, so that a resin composition having excellent storage stability can be obtained.

The energy ray-curable resin composition according to the present embodiment has (D) a photoradical polymerization initiator as an essential component. (D) The photoradical polymerization initiator is not particularly limited as long as it is a compound that generates a radical by irradiation with energy rays.

Examples of the (D) photoradical polymerization initiator used in the embodiment of the present invention include benzophenone, 4-phenylbenzophenone, benzoyl benzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, Benzoylisopropylether, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, thioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4- (2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy Roxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, camphorquinone, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone-1, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide And the like. Among these, α-hydroxyacetophenones are preferable because of their excellent curability. As α-hydroxyacetophenones, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy) Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and the like. Among these, 1-hydroxycyclohexylphenyl ketone is preferable. These can be used alone or in combination of two or more.

(D) The amount of photoradical polymerization initiator used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and most preferably 1 to 5 parts by mass per 100 parts by mass of (A). When it is in this range, curability does not deteriorate, and adhesiveness does not decrease. In addition, (D) component may be, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts by mass per 100 parts by mass of (A), any 2 of these It may be within the range of values of dogs.

Furthermore, in one embodiment of the present invention, an antioxidant may be contained.

The energy ray-curable resin composition of one embodiment of the present invention may contain a silane coupling agent for the purpose of further improving adhesion to a glass surface.

Additives such as various elastomers such as acrylic rubber and urethane rubber, photosensitizers, light stabilizers, solvents, extenders, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants and surfactants, within the scope not impairing the object of the present invention You may contain it.

The energy ray-curable resin composition of one embodiment of the present invention can be cured by irradiation with energy rays to form a cured product.

The energy ray-curable resin composition of one embodiment of the present invention can be used as an adhesive. This adhesive is used to assemble parts of electronic products such as liquid crystal panels, organic electroluminescent panels, touch panels, projectors, smartphones, mobile phones, digital cameras, digital movies, optical pickups, LEDs, solar cells, lithium-ion batteries, and CCDs. , CMOS, flash memory, DRAM, semiconductor laser, etc. It can be suitably used for packaging of semiconductor devices. Moreover, it is a suitable adhesive for bonding of optical elements used for the base of craft glass, fixing of plates, two or more lenses or prisms, cameras, binoculars, and microscopes.

There is no restriction|limiting in particular about the manufacturing method of the energy ray-curable resin composition of one embodiment of this invention as long as the said material can be fully mixed. Although it does not specifically limit as a mixing method of a material, A stirring method using a stirring force according to rotation of a propeller, a method using a conventional disperser such as a planetary stirrer by rotating revolution, etc. are mentioned. These mixing methods are preferable in that stable mixing can be performed at low cost.

After the above mixing, the energy ray-curable resin composition can be cured by irradiation of energy rays using the following light source.

In one embodiment of the present invention, the light source used for curing and bonding the energy ray-curable resin composition is not particularly limited, but a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium, etc.), a low pressure mercury lamp , A high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, a light-emitting diode (hereinafter referred to as an LED), and the like. These light sources are preferable in that they can efficiently irradiate an energy ray corresponding to the reaction wavelength of each photopolymerization initiator.

Each of the light sources has a different radiation wavelength and energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photopolymerization initiator or the like. In addition, natural light (sunlight) may also serve as a reaction initiating light source.

The light source may be subjected to direct irradiation, condensing irradiation with a reflector or the like, condensing irradiation with a fiber or the like. A low wavelength cut filter, a hot wire cut filter, a cold mirror, or the like can also be used.

The storage modulus of the cured product of the energy ray-curable resin composition is preferably 800 MPa or more and 1500 MPa or less at 25°C, and preferably 10 MPa or more and 1000 MPa or less at 70°C. By setting it as this value, even if exposed to a low temperature of 25°C or lower, it will not become too hard to deform the adherend, and even if exposed to a high temperature of 70°C or higher, it will not become too soft and displace the adherend. Can provide.

The storage modulus here is a real part of the complex modulus and refers to the magnitude of the stress component in phase when a sinusoidal strain is applied to the viscoelastic body. Here, the complex modulus is the ratio of the maximum stress and the maximum strain in dynamic viscoelasticity, and means a complex number calculation as a vector. Dynamic viscoelasticity refers to the behavior of the combination of viscous and elasticity when a material is subjected to normal sinusoidal deformation. It is obtained by measuring the stress to strain or strain to stress.

For the measurement of the storage modulus, it is preferable to use a known dynamic viscoelastic spectrometer (for example, the DMS series manufactured by S.I.I. Nanotechnology, or the RSA series manufactured by TA Instruments).

