TW202321394A - 2-cyanoacrylate adhesive composition - Google Patents

Abstract

A 2-cyanoacrylate adhesive composition comprising a 2-cyanoacrylate compound and a polyfunctional cyanoacrylate compound, wherein the storage modulus at 25 DEG C of a cured product obtained by homopolymerization of the 2-cyanoacrylate compound is no higher than 1.0*10<SP>7</SP> Pa.

Description

2-cyanoacrylate adhesive composition

The disclosure relates to a 2-cyanoacrylate adhesive composition.

Adhesive composition containing 2-cyanoacrylate compound, due to the specific anionic polymerizability of 2-cyanoacrylate compound, can be attached to the surface of the adherend by weak anions such as a little water. Polymerization starts, and various materials are firmly joined in a short time. Therefore, it has been used as a so-called instant adhesive in a wide range of fields such as industrial use, medical use, and household use.

For example, Japanese Patent No. 5267571 has proposed an adhesive composition, which contains 2-cyanoacrylate and polyfunctional cyanoacrylate with two or more 2-cyanoacryloyl groups, wherein the above (b ) the number average molecular weight of the multifunctional cyanoacrylate is 1,000 to 50,000, and when the above-mentioned 2-cyanoacrylate is 100 parts by mass, the (b) multifunctional cyanoacrylate is 1 to 400 parts by mass share.

[Problem to be solved by the invention]

Adhesive compositions containing 2-cyanoacrylate compounds have excellent shear adhesion strength because their cured products are hard and brittle or do not have a crosslinked structure, but on the other hand, have such a problem that peel adhesion strength is low. Problems. In addition, in recent years, adhesive compositions have been required to have excellent peel adhesion strength to various materials, for example, excellent peel adhesion strength to rubber such as ethylene propylene diene rubber (EPDM).

The inventors of the present invention obtained the knowledge that the cured product of the adhesive composition disclosed in Japanese Patent No. 5267571 has room for improvement in the peeling adhesive strength of rubber.

Furthermore, the inventors of the present invention obtained the following knowledge: a 2-cyanoacrylate-based adhesive composition containing a 2-cyanoacrylate compound and a multifunctional cyanoacrylate compound, wherein the above-mentioned 2-cyanoacrylate The storage elastic modulus at 25°C of the cured product obtained by homopolymerizing the ester compound is 1.0×10 ⁷ Pa or less. According to the 2-cyanoacrylate adhesive composition, compared with the 2-cyanoacrylate adhesive composition that does not contain the above-mentioned polyfunctional cyanide An adhesive composition based on an acrylate compound, the peel adhesive strength of the hardened product to rubber is improved, and the increase rate of the peel adhesive strength is excellent.

Therefore, the problem to be solved by the present disclosure is to provide a 2-cyanoacrylate adhesive composition whose hardened product has an excellent increase rate of peel adhesive strength to rubber such as EPDM. [Technical means to solve the problem]

