Composition

Abstract

A composition comprising an epoxy resin A1 having an epoxy group, an epoxy curing accelerator A2, an acrylic compound B1 having a (meth)acryl group, and a free-radical polymerization initiator B2, wherein the ratio (A / B) between the mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and the mass ratio B of the free-radical polymerization initiator B2 to the acrylic compound B1 is 1.0-15.

Description

[Technical field]

[0001] The present invention relates to a composition, preferably a resin composition. [Background technology]

[0002] Structural adhesives are used in a wide variety of applications as highly reliable adhesives that can withstand heavy loads for long periods of time. Known types of structural adhesives include epoxy adhesives, urethane adhesives, and second generation (SGA) acrylic adhesives.

[0003] These structural adhesives have different properties depending on the type: for example, epoxy adhesives tend to have high adhesive strength and low elongation, urethane adhesives tend to have high elongation and low adhesive strength, and acrylic adhesives tend to have performance between epoxy adhesives and urethane adhesives.

[0004] Furthermore, Patent Document 1 discloses an impact-resistant adhesive that uses three types of monomers: an acrylic-based monomer, an epoxy-based monomer / resin, and a bifunctional monomer that is chemically reactive with the acrylic-based monomer and the epoxy-based monomer / resin, with the aim of providing a room-temperature-curing adhesive that combines the room-temperature-curing and fast-curing properties of an acrylic-based adhesive with the heat resistance of an epoxy resin-based adhesive. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-197102 A Summary of the Invention [Problem to be solved by the invention]

[0006] The adhesive described in Patent Document 1 bonds an acrylic monomer network and an epoxy monomer network with a bifunctional monomer, but it is also known to form an interpenetrating polymer network (IPN) in which independent network structures composed of multiple types of monomers with different polymerization forms interpenetrate each other. By forming an IPN in this way, attempts have been made to utilize the characteristics of the networks composed of multiple monomers and achieve better characteristics. However, the cured product obtained with the aim of forming such an IPN structure has problems such as loss of transparency and occurrence of phase separation that can be recognized visually.

[0007] The present invention has been made in consideration of the above problems, and has an object to provide a resin composition that can form an IPN structure and give a cured product in which each polymer network has excellent compatibility. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems. As a result, it has been found that, apart from the compatibility of the monomers themselves, the growth rates of the networks constituting the IPN structure are different, so that only one network is formed first, making it difficult to form an interpenetrating structure, and the compatibility of each network in the IPN decreases. The present inventors have found that the above problems can be solved by controlling the growth rate of each polymer network, and have completed the present invention.

[0009] That is, the present invention is as follows. [1] an epoxy resin A1 having an epoxy group; Epoxy curing accelerator A2; an acrylic compound B1 having a (meth)acrylic group; A radical polymerization initiator B2, a ratio (A / B) of a mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and a mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is 1.0 to 15. composition. [2] one of the epoxy resin A1 and the acrylic compound B1 contains a bisphenol skeleton, The other of the epoxy resin A1 and the acrylic compound B1 contains a polyether skeleton, a polysiloxane skeleton, a polyurethane skeleton, a polybutadiene skeleton, or a polyisoprene skeleton. The composition described in [1]. [3] The molecular weight of the epoxy resin A1 is 100 to 5,000. The composition according to [1] or [2]. [4] The molecular weight of the acrylic compound B1 is 100 to 5000. The composition according to any one of [1] to [3]. [5] The mass ratio A is 0.02 to 0.10. The composition according to any one of [1] to [4]. [6] The mass ratio B is 0.0050 to 0.0200. The composition according to any one of [1] to [5]. [7] The content of the epoxy resin A1 is 25 to 75 mass% based on the total amount of the epoxy resin A1 and the acrylic compound B1. The composition according to any one of [1] to [6]. [8] The content of the acrylic compound B1 is 25 to 75 mass% based on the total amount of the epoxy resin A1 and the acrylic compound B1. The composition according to any one of [1] to [7]. [9] The epoxy resin A1 has two or more epoxy groups. The composition according to any one of [1] to [8].

[10] The acrylic compound B1 has two or more (meth)acrylic groups. The composition according to any one of [1] to [9].

