Resin composition, cured product, laminate, and method for producing laminate

Abstract

Provided are a resin composition from which an adhesive having excellent heat resistance and moisture resistance can be obtained, and a cured product using the same. Also provided are a laminate using the cured product, and a method for producing a laminate.　The resin composition contains 1,1-dicyanoethylene (A) and a polymerizable monomer (B) represented by general formula (I), and is characterized in that the content of 1,1-dicyanoethylene (A) is 2.0-99.9 mass % of the total of 1,1-dicyanoethylene (A) and the polymerizable monomer (B).　CHR1 = CR2R3 (I)

Description

Resin composition, cured product, laminate, and method for producing laminate

[0001] The present invention relates to a resin composition containing 1,1-dicyanoethylene and a specific polymerizable monomer, a cured product, a laminate, and a method for producing the laminate.

[0002] In fast-curing adhesive applications, 2-cyanoacrylic acid alkyl esters are used as the main raw material, as they undergo anionic polymerization even in weak Lewis base compounds such as water and alcohol. These applications require heat resistance and moisture resistance in addition to adhesive strength. For example, Patent Documents 1 and 2 propose adhesives that are imparted with heat resistance and moisture resistance by adding various additives.

[0003] Japanese Patent Application Laid-Open No. 52-78933 International Publication No. 2016 / 133166

[0004] The adhesives described in Patent Documents 1 and 2 have improved heat resistance and moisture resistance compared to conventional adhesives, but these are not sufficient, and further improvements are desired.

[0005] The present invention aims to provide a resin composition capable of producing an adhesive having excellent heat resistance and moisture resistance, a cured product using the same, a laminate using the cured product, and a method for producing the laminate.

[0006] The present inventors conducted studies and found that highly reactive 2-cyanoacrylic acid alkyl esters have the property of being difficult to copolymerize with other monomers, but are easily copolymerized with 1,1-dicyanoethylene. Based on this finding, the inventors conducted further studies and discovered that a cured product obtained from a resin composition containing 1,1-dicyanoethylene and a polymerizable monomer having a specific structure in a specific ratio not only has excellent adhesive properties, but also excellent heat resistance and moisture resistance, thereby completing the present invention.

[0007] That is, the present invention provides the following items [1] to [6]: [1] A resin composition containing 1,1-dicyanoethylene (A) and a polymerizable monomer (B) represented by the following general formula (I), characterized in that the content of the 1,1-dicyanoethylene (A) is 2.0 to 99.9 mass% of the total of the 1,1-dicyanoethylene (A) and the polymerizable monomer (B): CHR 1 =CR 2 R 3 (I) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group; R 2 is a cyano group, a carboxy group, -COOR 4 (R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; 3 is a carboxy group, -COOR 5 (R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group. ) is at least one selected from an ester group and an acid anhydride group represented by the following formula:

[0008] [2] The resin composition according to [1] above, wherein the polymerizable monomer (B) is one or more selected from the group consisting of 2-cyanoacrylic acid alkyl ester, 2-cyanopentadienoic acid alkyl ester, and methylidenemalonic acid dialkyl ester. [3] The resin composition according to [1] or [2] above, further comprising a Brønsted acidic compound. [4] A cured product obtained by curing the resin composition according to any of [1] to [3] above with a Lewis basic compound. [5] A laminate having a layer containing the cured product according to [4] above. [6] A method for producing a laminate, comprising a bonding step of bonding a first adherend and a second adherend with the resin composition according to any of [1] to [3] above.

[0009] According to the present invention, it is possible to provide a resin composition capable of producing an adhesive having excellent heat resistance and moisture resistance, a cured product using the same, a laminate using the cured product, and a method for producing the laminate.

[0010] [Resin Composition] The resin composition of the present invention is a resin composition containing 1,1-dicyanoethylene (A) and a polymerizable monomer (B) represented by the following general formula (I), characterized in that the content of the 1,1-dicyanoethylene (A) is 2.0 to 99.9 mass% of the total of the 1,1-dicyanoethylene (A) and the polymerizable monomer (B): 1 =CR 2 R 3 (I) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group; R 2 is a cyano group, a carboxy group, -COOR 4 (R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; 3 is a carboxy group, -COOR 5 (R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group. ) is at least one selected from an ester group and an acid anhydride group represented by the following formula:

[0011] <1,1-dicyanoethylene (A)> The resin composition of the present invention uses 1,1-dicyanoethylene (A). 1,1-dicyanoethylene (A) has excellent reactivity and is therefore preferred as a raw material for fast-curing adhesives. Furthermore, by using 1,1-dicyanoethylene (A) in combination with the polymerizable monomer (B) described below, a resin composition for adhesives having excellent heat resistance and moisture resistance can be obtained. 1,1-dicyanoethylene can be obtained by the manufacturing methods described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and U.S. Pat. No. 2,476,270.