Specific means for solving the foregoing problems are as follows. <1> A 2-cyanoacrylate-based adhesive composition, which contains a 2-cyanoacrylate compound and a multifunctional cyanoacrylate compound, and is obtained by homopolymerizing the above-mentioned 2-cyanoacrylate compound The storage elastic modulus of the cured product at 25°C is 1.0×10 ⁷ Pa or less. <2> The 2-cyanoacrylate-based adhesive composition as described in the above-mentioned <1>, wherein the 2-cyanoacrylate-based adhesive The composition is hardened, and the hardened product with a width of 5mm, a length of 50mm, and a thickness of 1mm is fixed on the tensile testing machine, marked at the fixed position of the clamp, and stretched at a tensile speed of 20mm/min until the distance between the above-mentioned clamps is reached. After reaching 40mm (L1), release the fixation of the above-mentioned jig, measure the length (L2) between the above-mentioned marks after 1 minute, and the elongation recovery rate (%) obtained by the following calculation formula is 70% or more: Elongation recovery rate ( %): {(L1-L2)/(L1-L0)}×100. <3> The 2-cyanoacrylate-based adhesive composition as described in <1> or <2> above, wherein the 2-cyanoacrylate The ester-based adhesive composition is hardened and the hardened product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm is fixed on a tensile testing machine, marked at the fixed position of the fixture, and stretched at a tensile speed of 20 mm/min until After the distance between the above-mentioned clamps becomes 40 mm (L1), release the fixation of the above-mentioned clamps, measure the length (L3) between the above-mentioned marks after 5 minutes, and the elongation recovery rate (%) obtained by the following formula is 80% or more: Elongation recovery rate (%): {(L1-L3)/(L1-L0)}×100 <4> 2-cyanoacrylate adhesive as described in any one of the above <1> to <3> A composition in which the above-mentioned 2-cyanoacrylate-based adhesive composition is cured so that the distance between the jigs is 20 mm (L0), and the cured product has a width of 5 mm, a length of 50 mm, and a thickness of 1 mm. Fix it on the tensile testing machine, mark the fixed position of the clamps, stretch at a tensile speed of 20mm/min until the distance between the clamps becomes 40mm (L1), release the fixation of the clamps, and measure the marks after 30 minutes The length (L4) between them, the elongation recovery rate (%) obtained by the following calculation formula is above 95%: Elongation recovery rate (%): {(L1-L4)/(L1-L0)}×100. <5> The 2-cyanoacrylate-based adhesive composition according to any one of <1> to <4> above, wherein the composition is measured in accordance with Japanese Industrial Standard (JIS) K 6854-3:1999 The peel adhesive strength (N/cm) of the above-mentioned 2-cyanoacrylate adhesive composition to the ethylene propylene diene rubber (EPDM) substrate was set as As1, and the above-mentioned 2- When the peel adhesive strength (N/cm) of the 2-cyanoacrylate adhesive composition after removing the polyfunctional cyanoacrylate compound from the cyanoacrylate adhesive composition is As2, the following formula is satisfied: Sub: (As1－As2/As2)×100≧150%. <6> The 2-cyanoacrylate adhesive composition according to any one of <1> to <5> above, wherein the 2 - The cyanoacrylate-based adhesive composition contains 0.01 to 50 parts by mass of the polyfunctional cyanoacrylate compound described above. <7> The 2-cyanoacrylate-based adhesive composition according to any one of the above <1> to <6>, wherein the 2-cyanoacrylate compound has an ether bond. <8> The 2-cyanoacrylate-based adhesive composition according to the above <7>, wherein the 2-cyanoacrylate compound has two or more ether bonds. <9> The 2-cyanoacrylate-based adhesive composition according to any one of the above <1> to <8>, wherein the 2-cyanoacrylate compound contains a compound represented by the following formula (1): compound of.

In formula (1), L ¹ each independently represents -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(R ¹ )CH ₂ - or -CH ₂ CH(R ¹ )-, R ¹ represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, R ² represents a straight-chain or branched chain alkyl group having 1 to 8 carbon atoms which may have a substituent, and p represents 1 to 5 an integer of . <10> The 2-cyanoacrylate adhesive composition according to any one of the above <1> to <9>, wherein the 2-cyanoacrylate compound exhibits a maximum value of loss tangent (tanδ (max)) temperature is below 65°C. <11> The 2-cyanoacrylate-based adhesive composition according to any one of <1> to <10> above, wherein the polyfunctional cyanoacrylate compound includes a dicyanoacrylate compound and ginseng At least one of the cyanoacrylate compounds. <12> The 2-cyanoacrylate adhesive composition according to any one of the above <1> to <11>, wherein the polyfunctional cyanoacrylate compound has a molecular weight or a number average molecular weight of 200 to 50000. [Efficacy of the invention]

According to the present disclosure, it is possible to provide a 2-cyanoacrylate-based adhesive composition whose cured product has an excellent rate of increase in peel adhesive strength to rubber such as EPDM.