[11] A resin composition comprising the composition according to any one of [1] to

[10] . Effect of the Invention

[0010] According to the present invention, it is possible to provide a composition which is capable of forming an IPN structure and giving a cured product in which each polymer network has excellent compatibility. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications are possible without departing from the gist of the present invention. In this specification, "(meth)acrylic" means at least one of acrylic and its corresponding methacrylic.

[0012] 1. Composition (resin composition) The composition of the present embodiment is preferably a resin composition. The resin composition of the present embodiment contains an epoxy resin A1 having an epoxy group, an epoxy curing accelerator A2, an acrylic compound B1 having a (meth)acrylic group, and a radical polymerization initiator B2, and a ratio (A / B) of a mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and a mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is 1.0 to 15.

[0013] As a result, the cured product of the resin composition of this embodiment has an interpenetrating polymer network (IPN) in which network A formed by the epoxy resin A1 and network B formed by the acrylic compound B1 are intertwined with each other.

[0014] In particular, in this embodiment, the ratio (A / B) of the mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and the mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is adjusted within a predetermined range to adjust the reaction rate of the epoxy resin A1 and the reaction rate of the acrylic compound B1, and bring the reaction rates of the two closer together. By controlling the formation rate of each network in this manner, it is possible to prevent one of the networks A and B from being formed first, resulting in a state in which the networks A and B do not interpenetrate each other (phase separation). As a result, the cured product obtained using the resin composition of this embodiment has good compatibility between the networks A and B, is highly transparent, and can achieve higher physical properties by the cooperation of both networks.

[0015] In this embodiment, the "compatibility" between network A and network B means that the networks form a homogeneous interpenetrating structure without phase separation. Therefore, compatibility meaning affinity resulting from properties such as hydrophilicity or hydrophobicity between monomers is distinguished from the compatibility of the above-mentioned networks.

[0016] 1.1.Network Combination In the present embodiment, examples of the combination of the epoxy resin A1 and the acrylic compound B1 include an embodiment 1 in which the epoxy resin A1 and the acrylic compound B1 both have hard segments, an embodiment 2 in which the epoxy resin A1 and the acrylic compound B1 both have soft segments, and an embodiment 3 in which one of the epoxy resin A1 and the acrylic compound B1 has a hard segment and the other has a soft segment.

[0017] Here, the term "hard segment" refers to a portion that has a rigid chemical structure, such as a bisphenol skeleton or polybisphenol skeleton, that is susceptible to restriction of intramolecular bond rotation due to steric hindrance and that can contribute to the strength and hardness of the cured product, whereas the term "soft segment" refers to a portion that has a flexible chemical structure, such as a polyether skeleton, polysiloxane skeleton, polyurethane skeleton, polybutadiene skeleton, or polyisoprene skeleton, that is unlikely to be restricted in intramolecular bond rotation due to steric hindrance and that can contribute to the flexibility and elongation of the cured product.

[0018] According to the present embodiment, it is possible to suppress phase separation of the IPN and improve compatibility, and therefore it is possible to combine desired physical properties in each of Aspect 1 in which both segments are hard segments, Aspect 2 in which both segments are soft segments, and Aspect 3 in which hard segments and soft segments are mixed.

[0019] Among these, the embodiment 3 in which hard segments and soft segments are mixed is preferred, and more specifically, it is preferred that one of the epoxy resin A1 and the acrylic compound B1 contains a hard segment such as a bisphenol skeleton, and the other of the epoxy resin A1 and the acrylic compound B1 contains a soft segment such as a polyether skeleton, a polysiloxane skeleton, a polyurethane skeleton, a polybutadiene skeleton, or a polyisoprene skeleton, which tends to further improve tensile elongation, etc.

[0020] 1.2. Ratio (A / B) The ratio (A / B) of the mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and the mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is 1.0 to 15, preferably 1.5 to 12.5, more preferably 2.0 to 10, and even more preferably 2.5 to 7.5. By having the ratio (A / B) within the above range, the reaction rate of the epoxy resin A1 and the reaction rate of the acrylic compound B1 can be made close to each other, and a network A formed by the epoxy resin A1 and a network B formed by the acrylic compound B1 can be formed while suppressing phase separation in the IPN caused by one network being formed first. As a result, the compatibility of each network in the IPN is improved in the obtained cured product, and it is possible to achieve high transparency and other higher physical properties. On the other hand, when the ratio (A / B) is outside the above range, either the reaction rate of the epoxy resin A1 or the reaction rate of the acrylic compound B1 becomes too high, so that one network is formed first, making it difficult to form a structure in which networks A and B interpenetrate, resulting in phase separation and impaired compatibility and transparency.