[0012] <Polymerizable Monomer (B)> The polymerizable monomer (B) is a monomer represented by the following general formula (I): CHR 1 =CR 2 R 3 (I)

[0013] In general formula (I), R 1is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group.

[0014] R 1 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group.

[0015] R 1 The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.

[0016] R 1 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

[0017] R 1 Among these, is preferably a hydrogen atom, an alkyl group, or an alkenyl group, and more preferably a hydrogen atom.

[0018] In general formula (I), R 2 is a cyano group, a carboxy group, -COOR 4 (R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0019] R 2 Ha-COOR 4 In this case, R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. 4Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. 4 Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0020] R 2 may be an acid anhydride group, and examples thereof include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0021] R 2 Among these, a cyano group, a carboxy group, and —COOR 4 (R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.) is preferred, and a cyano group is more preferred.

[0022] R 3 is a carboxy group, -COOR 5 (R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group. R is at least one selected from ester groups and acid anhydride groups represented by the following formula: 3 Ga-COOR 5 If R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group. 5 Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. 5Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0023] R 5 Examples of the divalent or higher valent linking group include linking groups derived from divalent or higher valent alcohols such as ethylene glycol and glycerin. 5 Specific examples of compounds in which is a divalent or higher linking group include a compound obtained by esterifying ethylene glycol with two 2-cyanoacrylic acids (so-called "bifunctional cyanoacrylate") and a compound obtained by esterifying glycerin with three 2-cyanoacrylic acids (so-called "trifunctional cyanoacrylate"). Examples of compounds constituting the linking group include diols such as ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, and trivalent or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. In the present invention, from the viewpoint of availability, the divalent or higher linking group is preferably a divalent or trivalent linking group.

[0024] R 3 may be an acid anhydride group, and examples thereof include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0025] R 3 is a carboxy group, -COOR from the viewpoint of improving adhesiveness. 5 (R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group. 5 (In this case, R5 is an alkyl group having 1 to 6 carbon atoms or a divalent or trivalent linking group.

[0026] From the viewpoint of improving adhesive strength when the resin composition is used as an adhesive, the polymerizable monomer (B) is preferably at least one selected from 2-cyanoacrylic acid alkyl esters, 2-cyanopentadienoic acid alkyl esters, and methylidenemalonic acid dialkyl esters, and more preferably 2-cyanoacrylate ethyl ester.

[0027] The method for producing the polymerizable monomer (B) is not particularly limited, and known methods can be used alone or in combination. Alternatively, commercially available products can be used as the polymerizable monomer (B), such as ethyl 2-cyanoacrylate (manufactured by Aldrich).

[0028] <Content of Each Component> In the resin composition of the present invention, the content of the 1,1-dicyanoethylene (A) is 2.0 to 99.9 mass% of the total of the 1,1-dicyanoethylene (A) and the polymerizable monomer (B). When the content of 1,1-dicyanoethylene (A) is equal to or greater than the lower limit, the heat resistance and moisture resistance of the cured product obtained from the resin composition are improved. On the other hand, when the content of 1,1-dicyanoethylene (A) is equal to or less than the upper limit, the rapid curing property of the resin composition is improved. From the above viewpoints, the content of the 1,1-dicyanoethylene (A) is preferably 7.0 to 99.9 mass%, more preferably 30.0 to 99.9 mass%, even more preferably 50.0 to 99.9 mass%, and even more preferably 70.0 to 99.9 mass%, of the total of the 1,1-dicyanoethylene (A) and the polymerizable monomer (B). The content of the polymerizable monomer (B) is preferably 0.1 to 93.0 mass%, more preferably 0.1 to 70.0 mass%, even more preferably 0.1 to 50.0 mass%, and still more preferably 0.1 to 30.0 mass%, based on the total amount of 1,1-dicyanoethylene (A) and the polymerizable monomer (B).

[0029] The total content of 1,1-dicyanoethylene (A) and polymerizable monomer (B) in the resin composition of the present invention is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably substantially 100% by mass.

[0030] <Bronsted Acidic Compound> The resin composition of the present invention preferably further contains a Bronsted acidic compound. When the resin composition of the present invention contains a Bronsted acidic compound, the reactivity of 1,1-dicyanoethylene (A) can be controlled, and storage stability is improved. More specifically, since 1,1-dicyanoethylene (A) cures with even a small amount of moisture, it is preferable to completely remove moisture during the production process. However, since completely removing moisture is practically difficult, it is preferable to suppress curing (suppress the initiation of polymerization) by protonating water using a Bronsted acidic compound.

[0031] From the viewpoints of improving reactivity and easy availability, examples of the Bronsted acidic compound that can be used in the present invention include inorganic acids, carboxylic acids, and organic sulfonic acids. Among these, one or more acids selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid are preferred. Compounds that react with water to produce a compound that exhibits Bronsted acidity, such as sulfur dioxide and diphosphorus pentoxide, may also be used.