Hereinafter, aspects for implementing the present disclosure will be described in detail. However, this disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and this disclosure is not limited.

In the present disclosure, the numerical range represented by "-" includes the numerical values described before and after "-" as the minimum value and the maximum value, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. In addition, in the numerical range described in this indication, the upper limit or the lower limit of the numerical range can be replaced with the value shown in the synthesis example. Moreover, in this indication, the combination of 2 or more preferable aspects is a more preferable aspect.

(2-cyanoacrylate-based adhesive composition) The 2-cyanoacrylate-based adhesive composition disclosed herein contains a 2-cyanoacrylate compound and a multifunctional cyanoacrylate compound, and the above-mentioned 2-cyanoacrylate The storage elastic modulus at 25°C of the hardened product obtained by homopolymerizing the acrylate compound is 1.0×10 ⁷ Pa or less.

As a result of earnest research, the present inventors have found that by adopting the above-mentioned constitution, it is possible to provide a 2-cyanoacrylate-based adhesive composition whose hardened product has an excellent increase rate of peel adhesive strength to rubber such as EPDM. The mechanism of action of the excellent effect obtained by this is not clear, but it is presumed as follows. It is presumed that the 2-cyanoacrylate-based adhesive composition contains a 2-cyanoacrylate compound (hereinafter also referred to as 2-cyanoacrylate compound) whose hardened product obtained by homopolymerization has a storage modulus of elasticity at 25°C of 1.0×10 ⁷ Pa or less. The cured product obtained by homopolymerizing 2-cyanoacrylate compounds is called a homopolymer), and the multifunctional cyanoacrylate compound, so that the cured product of the 2-cyanoacrylate adhesive composition disclosed in this disclosure ( The entropy elasticity of the cured product (hereafter referred to only as hardened product) is improved, so the followability to the deformation of the adherend is improved, so the peel adhesion strength of the hardened product to rubber such as EPDM and its rate of increase are improved.

<2-cyanoacrylate compound> The 2-cyanoacrylate-based adhesive composition of the present disclosure contains a cured product obtained by homopolymerization having a storage elastic modulus of 1.0×10 ⁷ Pa or less at 25°C. - a cyanoacrylate compound (hereinafter also referred to as a specific 2-cyanoacrylate compound). The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain two or more specific 2-cyanoacrylate compounds. The 2-cyanoacrylate adhesive composition ^contains a 2-cyanoacrylate compound (hereinafter also referred to as 2-cyanoacrylate compounds are homopolymerized and the cured products are called homopolymers) and multifunctional cyanoacrylate compounds, so the elongation recovery rate of the cured products tends to increase. It is speculated that this is because the entropy elasticity of the cured product of the 2-cyanoacrylate-based adhesive composition disclosed in the present disclosure (hereinafter also simply referred to as the cured product) is increased by entropy elasticity, thereby accelerating the deformation of the cured product to a state before elongation, and the elongation of the cured product Increased response rate.

The storage elastic modulus at 25°C of the homopolymer is preferably 9.0×10 ⁶ Pa or less from the standpoint of the increase rate of the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. In addition, the lower limit of the storage elastic modulus of the homopolymer at 25° C. is not particularly limited, and can be, for example, 1.0×10 ⁴ Pa or more.

In this disclosure, the measurement of the storage modulus of elasticity of a cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound is carried out as follows. After injecting the 2-cyanoacrylate compound between the clamps of the dynamic viscoelasticity measuring device coated with triethanolamine, the dynamic viscoelasticity measuring device is used to measure under the conditions of a frequency of 1 Hz, a temperature of 25 ° C, and a thickness of 300 μm. Stores the modulus of elasticity. It was confirmed that the storage elastic modulus of the 2-cyanoacrylate compound did not change, and this was made into a cured product of the 2-cyanoacrylate compound. Next, using the above cured product, measure the storage elasticity of the cured product by shearing in the range of -50°C to 150°C under the conditions of a frequency of 1 Hz, a heating rate of 2°C/min, and a relative humidity of 50%. Modulus, obtain the storage elastic modulus of the cured product at 25°C. In addition, as a dynamic viscoelasticity measurement apparatus, MCR301 (model) by Anton Paar Corporation or an apparatus equivalent thereto can be used.