[0021] 1.3.Epoxy Resin A1 The epoxy resin A1 is not particularly limited as long as it is a compound having an epoxy group, and examples thereof include compounds having a bisphenol type epoxy resin, a polybisphenol type epoxy resin, a polyether type epoxy resin, a polysiloxane type epoxy resin, a polyurethane type epoxy resin, a polybutadiene type epoxy resin, a polyisoprene type epoxy resin, an aliphatic type epoxy resin, an alicyclic type epoxy resin, or an aromatic type epoxy resin. The epoxy resin A1 may be used alone or in combination of two or more kinds.

[0022] Among these, bisphenol type epoxy resins and polybisphenol type epoxy resins are susceptible to restriction of intramolecular bond rotation due to steric hindrance and have a rigid chemical structure, and this portion is also called a hard segment. On the other hand, polyether type epoxy resins, polysiloxane type epoxy resins, polyurethane type epoxy resins, polybutadiene type epoxy resins, and polyisoprene type epoxy resins are less susceptible to restriction of intramolecular bond rotation due to steric hindrance and have a flexible chemical structure, and this portion is also called a soft segment.

[0023] The bisphenol type epoxy resin is not particularly limited as long as it is a compound in which the hydroxyl group of bisphenol is modified to an epoxy group, and examples thereof include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin, and bisphenol Z type epoxy resin. By using a bisphenol type epoxy resin, the strength and elastic modulus of the obtained cured product tend to be further improved.

[0024] The polybisphenol type epoxy resin is not particularly limited, but may be, for example, a compound in which the hydroxyl group of the polybisphenol obtained by condensing the above-mentioned bisphenol with epichlorohydrin is modified into an epoxy group. By using the polybisphenol type epoxy resin, the strength and elastic modulus of the obtained cured product tend to be further improved.

[0025] The polyether type epoxy resin is not particularly limited as long as it is a compound in which the hydroxyl group of polyether is modified into an epoxy group. The polyether is not particularly limited, but examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. By using the polyether type epoxy resin, the elongation of the obtained cured product tends to be further improved.

[0026] The polysiloxane type epoxy resin is not particularly limited as long as it is a compound in which the hydroxyl group or alkoxy group of polysiloxane is modified into an epoxy group. The polysiloxane is not particularly limited, but examples thereof include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, etc. By using the polysiloxane type epoxy resin, the elongation of the obtained cured product tends to be further improved.

[0027] The polyurethane type epoxy resin is not particularly limited as long as it is a compound in which the hydroxyl group of polyurethane is modified into an epoxy group. The polyurethane is not particularly limited, but examples thereof include polyester polyurethane, polyether polyurethane, polycarbonate polyurethane, etc. By using the polyurethane type epoxy resin, the elongation of the obtained cured product tends to be improved.

[0028] The polybutadiene type epoxy resin and the polyisoprene type epoxy resin are not particularly limited as long as they are compounds obtained by modifying polybutadiene or polyisoprene with an epoxy group. By using the polybutadiene type epoxy resin and the polyisoprene type epoxy resin, the elongation of the obtained cured product tends to be further improved.

[0029] The aliphatic epoxy resin is not particularly limited as long as it is an epoxy resin other than the above and is a compound obtained by modifying an aliphatic hydrocarbon with an epoxy group. The aliphatic hydrocarbon is not particularly limited, but examples thereof include ethane, n-propane, isopropane, n-butane, isobutane, sec-butane, t-butane, n-pentane, neopentane, n-hexane, n-heptane, n-octane, n-ethylhexane, and n-nonane.

[0030] The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin other than those mentioned above and is a compound in which an alicyclic hydrocarbon is modified with an epoxy group. Examples of the alicyclic hydrocarbon include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cyclooctane.

[0031] The aromatic epoxy resin is not particularly limited as long as it is an epoxy resin other than those mentioned above and is a compound obtained by modifying an aromatic hydrocarbon with an epoxy group. Examples of the aromatic hydrocarbon include, but are not particularly limited to, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, and aralkyl novolac epoxy resin.