[0032] When the resin composition of the present invention contains a Brønsted acidic compound, the content thereof is preferably 0.0001 to 2.0 mass%, more preferably 0.001 to 1.0 mass%, and even more preferably 0.001 to 0.05 mass%, of the total amount of the resin composition. When the content of the Brønsted acidic compound is within the above range, storage stability is improved and high tensile shear bond strength is obtained.

[0033] From the viewpoint of storage stability, the content of the 1,1-dicyanoethylene (A) in the total amount of the resin composition is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, and even more preferably 10% by mass or less.

[0034] <Other Components> In addition to the above-described components, the resin composition of the present invention may further contain other components such as a solvent, a filler, a thickener, an antioxidant, a plasticizer, a flame retardant, a stabilizer, and an antioxidant. When the resin composition of the present invention contains other components, the content thereof is preferably 0.001% by mass or more, and preferably 10% by mass or less, and more preferably 3% by mass or less, of the total amount of the resin composition.

[0035] <Method for producing resin composition> There are no particular limitations on the method for producing the resin composition of the present invention, and for example, the resin composition can be produced by a production method including a mixing step of mixing 1,1-dicyanoethylene (A), the polymerizable monomer (B), and other components as necessary, but it is preferable to produce the resin composition in a dry atmosphere because mixing in air causes the polymerization reaction to proceed due to moisture in the air. The method for mixing the components is also no particular limitation, and they can be mixed by any known method.

[0036] [Cured Product] The cured product of the present invention is obtained by curing the above-described resin composition of the present invention with a Lewis basic compound, and more specifically, is a copolymer obtained by copolymerizing each component in the resin composition using a Lewis basic compound as a catalyst.

[0037] <Lewis Basic Compound> The Lewis basic compound used in the present invention is not particularly limited, and may be, for example, one or more selected from water, alcohols, and alkylamines, and examples of the alcohols include methanol, ethanol, propanol, etc. Examples of the alkylamines include tertiary amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, and N,N-dimethylisopropylamine.

[0038] <Method for Producing Cured Product> There are no particular limitations on the method for producing the cured product, and the cured product can be obtained by mixing the resin composition of the present invention with a Lewis basic compound at room temperature (23°C). However, the cured product can generally be obtained by reacting the resin composition of the present invention with moisture in the air (Lewis basic compound). The amount of the Lewis basic compound is not particularly limited, but is preferably 0.001 to 1.0 part by mass, and more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the resin composition. When the content of the Lewis basic compound is within the above range, the resin composition reacts quickly.

[0039] [Laminate and manufacturing method thereof] The laminate of the present invention is a laminate having a layer containing the cured product, and although there are no particular limitations on the lamination configuration, it is preferable that the cured product is placed between two adherends. By placing the cured product between the two adherends, the adherends can be firmly bonded to each other.

[0040] The adherend used in the laminate of the present invention is not particularly limited, and examples thereof include synthetic resins, metals, ceramics, fabrics, etc. Examples of synthetic resins include polyolefin resins such as polyethylene, polypropylene, copolymers of ethylene and one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, and ethylene-acrylic acid copolymers, polyurethane resins, polyamide resins, polyester resins, and polycarbonate resins. Examples of metals include steel sheets such as stainless steel sheets, cold-rolled steel sheets, and galvannealed steel sheets.

[0041] There is no particular limitation on the thickness of the adherends that constitute the laminate. On the other hand, the thickness of the layer containing the cured product is preferably 0.01 to 2.0 mm, more preferably 0.015 to 1.5 mm, and even more preferably 0.02 to 1.2 mm, from the viewpoint of firmly bonding the adherends together.

[0042] Although there are no particular limitations on the method for producing the laminate, it is preferable to produce the laminate by the method for producing a laminate of the present invention, which includes a bonding step of bonding a first adherend and a second adherend with the resin composition. There are no particular limitations on the method for bonding a first adherend and a second adherend with the resin composition, but for example, the first adherend and the second adherend can be bonded by applying the resin composition to one adherend, placing the other adherend on top of it, and curing the mixture.

[0043] The method for applying the resin composition to the adherend is not particularly limited, but examples thereof include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, and gravure coating.

[0044] There is no particular limitation on the amount of the resin composition applied to the adherend, but it is preferably 0.01 to 3.0 μL / mm 2 It is preferable that the concentration is 0.05 to 2.5 μL / mm 2 More preferably, it is 0.1 to 2.0 μL / mm 2 When the coating amount is equal to or greater than the lower limit, the objects to be bonded can be firmly bonded together, whereas when the coating amount is equal to or less than the upper limit, the objects to be bonded can be bonded together with an appropriate amount.