From the standpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, the cured product obtained by homopolymerizing a specific 2-cyanoacrylate compound shows the maximum value of loss tangent The temperature of (tanδ(max)) is preferably at most 65°C, more preferably at most 55°C, further preferably at most 45°C, particularly preferably at most 40°C. The lower limit of the above-mentioned temperature is not particularly limited, and may be, for example, -20°C or higher.

In the present disclosure, the measurement of the temperature showing the maximum value of the loss tangent of a specific 2-cyanoacrylate compound is carried out in the following manner. After injecting the specific 2-cyanoacrylate compound between the clamps of the dynamic viscoelasticity measuring device coated with triethanolamine, the dynamic viscoelasticity measuring device is used to measure the frequency at 1 Hz, the temperature is 25 ℃, and the thickness is 300 μm. Determine the storage modulus of elasticity. It was confirmed that the storage elastic modulus of the specific 2-cyanoacrylate compound did not change, and this was made into a cured product of the specific 2-cyanoacrylate compound. Using the above-mentioned cured product, under the condition of frequency of 1Hz and heating rate of 2°C/min, the dynamic viscoelasticity spectrum is obtained in the range of -50°C to 150°C, and the temperature at which the loss tangent (tanδ) becomes the maximum value is measured. . When two or more peaks are observed, the loss tangent (tan δ) which becomes the largest peak is made the maximum value. In addition, the dynamic viscoelasticity measurement apparatus which can be used is as above-mentioned.

The specific 2-cyanoacrylate compound preferably has an ether bond from the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. In addition, from the same viewpoint, the specific 2-cyanoacrylate compound preferably has 2 or more ether bonds, more preferably has 2 to 5 ether bonds, and still more preferably has 2 to 4 ether bonds. The ether bond preferably has 2 or 3 ether bonds. Furthermore, the 2-cyanoacrylate-based adhesive composition disclosed herein may contain two or more specific 2-cyanoacrylate compounds having different numbers of ether linkages.

The specific 2-cyanoacrylate compound preferably includes a compound represented by the following formula (1) from the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product.

In formula (1), L ¹ each independently represents -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(R ¹ )CH ₂ - or, -CH ₂ CH(R ¹ )-, from From the standpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, it is preferably -CH ₂ CH ₂ -, -CH(R ¹ )CH ₂ -, or -CH ₂ CH (R ¹ )-, more preferably represents -CH(R ¹ )CH ₂ - or -CH ₂ CH(R ¹ )-.

In formula (1), R ¹ represents an alkyl group having 1 to 6 carbon atoms that may have a substituent, preferably an alkyl group having 1 to 3 carbon atoms, and may be a straight chain alkyl group or a branched chain group. alkyl. As said substituent, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group are mentioned. Examples of R ¹ include methyl, ethyl, propyl, butyl, etc.; from the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, preferably Methyl or ethyl, more preferably methyl.

In formula (1), R ² represents an alkyl group having 1 to 8 carbon atoms that may have a substituent, preferably an alkyl group having 1 to 4 carbon atoms, and may be a straight chain alkyl group or a branched chain group. alkyl. Examples of the aforementioned substituents include the aforementioned substituents among R ¹ . ^R2 in formula (1) is more preferably an alkyl group having 1 to 3 carbon atoms, and more preferably methyl group, ethyl, n-propyl or isopropyl, more preferably methyl or ethyl, particularly preferably methyl.

In the formula (1), p represents an integer of 1 to 5, and is preferably an integer of 1 to 4 from the viewpoint of the increase rate of the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, and more preferably Preferably, it is an integer of 1-3, More preferably, it is 2 or 3.