[0032] As a method for modification with an epoxy group, a conventionally known method can be used, and each of the compounds exemplified above, such as the bisphenol type epoxy resin, may contain a group connecting the epoxy group to each skeleton, which is derived from the modification method.

[0033] In the present embodiment, the bisphenol type epoxy resin or the like can be rephrased as an epoxy resin having a bisphenol skeleton. The "skeleton" here means a structure derived from a compound before epoxy modification, for example, bisphenol, in the chemical formula of the epoxy resin.

[0034] The molecular weight of the epoxy resin A1 is preferably 100 to 5000, more preferably 200 to 4000, further preferably 250 to 3000, and further preferably 300 to 2000. When the molecular weight of the epoxy resin A1 is within the above range, the tensile elongation of the cured product tends to be improved. When the epoxy resin A1 has a polymer skeleton such as the polybisphenol skeleton or polyether skeleton, the molecular weight of the epoxy resin A1 is the weight average molecular weight measured by gel permeation chromatography (GPC).

[0035] The number of epoxy groups contained in the epoxy resin A1 is 1 or more, preferably 2 or more, more preferably 2 to 10, further preferably 2 to 4, and even further preferably 2.

[0036] The content of epoxy resin A1 is preferably 25 to 75 mass %, more preferably 30 to 70 mass %, and further preferably 35 to 65 mass %, based on the total amount of epoxy resin A1 and acrylic compound B1. When the content ratio of epoxy resin A1 to acrylic compound B1 is within the above range, the compatibility between network A and network B is further improved, and the cooperation of both networks tends to enable the achievement of higher physical properties.

[0037] 1.4.Epoxy curing accelerator A2 The resin composition of this embodiment includes an epoxy curing accelerator A2, and may include an epoxy curing agent A3, which will be described later, if necessary. Here, the epoxy curing accelerator A2 promotes the reaction between the epoxy groups of the epoxy resin A1, more specifically, the reaction between the hydroxyl group of the ring-opened epoxy group and another epoxy group, and promotes homopolymerization of the epoxy resin A1. In contrast, the epoxy curing agent A3 is a bifunctional or higher compound having a functional group that reacts with the epoxy group of the epoxy resin A1 to form a chemical bond, and copolymerizes with the epoxy resin A1. Note that, when the epoxy curing agent A3 coexists, the epoxy curing accelerator A2 also promotes the reaction between the epoxy resin A1 and the epoxy curing agent A3.

[0038] The epoxy curing accelerator A2 is not particularly limited, but examples thereof include imidazole compounds such as 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-phenylimidazole; phosphorus compounds such as triphenylphosphine; tertiary amine compounds such as dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]undec-7-ene; and organometallic compounds. The curing accelerator may be used alone or in combination of two or more.

[0039] Among the epoxy curing accelerators A2, imidazole-based compounds are preferred. Among the imidazole-based compounds, one or more selected from the group consisting of 1-benzyl-2-methylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, and 2-methylimidazole are preferred.

[0040] The mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 is preferably 0.02 to 0.10, preferably 0.02 to 0.08, and preferably 0.03 to 0.06. The mass ratio A makes it possible to adjust the formation rate of the network A.

[0041] 1.5.Epoxy Hardener A3 The resin composition of the present embodiment may further contain an epoxy curing agent A3. The epoxy curing agent A3 is not particularly limited, but examples thereof include bisphenols, biphenol, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 4,4,4-trihydroxytriphenylmethane, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene, 2,6-bis(dihydroxybenzyl)-4-methylphenol, 1,1,2,2-tetraki ...4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, 4,4'-{ Examples of the amine compounds include phenol-based compounds such as bis(4-hydroxy-3-methylphenyl)ethane, hydroquinone, resorcinol, naphthalenediol, phenol novolac resin, and cresol novolac resin; acid anhydride-based compounds such as methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; aromatic amine compounds such as diaminodiphenylmethane and methylaniline; aliphatic amine compounds such as triethylenetetramine; and amine compounds such as isophoronediamine, methylcyclohexylamine, and the like.

[0042] 1.6. Acrylic Compounds B1 The acrylic compound B1 is not particularly limited as long as it is a compound having a (meth)acrylic group, and examples thereof include compounds having a bisphenol type acrylic compound, a polybisphenol type acrylic compound, a polyether type acrylic compound, a polysiloxane type acrylic compound, a polyurethane type acrylic compound, a polybutadiene type acrylic compound, a polyisoprene type acrylic compound, an aliphatic type acrylic compound, an alicyclic type acrylic compound, and an aromatic type acrylic compound. The acrylic compound B1 may be used alone or in combination of two or more types.