The energy ray-curable resin composition of one embodiment of the present invention can be preferably used as an adhesive because curing shrinkage of a cured product obtained by irradiation with energy rays is low and exhibits high elongation. Examples of the adherend used as an adhesive include ceramics such as glass, silica, alumina, silicon nitride, and aluminum nitride, metals such as iron, copper, zinc, aluminum, and magnesium, and various plastics. The energy ray-curable resin composition of one embodiment of the present invention exhibits particularly excellent adhesion to engineering plastics.

Engineering plastics include polyamide (PA), polycarbonate (PC), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), glass fiber reinforced polyethylene terephthalate (GF-PET), and ultra-high molecular weight polyethylene. (UHPE), Syndiotactic Polystyrene (SPS), Amorphous Polyarylate (PAR), Polysulfone (PSF), Polyethersulfone (PES), Polyphenylene Sulfide (PPS), Polyetheretherketone (PEEK), PolyE Mid (PI), polyetherimide (PEI), fluororesin, liquid crystal polymer (LCP), and the like. The energy ray-curable resin composition of an embodiment of the present invention is an engineering plastic having an aromatic ring: polycarbonate (PC), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), glass fiber reinforced polyethylene. Terephthalate (GF-PET), syndiotactic polystyrene (SPS), amorphous polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), polyetheretherketone ( PEEK), polyimide (PI), polyetherimide (PEI), and liquid crystal polymers (LCP).

The energy ray-curable resin composition of one embodiment of the present invention can be applied to a bonding or fixing application of dissimilar materials. Among the different materials, it can be suitably used for bonding or fixing applications of polyphenylene sulfide and liquid crystal polymers, bonding or fixing applications of polyphenylene sulfide and zinc.

One embodiment of the present invention can provide an energy ray-curable resin composition having low curing shrinkage of a cured product obtained by irradiation with energy rays, and having very high adhesion to various adherends and excellent in cooling and heat cycle resistance. .

In one embodiment of the present invention, the adhesion may be, for example, adhesion of two or more adherends.

One embodiment of the present invention is a method for producing a bonded body including a step of applying the energy ray-curable resin composition according to the embodiment of the present invention to an adherend, and a step of curing the composition by irradiation of energy rays. The conjugate may contain two or more adherends. The production method may include a step of bonding two or more adherends together. At least one of the two or more adherends may be an adherend to which the composition is applied. The bonding step may include a step of bonding the adherend to which the composition is applied and the adherend to which the composition is not applied. In addition, one embodiment of the present invention is a conjugate obtained by the above production method.

One embodiment of the present invention is a method of bonding two or more adherends using the energy ray-curable resin composition according to the embodiment of the present invention. This method may include a step of applying the composition to an adherend. The method may include a step of curing the composition by irradiation with energy rays. The method may include a step of bonding two or more adherends together. At least one of the two or more adherends may be an adherend to which the composition is applied. The bonding step may include a step of bonding the adherend to which the composition is applied and the adherend to which the composition is not applied. The method may include a method of fixing an adherend.

As described above, embodiments of the present invention have been described, but these may adopt various configurations other than the above as examples of the present invention. Moreover, it is also possible to employ a combination of the configurations described in the above embodiments.

Example

Hereinafter, the present invention will be described in more detail with reference to experimental examples. The present invention is not limited to these.

In the experimental example, the following compounds were used.

(A1) The following was used as a monofunctional (meth)acrylate of a component.

(a-1) As a monofunctional (meth)acrylate having an alicyclic hydrocarbon group

(A-1) Isobornyl Methacrylate (Kyoeisha Chemical Co., Ltd. "Light Ester 　IB-X")

(A-2) Dicyclopentenyloxyethyl acrylate ("Pancryl FA-512AS" manufactured by Hitachi Chemical Industries, Ltd.)

(A-6) Dicyclopentanyl methacrylate ("Pancryl FA-513M" manufactured by Hitachi Chemical Industries, Ltd.)

(A-7) Dicyclopentenyl acrylate ("Pancryl FA-511AS" manufactured by Hitachi Chemical Industries, Ltd.)

(a-2) As a hydroxyl group-containing monofunctional (meth)acrylate

(A-3) 2-hydroxyethyl methacrylate ("2-hydroxyethyl methacrylate" manufactured by Nippon Shokubai)

(A-8) 2-hydroxypropyl methacrylate ("2-hydroxypropyl methacrylate" manufactured by Nippon Shokubai Co., Ltd.)