Specific examples of the compound represented by formula (1) include: 2-(2-methoxyethoxy)ethyl 2-cyanoacrylate, 2-(2-ethoxyethyl 2-cyanoacrylate) Oxy)ethyl ester, 2-(2-propoxyethoxy)ethyl 2-cyanoacrylate, 2-[2-(1-methylethoxy)ethoxy]ethyl 2-cyanoacrylate ester, 2-[2-(2-methylpropoxy)ethoxy]ethyl 2-cyanoacrylate, 2-[2-(1-methylpropoxy)ethoxy ]ethyl ester, 2-[2-(1-ethylpropoxy)ethoxy]ethyl 2-cyanoacrylate, 2-(2-methoxy-1-methylethoxy base) ethyl ester, 2-(2-methoxy-2-methylethoxy) ethyl 2-cyanoacrylate, 2-(2-ethoxy-1-methylethoxy) 2-cyanoacrylate base) ethyl ester, 2-(2-ethoxy-2-methylethoxy) ethyl 2-cyanoacrylate, 1-(2-methoxyethoxy)propane-2-cyanoacrylate -ester, 2-(2-methoxyethoxy)propan-1-cyanoacrylate, 1-(2-ethoxyethoxy)propan-2-cyanoacrylate, 2 - 2-(2-ethoxyethoxy)propan-1-cyanoacrylate, 1-(2-methoxy-1-methylethoxy)propan-2-cyanoacrylate, 2-cyanoacrylate 1-(2-methoxy-2-methylethoxy)propan-2-ester, 2-cyanoacrylate 2-(2-methoxy-1-methylethoxy) Propan-1-ester, 2-(2-methoxy-2-methylethoxy)propan-1-ester, 2-cyanoacrylate 1-(2-ethoxy-1- Methylethoxy) propane-2-ester, 2-cyanoacrylate 1-(2-ethoxy-2-methylethoxy)propane-2-ester, 2-cyanoacrylate 2-(2- Ethoxy-1-methylethoxy)propan-1-ester, 2-(2-ethoxy-2-methylethoxy)propan-1-ester of 2-cyanoacrylate, 2-cyanoacrylate 1-(2-propoxy-1-methylethoxy)propane-2-acrylate, 1-(2-propoxy-2-methylethoxy)propane-2-cyanoacrylate Ester, 2-(2-propoxy-1-methylethoxy) propane-1-ester, 2-(2-propoxy-2-methylethoxy) cyanoacrylate Base) propane-1-ester, 2-cyanoacrylate 1-(2-butoxy-1-methylethoxy)propane-2-ester, 2-cyanoacrylate 1-(2-butoxy- 2-methylethoxy)propan-2-ester, 2-(2-butoxy-1-methylethoxy)propan-1-ester, 2-cyanoacrylic acid 2-( 2-butoxy-2-methylethoxy)propan-1-ester, 2-cyanoacrylate 1-(2-hexyloxy-1-methylethoxy)propan-2-ester, 2- 1-(2-hexyloxy-2-methylethoxy)propane-2-cyanoacrylate, 2-(2-hexyloxy-1-methylethoxy)propane-2-cyanoacrylate 1-ester, 2-(2-hexyloxy-2-methylethoxy)propan-1-cyanoacrylate, 2-cyanoacrylate triethylene glycol monomethyl ether, 2-cyanoacrylate Triethylene glycol monoethyl ether cyanoacrylate, triethylene glycol monopropyl ether 2-cyanoacrylate, triethylene glycol monobutyl ether 2-cyanoacrylate, triethylene glycol 2-cyanoacrylate Alcohol Monohexyl Ether, Triethylene Glycol Mono 2-Ethyl Hexyl Ether 2-Cyanoacrylate, Tripropylene Glycol Monomethyl Ether 2-Cyanoacrylate, Tripropylene Glycol Monoethyl Ether 2-Cyanoacrylate, Tripropylene glycol monopropyl ether 2-cyanoacrylate, Tripropylene glycol monobutyl ether 2-cyanoacrylate, Tripropylene glycol monopentyl ether 2-cyanoacrylate, Tripropylene glycol monohexyl ether 2-cyanoacrylate , 2-tetrapropylene glycol monomethyl ether cyanoacrylate, 2-tetrapropylene glycol monoethyl ether cyanoacrylate, 2-tetrapropylene glycol monopropyl ether cyanoacrylate, 2-tetrapropylene glycol monobutyl cyanoacrylate Ether ester, tetrapropylene glycol monohexyl ether 2-cyanoacrylate, etc. Among the above, 2-cyanoacrylic acid 2-(2-methoxyethoxy) is preferred from the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. Ethyl 1-(2-methoxy-1-methylethoxy)propan-2-ester, 2-cyanoacrylate 1-(2-methoxy-2-methylethoxy)propan-2 -ester, 2-(2-methoxy-1-methylethoxy)propan-1-ester of 2-cyanoacrylate or 2-(2-methoxy-2-methylethyl) Oxy)propan-1-ester, more preferably 2-cyanoacrylate 1-(2-methoxy-1-methylethoxy)propane-2-ester, 2-cyanoacrylate 1-(2- Methoxy-2-methylethoxy)propan-2-ester, 2-(2-methoxy-1-methylethoxy)propan-1-ester or 2-cyanoacrylate 2-(2-Methoxy-2-methylethoxy)propan-1-acrylate.