[0045] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The compounds used in the examples and comparative examples are as follows.

[0046] <1,1-dicyanoethylene (A)> 1,1-dicyanoethylene

[0047] <Polymerizable monomer (B)> Ethyl 2-cyanoacrylate (manufactured by Aldrich) Butyl 2-cyanoacrylate (manufactured by United States Biological Co.) Diethyl methylidenemalonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Brønsted acidic compound> Methanesulfonic acid

[0048] <Laminate Material> Steel plate (manufactured by Standard Test Piece Co., Ltd., length 25 mm, width 100 mm, thickness 1.6 mm)

[0049] Example 1: Under dry nitrogen, 0.02 g of 1,1-dicyanoethylene (A) and 0.98 g of ethyl 2-cyanoacrylate (polymerizable monomer (B)) were mixed. A resin composition was prepared by further blending this mixture with a Brønsted acid compound (methanesulfonic acid) so that its content was 0.01% by mass relative to the total amount of the resin composition. This resin composition was evaluated in accordance with JIS K6861:1995. Specifically, 100 μL of the resulting resin composition was applied to a 12.5 mm x 25 mm area of ​​a steel plate, and another steel plate was placed on top of this applied surface. The two steel plates were then left to stand for one day at room temperature (23°C) and 50% RH to incorporate moisture as a Lewis base compound, thereby curing the resin composition and bonding the two steel plates together to obtain a laminate. The tensile shear adhesive strength of each laminate was then measured under the following conditions. The results are shown in Table 1.

[0050] <Normal state adhesion test> The tensile shear adhesive strength of the laminate was measured at a tension speed of 20 mm / min using a universal material testing machine Model 5969 (manufactured by Instron) at 25% RH and 25°C. <Heat-resistant adhesion test> The laminate was left to stand in a constant temperature and humidity chamber at 25% RH and 120°C for 3 days, and then the tensile shear adhesive strength of the laminate was measured at 25% RH and 25°C using a universal material testing machine Model 5969 (manufactured by Instron) at a tension speed of 20 mm / min.

[0051] <Moisture Resistance Adhesion Test> The laminate was allowed to stand in a thermo-hygrostat chamber at 90% RH and 40°C for 1 day, and then the tensile shear adhesive strength of the laminate was measured at 25% RH and 25°C using a universal material testing machine Model 5969 (manufactured by Instron) at a tensile speed of 20 mm / min.

[0052] <Method for evaluating storage stability> Resin compositions prepared according to the formulations described in the Examples and Comparative Examples were left to stand for 3 hours in a test environment of a temperature of 50°C and a humidity of 50%, and the storage stability was evaluated by checking whether or not precipitates were generated.

[0053] Examples 2 to 16, Comparative Examples 1 to 4 Laminates were prepared in the same manner as in Example 1, except that resin compositions were prepared according to the formulations shown in Tables 1 to 3, and the tensile shear adhesive strength was measured in the same manner. The results are shown in Tables 1 to 3.

[0054] Examples 17 to 22 Resin compositions prepared according to the formulations shown in Table 4 were left to stand for 3 hours in a test environment of 50°C and 50% humidity to allow moisture from the air to be mixed in, and the presence or absence of precipitates was evaluated. The results are shown in Table 4.

[0055]

[0056]

[0057]

[0058]

[0059] As is clear from the results in Table 1, the resin composition of the present invention exhibits excellent heat resistance and moisture resistance when used as an adhesive. Furthermore, the results in Table 4 show that the resin composition of the present invention also has excellent storage stability.

Claims

1. A resin composition comprising 1,1-dicyanoethylene (A) and a polymerizable monomer (B) represented by the following general formula (I): A resin composition, characterized in that the content of the 1,1-dicyanoethylene (A) is 2.0 to 99.9 mass% in the total of the 1,1-dicyanoethylene (A) and the polymerizable monomer (B). CHR 1 =CR 2 R 3 (I) (In general formula (I), R 1 is at least one selected from a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group, R 2 is a cyano group, a carboxy group, -COOR 4 (R 4 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; R 3 is a carboxy group, -COOR 5 (R 5 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent or higher linking group; and is at least one selected from an ester group and an acid anhydride group represented by the following formula:

2. The resin composition according to claim 1, wherein the polymerizable monomer (B) is at least one selected from the group consisting of 2-cyanoacrylic acid alkyl esters, 2-cyanopentadienoic acid alkyl esters, and methylidenemalonic acid dialkyl esters.

3. The resin composition according to claim 1 or 2, further comprising a Bronsted acidic compound.

4. A cured product obtained by curing the resin composition according to claim 1 or 2 with a Lewis basic compound.

5. A laminate comprising a layer comprising the cured product according to claim 4.

6. A method for producing a laminate, comprising a bonding step of bonding a first adherend and a second adherend with the resin composition according to claim 1 or 2.