[0043] Among these, bisphenol-type acrylic compounds and polybisphenol-type acrylic compounds are easily restricted in intramolecular bond rotation due to steric hindrance and have a rigid chemical structure, and this portion is also called a hard segment. On the other hand, polyether-type acrylic compounds, polysiloxane-type acrylic compounds, polyurethane-type acrylic compounds, polybutadiene-type acrylic compounds, and polyisoprene-type acrylic compounds are not easily restricted in intramolecular bond rotation due to steric hindrance and have a flexible chemical structure, and this portion is also called a soft segment.

[0044] The bisphenol type acrylic compound is not particularly limited as long as it is a compound in which the hydroxyl group of bisphenol is modified to a (meth)acrylic group, and examples thereof include bisphenol A type acrylic compound, bisphenol AP type acrylic compound, bisphenol AF type acrylic compound, bisphenol B type acrylic compound, bisphenol BP type acrylic compound, bisphenol C type acrylic compound, bisphenol E type acrylic compound, bisphenol F type acrylic compound, bisphenol G type acrylic compound, bisphenol M type acrylic compound, bisphenol S type acrylic compound, bisphenol P type acrylic compound, bisphenol PH type acrylic compound, bisphenol TMC type acrylic compound, and bisphenol Z type acrylic compound. By using a bisphenol type acrylic compound, the strength and elastic modulus of the obtained cured product tend to be further improved.

[0045] The polybisphenol type acrylic compound is not particularly limited, but may be, for example, a compound in which the hydroxyl group of the polybisphenol obtained by condensing the above-mentioned bisphenol with epichlorohydrin is modified into a (meth)acrylic group. By using the polybisphenol type acrylic compound, the strength and elastic modulus of the obtained cured product tend to be further improved.

[0046] The polyether type acrylic compound is not particularly limited as long as it is a compound in which the hydroxyl group of polyether is modified into a (meth)acrylic group. The polyether is not particularly limited, but examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. By using the polyether type acrylic compound, the elongation of the obtained cured product tends to be further improved.

[0047] The polysiloxane type acrylic compound is not particularly limited as long as it is a compound in which the hydroxyl group or alkoxy group of polysiloxane is modified into a (meth)acrylic group.The polysiloxane is not particularly limited, but examples thereof include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, etc.By using the polysiloxane type acrylic compound, the elongation of the obtained cured product tends to be further improved.

[0048] The polyurethane-type acrylic compound is not particularly limited as long as it is a compound in which the hydroxyl group of polyurethane is modified to a (meth)acrylic group. The polyurethane is not particularly limited, but examples thereof include polyester-based polyurethane, polyether-based polyurethane, polycarbonate-based polyurethane, etc. By using the polyurethane-type acrylic compound, the elongation of the obtained cured product tends to be further improved.

[0049] The polybutadiene-type acrylic compound and the polyisoprene-type acrylic compound are not particularly limited as long as they are compounds obtained by modifying polybutadiene or polyisoprene with a (meth)acrylic group. By using the polybutadiene-type acrylic compound and the polyisoprene-type acrylic compound, the elongation of the obtained cured product tends to be further improved.

[0050] The aliphatic acrylic compound is not particularly limited as long as it is an acrylic compound other than the above and is a compound obtained by modifying an aliphatic hydrocarbon with a (meth)acrylic group. The aliphatic hydrocarbon is not particularly limited, but examples thereof include ethane, n-propane, isopropane, n-butane, isobutane, sec-butane, t-butane, n-pentane, neopentane, n-hexane, n-heptane, n-octane, n-ethylhexane, and n-nonane.

[0051] The alicyclic acrylic compound is not particularly limited as long as it is an acrylic compound other than the above and is a compound in which an alicyclic hydrocarbon is modified with a (meth)acrylic group. The alicyclic hydrocarbon is not particularly limited, but examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cyclooctane.

[0052] The aromatic acrylic compound is not particularly limited as long as it is an acrylic compound other than the above and is a compound obtained by modifying an aromatic hydrocarbon with a (meth)acrylic group. The aromatic hydrocarbon is not particularly limited, but examples thereof include phenol novolac acrylic compounds, cresol novolac acrylic compounds, naphthalene acrylic compounds, biphenyl acrylic compounds, and aralkyl novolac acrylic compounds.