From the standpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, the specific 2-cyanoacrylate relative to the total mass of the 2-cyanoacrylate adhesive composition The compound content is preferably at least 50% by mass, more preferably at least 60% by mass, further preferably at least 70% by mass, most preferably at least 80% by mass. The upper limit of the content of a specific 2-cyanoacrylate compound is not specifically limited, For example, it can be 99.9 mass % or less.

When the specific 2-cyanoacrylate compound contains a compound represented by formula (1), from the viewpoint of the increase rate of the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, relative to 2- The total mass of the specific 2-cyanoacrylate compound contained in the cyanoacrylate adhesive composition, the content of the compound represented by the formula (1) is preferably 70% by mass or more, more preferably 80% by mass or more , more preferably at least 90% by mass, particularly preferably at least 95% by mass, or 100% by mass.

＜Multifunctional cyanoacrylate compound＞ The 2-cyanoacrylate adhesive composition disclosed herein contains a multifunctional cyanoacrylate compound. The 2-cyanoacrylate-based adhesive composition disclosed herein may contain two or more types of multifunctional cyanoacrylate compounds. In addition, the polyfunctional cyanoacrylate compound is preferably a polyfunctional 2-cyanoacrylate compound from the viewpoint of the increase rate of the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. Furthermore, in the present disclosure, the polyfunctional cyanoacrylate compound means a compound having two or more cyanoacryl groups.

Examples of polyfunctional cyanoacrylate compounds include 2-cyanoacrylate esters of the following compounds: polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, polyamide polyols , polyester polyamide polyol, acrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, ethylene-butylene copolymer polyol, polyisoprene polyol, hydrogenated polyisoprene Polyethylene polyols, polyvinyl butyral, polyvinyl formaldehyde, polyvinyl alcohol, phenolic resins, silane compounds with hydroxyl groups at both ends, siloxane compounds with hydroxyl groups at both ends, etc. From the viewpoint of the flexibility and toughness of the cured product, the polyfunctional cyanoacrylate compound preferably contains polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, Polyamide polyol, polyester polyamide polyol, acrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and hydrogenated polyisoprene polyol At least one of the group consisting of, more preferably comprising polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, poly At least one of 2-cyanoacrylates of compounds in the group consisting of isoprene polyol and hydrogenated polyisoprene polyol. Among the above, the polyfunctional cyanoacrylate compound preferably includes polyoxyalkylene polyol, more preferably includes polyoxypropylene glycol. In addition, the polyfunctional cyanoacrylate compound may contain glyceryl ether.