(a-3) As a monofunctional (meth)acrylate having a carboxyl group or a phosphate ester group

(A-4) 2-methacryloyloxyethyl succinic acid (Kyoeisha Chemical Co., Ltd. "Light Ester HO-MS")

(A-9) 2-acryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd. ``Light Ester Light Acrylate P-1A(N)'')

(A2) The following was used as the polyfunctional (meth)acrylate of a component.

(A-5) As an oligomer having two or more (meth)acryloyl groups in the molecule, methacrylic-modified polybutadiene at both ends ("NISSO polybutadiene TE-2000" manufactured by Nippon Soda) Molecular weight 2100, structural formula is general formula (C))

[Formula 3]

General formula (C)

(R in general formula (C) is a structural formula represented by general formula (Y))

General formula (Y)

(A-10) As an oligomer having two or more (meth)acryloyl groups in the molecule, acrylic-modified hydrogenated polybutadiene at both ends ("NISSO polybutadiene TEAI-1000" manufactured by Nippon Soda) (number of polystyrene conversion by GPC Average molecular weight 1000, structural formula is general formula (D))

[Formula 4]

General formula (D)

(R in general formula (D) is a structural formula represented by general formula (Z))

General formula (Z)

The molecular weight (number average molecular weight (Mn)) of the component (A2) was measured by gel permeation chromatography (GPC). As a column, "TSK guardcolumn MP (xL)" manufactured by Tosoh Corporation was used, the column temperature was set to 40°C, and the measurement was performed using tetrahydrofuran as an eluent. The measurement sample was prepared at a concentration of 1.0 mg/ml, and 0.1 ml was injected into the column for measurement. The molecular weight calibration curve was calibrated using a polystyrene sample with known molecular weight.

The following was used as the polyolefin particle of (B) component.

(B-1) Polyethylene particles <1> (“SK-PE-20L” manufactured by Seishin Corporation)

(B-2) Polyethylene particles <2> (CERIDUST PE-130, manufactured by Clariant Japan)

(B-3) Polyethylene particles <3> (Mitsui Chemical Co., Ltd. ``Miperon XM220'')

(B-4) Polyethylene particles <4> (Mitsui Chemical Co., Ltd. ``Miperon PM220'')

(B-5) Polyethylene particles <5> ("Maleic anhydride XM220" manufactured by Mitsui Chemicals)

(B-6) Polyethylene particles <6> ("carbonyl modified XM220" manufactured by Mitsui Chemicals)

(B-7) Polypropylene particles <1> ("PPW-5" manufactured by Seishin Corporation)

(B-8) Polypropylene particles <2> (CERIDUST PP-6071, manufactured by Clariant Japan)

(B-9) Polyethylene particles <7> (Mitsui Chemical Co., Ltd. ``Hijax 2100JPD''

Table 1 shows the density and average particle diameter of each polyolefin particle used for the component (B).

(C) The following was used as the inorganic filler of the component.

(C-1) Glass filler ("CF0023-05C" manufactured by Nippon Frit)

(C-2) Fused silica <1> ("FB-950" manufactured by Denki Chemical Industries)

(C-3) Fused silica <2> ("FB-5D" manufactured by Denki Chemical Industries)

(C-4) Crystalline quartz <1> ("Crystallite A-2" manufactured by Tatsumori)

(C-5) Crystalline quartz <2> ("Crystallite 3K-S" manufactured by Tatsumori)

(C-6) Finely divided silica (``SFP-20M'' manufactured by Denki Chemical Industries, Ltd.)

(C-7) Crystalline quartz <3> ("Crystallite 5X" manufactured by Tatsumori)

(C-8) Dry silica (Evonik company ``Aellosil R-974'')

Table 2 shows the density and average particle diameter of the inorganic filler used for the component (C).

The density of (B) component was measured by the density gradient pipe method in conformity with JIS K 6760.

The density of (C) component was measured by the liquid immersion method in conformity with JIS Z 8901.

The average particle diameter of the component (B) and the component (C) was measured using a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation).

The following was used as a photoinitiator of (D) component.

(D-1) 1-hydroxy-cyclohexylphenyl ketone ("Irgacure 184" manufactured by BASF)

(D-2) Benzyl dimethyl ketal ("Irgacure 651" manufactured by BASF)

(Experimental Examples 1 to 23)

The raw materials of the kinds shown in Table 3, Table 4, and Table 5 were mixed at the composition ratio (unit is mass parts) shown in Table 3, Table 4, Table 5, and the resin composition was prepared, and evaluation mentioned later was performed. Various evaluation results are shown in Table 3, Table 4, and Table 5. Unless otherwise specified, it was carried out in an environment of 23°C and 50% humidity.