[0053] As a modification method using a (meth)acrylic group, a conventionally known method can be used, and each of the compounds exemplified above, such as the bisphenol-type acrylic compound, may contain a group connecting the (meth)acrylic group to each skeleton, derived from the modification method.

[0054] In the present embodiment, the bisphenol-type acrylic compound and the like can be rephrased as an acrylic compound having a bisphenol skeleton. The term "skeleton" used here means a structure derived from a compound before (meth)acrylic modification, for example, a bisphenol, in the chemical formula of the acrylic compound.

[0055] The molecular weight of the acrylic compound B1 is preferably 100 to 5000, more preferably 200 to 4000, further preferably 250 to 3000, and further preferably 300 to 2000. When the molecular weight of the acrylic compound B1 is within the above range, the tensile elongation of the cured product tends to be further improved. When the acrylic compound B1 has a polymer skeleton such as the polybisphenol skeleton or polyether skeleton, the molecular weight of the acrylic compound B1 is the weight average molecular weight measured by gel permeation chromatography (GPC).

[0056] The number of (meth)acrylic groups contained in the acrylic compound B1 is 1 or more, preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 4, and still more preferably 2.

[0057] The content of the acrylic compound B1 is preferably 25 to 75 mass %, more preferably 30 to 70 mass %, and further preferably 35 to 65 mass %, based on the total amount of the epoxy resin A1 and the acrylic compound B1. When the content ratio of the epoxy resin A1 and the acrylic compound B1 is within the above range, the compatibility between the network A and the network B is further improved, and the cooperation of both networks tends to enable the achievement of higher physical properties.

[0058] 1.7. Radical Polymerization Initiator B2 The radical polymerization initiator B2 is not particularly limited, and examples thereof include azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), azobisdimethylvaleronitrile, and azobismethoxyvaleronitrile; di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide. Examples of known radical polymerization initiators include peroxides such as acetylcyclohexylsulfonyl peroxide and 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate; percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; and perester compounds such as t-butyl peroxyneodecanate, α-cumyl peroxyneodecanate and t-butyl peroxyneodecanate.

[0059] The mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is preferably 0.0050 to 0.0200, preferably 0.0075 to 0.0175, and preferably 0.0100 to 0.0150. The mass ratio B can adjust the formation rate of the network B.

[0060] 1.8. Other Additives The composition of the present embodiment may contain other additives in addition to the above. The other additives are not particularly limited, but may include, for example, a filler, a polymerization inhibitor, and the like.

[0061] 2.Curing method The method for curing the resin composition of the present embodiment is not particularly limited, but for example, a method of curing the resin composition by heating can be mentioned. In this case, the resin composition can be used as an adhesive by contacting the adherend with the resin composition and curing it. The adherend is not particularly limited, but examples thereof include different materials such as automobile structural materials, marine and aerospace structural materials, etc. EXAMPLES

[0062] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0063] [Examples 1 to 7 and Comparative Examples 1 to 5] The raw materials listed in Table 1 were mixed for 10 minutes at 2200 rpm using a hybrid mixer. The resulting mixture was applied onto a PET film, sandwiched between another PET film, and heated in an oven at 200°C for 2 hours to obtain a cured product. The raw materials used are listed below.

[0064] (Epoxy Resin A1) Bisphenol A diglycidyl ether: Mitsubishi Chemical Holdings, JER-828, molecular weight: 378 g / mol, number of epoxy groups: 2 Polytetramethylene glycol diglycidyl ether: Sakamoto Pharmaceutical Co., Ltd., SR-PTMG, molecular weight: 2900 g / mol 1,6-Hexanediol diglycidyl ether: Sakamoto Pharmaceutical Co., Ltd., SR-16HL

[0065] (Epoxy curing accelerator A2) 1-Benzyl-2-methylimidazole: Shikoku Kasei, 1B2MZ

[0066] (Acrylic Compound B1) Acrylic acid adduct of bisphenol A diglycidyl ether: Osaka Organic Industrial Co., Ltd., Viscoat #540, molecular weight 480, number of acrylic groups 2 Polytetramethylene glycol diacrylate: Shin-Nakamura Chemical, NK Ester A-PTMG65 Dicyclopentenyl methacrylate: Showa Denko Materials, Fancryl FA-513M

[0067] (Radical polymerization initiator B2) Diisopropylbenzene hydroperoxide: NOF Corp., Percumyl P

[0068] [FT-IR measurement conditions] The cured product obtained as described above was subjected to FT-IR (Fourier transform infrared spectroscopy). Specifically, FT-IR measurement was performed using a PerkinElmer Frontier by the ATR method. The measurement was performed by performing background measurement using a single reflection ATR, setting the sample, and measuring the sample surface with 16 scans. -1 The decrease in the peaks due to the nearby epoxy groups and the peak at 1640–1620 cm -1 The reaction rate of the acrylic group and the reaction rate of the epoxy group in each Example were confirmed from the decrease in the peak derived from the C=C bond contained in the nearby (meth)acrylic group.

[0069] [Tensile elongation] The cured product obtained as described above was cut into a 1BA type dumbbell test piece shape as specified in Appendix A of JIS K 7161-1: 2014. A tensile test was then carried out in accordance with JIS K 7161-1: 2014 using a universal testing machine Instron model 3365 (manufactured by Instron) in an atmosphere at 23°C to determine the tensile elongation.

[0070] [Haze] The haze value of the cured product obtained as described above was measured using a haze meter NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136-2000.

[0071] [Dynamic Viscoelasticity] The number of maximum values ​​of tan δ of the cured product obtained as described above was determined using a dynamic viscoelasticity measuring device DMS7100 manufactured by SII Corporation. The measurement conditions were as follows. If the number of maximum values ​​was one, it was determined that an interpenetrating polymer network (IPN) was formed in which network A formed by epoxy resin A1 and network B formed by acrylic compound B1 were intertwined with each other, and if the number of maximum values ​​was two or more, it was determined that an IPN was not formed. Measurement mode: Tensile mode Frequency: 1.0Hz Heating rate: 2℃ / min Measurement temperature range: -100~250℃ Test piece dimensions: 0.5 x 5.0 x 4.0 mm

[0072] [compatibility] The cured product obtained as described above was visually observed, and the compatibility was evaluated according to the following evaluation criteria. ◯: The cured product is transparent, and no cloudiness or opacity due to phase separation is observed. ×: The cured product is opaque, and cloudiness or opacity due to phase separation is observed.

[0073] [Table 1] [Industrial Applicability]

[0074] The polyfunctional compound of the present invention has industrial applicability as a resin composition capable of forming a uniform IPN structure.

Claims

1. An epoxy resin A1 having an epoxy group; Epoxy curing accelerator A2; an acrylic compound B1 having a (meth)acrylic group; A radical polymerization initiator B2, a ratio (A / B) of a mass ratio A of the epoxy curing accelerator A2 to the epoxy resin A1 and a mass ratio B of the radical polymerization initiator B2 to the acrylic compound B1 is 2.0 to 10; The acrylic compound B1 contains a bisphenol skeleton, The epoxy resin A1 contains a polyether skeleton, a polysiloxane skeleton, a polyurethane skeleton, a polybutadiene skeleton, or a polyisoprene skeleton. Compositions (excluding those containing magnetic powder).

2. The molecular weight of the epoxy resin A1 is 100 to 5000. The composition of claim 1.

3. The molecular weight of the acrylic compound B1 is 100 to 5000. The composition according to claim 1 or 2.

4. The mass ratio A is 0.02 to 0.

10. The composition according to any one of claims 1 to 3.

5. The mass ratio B is 0.0050 to 0.0200; The composition according to any one of claims 1 to 4.

6. The content of the epoxy resin A1 is 25 to 75 mass% based on the total amount of the epoxy resin A1 and the acrylic compound B1. The composition according to any one of claims 1 to 5.

7. The content of the acrylic compound B1 is 25 to 75 mass% based on the total amount of the epoxy resin A1 and the acrylic compound B1. The composition according to any one of claims 1 to 6.

8. The epoxy resin A1 has two or more epoxy groups. The composition according to any one of claims 1 to 7.

9. The acrylic compound B1 has two or more (meth)acrylic groups. The composition according to any one of claims 1 to 8.

10. A resin composition comprising the composition according to any one of claims 1 to 9.

Images