〔Viscosity〕

The viscosity at a predetermined rotational speed (rpm) was measured using a type B viscometer. It was calculated as thixotropic coefficient (TI) = ((Viscosity at 2 rpm)/(Viscosity at 20 rpm)).

[Photo-curing conditions]

At the time of photocuring, an ultra-high pressure mercury lamp mounting device (“UL-750” manufactured by HOYA) was used to cure under conditions of irradiation intensity of 200mW/cm2 with a wavelength of 365nm and accumulated light quantity of 4,000mJ/cm2.

[Evaluation of fixation time]

After applying a resin composition to a diameter of 8 mm and a thickness of 80 μm on the first glass test piece (brand name ``Heat-resistant Pyrex (registered trademark) glass, 25 mm long × 25 mm wide × 2.0 mm thick), a second glass test piece of the same shape was attached. After matching and irradiation with UV light, the time until two glass test pieces did not move was measured, and it was set as the fixation time. The measurement time was up to 120 seconds.

[Hardening shrinkage rate]

The specific gravity (dL) of the resin composition before curing is in accordance with JIS Z 8804 (Method for measuring liquid specific gravity-3. Method for measuring specific gravity using a specific gravity bottle), and the specific gravity (dS) of the resin composition after curing is JIS Z 8807 (Method for measuring solid specific gravity) -4.Measurement method for weighing in liquid) was measured at 23°C. The cure shrinkage rate r(%) was calculated according to r(%)={1-(dL/dS)}×100. In the measurement of the specific gravity of the solid, a test piece cured under the above light irradiation conditions and having a shape of 25 mm long × 25 mm wide × 2 mm thick was used.

〔Storage modulus of elasticity〕

A cured adhesive having a shape of 5 mm long × 50 mm wide × 1 mm thick was prepared under the above photocuring conditions, set at a distance of 20 mm between chuck with a dynamic viscoelastic spectrometer (DMS-210 manufactured by SII Nanotechnology), frequency 1 Hz, and heating rate Measured in 2°C/min, tensile mode, values of 23°C and 70°C were read.

[Evaluation of tensile adhesion strength]

Tensile adhesive strength was 12.5 mm long × 5.0 mm wide × 2.0 mm thick, 5.0 μl of the adhesive was applied two points at an interval of 9 mm on the first test piece, and then a second test piece of the same shape was attached. The gap between the two test pieces was 1 mm. Thereafter, UV light was irradiated to the gaps of the test pieces under the above conditions and cured to prepare a test piece. The produced test piece was measured for tensile adhesion strength at a tensile speed of 50 mm/min using a tensile tester in an environment of 23° C. and humidity 50% RH. The test piece was used as follows. For example, in the table, PPS/LCP refers to a test piece that is a PPS test piece and an LCP test piece attached together. Abbreviation PPS: Glass fiber reinforced polyphenylene sulfide ("Sastir GS-40, a product containing 40% glass fiber" manufactured by Tosoh Corporation) (Linear expansion coefficient: 31 ppm/℃) Symbol LCP: Glass fiber reinforced liquid crystal polymer (manufactured by Polyplastics) 「Vectra E-130i, a product containing 30% glass fiber」) (Coefficient of linear expansion: 50 ppm/℃) Abbreviation Zn: Zinc die-cast (“ZnDC2” manufactured by Awa Co., Ltd.) (Linear expansion coefficient: 27 ppm/℃)

[Cooling heat cycle resistance evaluation]

After producing the same test piece as the tensile bonding strength evaluation, a test of 300 cycles in a thermostat incorporating a cooling/heating cycle program of 10°C/min with a heating/lowering rate of -30°C x 30 minutes to 80°C x 30 minutes as one cycle Was carried out. After the test piece was taken out, the test piece was allowed to stand in a room at a temperature of 23° C. and a humidity of 50% RH for 30 minutes, and then the tensile bonding strength (unit: MPa) was measured under the same conditions as the tensile bonding strength. The ratio of the strength after the test to the strength before the test was determined as the strength retention rate (%).

[Storage stability evaluation]

A sealed sample containing 20 ml of the resin composition in a 30 ml vial bottle was prepared. The sample was allowed to stand in an atmosphere at a temperature of 23° C. and a humidity of 50% RH for 1 month, and the height of the separation layer of the liquid layer after 1 month was measured.

The energy ray-curable resin composition of this example showed good effects. In Experimental Example 12, the effect of storage stability was small because the average particle diameter of the component (B) was large. Since Experimental Example 20 does not contain the component (B), Experimental Example 21 does not contain the component (C), and Experimental Example 22 did not show the effect of the present invention because the content ratio of the component (B) was small. .

In addition, isobornyl (meth)acrylate is selected as the monofunctional (meth)acrylate having a saturated alicyclic hydrocarbon group, and dicyclopentenyloxyethyl (dicyclopentenyloxyethyl) is selected as the monofunctional (meth)acrylate having an unsaturated alicyclic hydrocarbon group. Meth)acrylate is selected, 2-hydroxyethyl (meth)acrylate is selected as the monofunctional (meth)acrylate containing a hydroxyl group, and 2-(meth)acrylate is selected as a monofunctional (meth)acrylate having a carboxyl group or a phosphate ester group. )Acryloyloxyethylsuccinic acid is selected, an oligomer having a main chain skeleton of polybutadiene is selected as an oligomer having two or more (meth)acryloyl groups in the molecule, and 1-hydroxycyclohexylphenylketone as a photo radical polymerization initiator When selected, it had a particularly excellent effect (comparison of Experimental Example 1 and Experimental Example 23).

The energy ray-curable resin composition of the present invention has, for example, the following characteristics (however, the following characteristics are examples for explaining the industrial applicability of the present invention, and the present invention is not limited to these characteristics). The energy ray-curable resin composition of the present invention has equally high adhesive strength to various adherends such as glass, metal, and plastic. The energy ray-curable resin composition of the present invention has particularly high adhesion to engineering plastics. Since the energy ray-curable resin composition of the present invention has a low curing shrinkage rate and high elongation, it is excellent in heat-cooling and heat-resistance cycle resistance in bonding different types of adherends. Accordingly, the energy ray-curable resin composition of the present invention can be applied to bonding or fixing of different materials such as glass and metal, glass and ceramic, glass and plastic, other plastics, plastic and metal, and plastic and ceramic. The energy ray-curable resin composition of the present invention can be suitably used for assembling parts of electronic products where high performance of devices is progressing, or for mounting packages of semiconductor devices. The energy ray-curable resin composition of the present invention can be suitably used for bonding or fixing parts in the field of bonding optoelectronics, such as optical elements used in lenses, prisms, cameras, binoculars, microscopes, and the like. The present invention is very useful in industry.

Claims (15)

(A) 100 parts by mass of (meth)acrylate, (B) 25 to 150 parts by mass of polyolefin particles, (C) an inorganic filler and (D) a photoradical polymerization initiator,
(A) (meth)acrylate contains 20 to 90 parts by mass of (A1) monofunctional (meth)acrylate, and (A2) polyfunctional (meth)acrylate,
(A1) monofunctional (meth)acrylate is (a-1) monofunctional (meth)acrylate having an alicyclic hydrocarbon group, (a-2) monofunctional (meth)acrylate containing a hydroxyl group, and (a-3) It contains a monofunctional (meth)acrylate having a carboxyl group or a phosphoric ester group,
(a-1) monofunctional (meth)acrylate having an alicyclic hydrocarbon group (a-11) having a monofunctional (meth)acrylate having a saturated alicyclic hydrocarbon group and (a-22) having an unsaturated alicyclic hydrocarbon group Contains monofunctional (meth)acrylate,
(A2) the polyfunctional (meth)acrylate is an oligomer having two or more (meth)acryloyl groups in the molecule,
(A2) The main chain skeleton of the oligomer having two or more (meth)acryloyl groups in the molecule is one or more selected from the group consisting of polybutadiene, polyisoprene, hydrogenated products of polybutadiene, and hydrogenated products of polyisoprene. glue. The method according to claim 1,
(B) Energy ray-curable adhesive in which the polyolefin particles are polyethylene particles and/or polypropylene particles. The method according to claim 1,
(B) An energy ray-curable adhesive having a polyolefin particle density of 0.85 to 0.95 g/cm 3 and an average particle diameter of 5 to 30 μm. The method according to claim 1,
(C) An energy ray-curable adhesive having an inorganic filler having a density of 2.00 to 3.00 g/cm 3 and an average particle diameter of 0.001 to 40 μm. The method according to claim 1,
(C) Energy ray-curable adhesive wherein the inorganic filler is at least one selected from the group consisting of fused silica, spherical silica, fumed silica, finely divided silica, quartz, quartz glass, and glass filler. A cured product obtained by curing the energy ray-curable adhesive according to claim 1. An adhesive for energy ray-curable heterogeneous materials comprising the energy ray-curable adhesive according to claim 1. An energy ray-curable adhesive for engineering plastics comprising the energy ray-curable adhesive according to claim 1. A bonded body using the energy ray-curable adhesive for dissimilar materials according to claim 7. A method of bonding two or more adherends using the energy ray-curable adhesive according to claim 1. delete delete delete delete delete