The polyoxyalkylene polyol is not particularly limited, and it is possible to use: polyethylene glycol, polyethylene triol, polyethylene tetraol, polypropylene glycol, polypropylene triol, polypropylene glycol Tetrol, polytetramethylene glycol, etc.; and, copolymers with polyols or other diols, etc. In addition, the polyester polyol is not particularly limited, and general polyester polyols produced by reacting dibasic acids such as adipic acid with diols, triols, etc., ring-opened caprolactone, etc., can be used. Polycaprolactone polyols obtained by polymerization, etc. Moreover, it does not specifically limit as polycarbonate diol, The general polycarbonate diol derived from ethylene carbonate etc., the polycarbonate diol obtained by copolymerizing carbonate and diol, etc. are not specifically limited. In addition, from the viewpoint of flexibility, toughness, and warm water resistance of the cured product, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, hydrogenated polyisoprene polyol, 2-Cyanoacrylate ester of pentadiene polyol.

The polyfunctional cyanoacrylate preferably contains at least one of a dicyanoacrylate compound and a thirane cyanoacrylate compound. The dicyanoacrylate compound is more preferable than the cyanoacrylate compound from the standpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. The dicyanoacrylate compound is preferably an alkanediol dicyanoacrylate compound or a polyoxyalkylene compound from the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. Polyol dicyanoacrylate compound. The reference cyanoacrylate compound is preferably a polyoxyalkylene polyol tricyanoacrylate compound from the standpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. As for the carbon number of the aliphatic group which an alkane diol biscyanoacrylate compound has, Preferably it is 2-18, More preferably, it is 4-12. In addition, the above-mentioned aliphatic group may be linear, branched, or cyclic. Examples of the alkanediol dicyanoacrylate compound include: 1,6-hexanediol-dicyanoacrylate, 1,4-butanediol-dicyanoacrylate, 1,8-octanediol- Dicyanoacrylate, 1,9-nonanediol-dicyanoacrylate, 1,10-decanediol-dicyanoacrylate, 1,12-dodecanediol-dicyanoacrylate, 1,5-pentanediol-dicyanoacrylate, 1,16-hexadecanediol-dicyanoacrylate, 1,18-octadecanediol-dicyanoacrylate, etc. Among the above, 1,6-hexanediol-biscyanoacrylate, 1,8 -octanediol-dicyanoacrylate, 1,9-nonanediol-dicyanoacrylate, 1,10-decanediol-dicyanoacrylate, 1,12-dodecanediol-bis Cyanoacrylate, 1,16-hexadecanediol-dicyanoacrylate, 1,18-octadecanediol-dicyanoacrylate, more preferably 1,6-hexanediol-dicyanoacrylate acrylate or 1,10-decanediol-dicyanoacrylate. As the polyoxyalkylene polyol constituting the polyoxyalkylene polyol dicyanoacrylate compound or the polyoxyalkylene polyol tricyanoacrylate compound, polyoxypropylene glycol (PPG), polyoxypropylene glycol (PPG), polyoxyalkylene polyol Ethylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, etc. . Among the above, polyoxypropylene glycol (PPG)-dicyanoacrylate or polyoxypropylene glycol ( PPG) - paracyanoacrylate.

The molecular weight or number average molecular weight (Mn) of the polyfunctional cyanoacrylate compound is preferably 200 to 50,000, more preferably from the viewpoint of the rate of increase in peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product. Preferably, it is 200 to 25,000, and more preferably, it is 200 to 23,000. In addition, in the present disclosure, Mn is a value obtained in terms of standard polystyrene using gel permeation chromatography (GPC).

From the viewpoint of the rate of increase in the peel adhesion strength of the cured product to rubber such as EPDM and the elongation recovery rate of the cured product, compared to the 2-cyanoacrylic acid contained in the 2-cyanoacrylate adhesive composition of the present disclosure, 100 parts by mass of the ester compound, the content of the polyfunctional cyanoacrylate compound is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, further preferably 0.5 to 20 parts by mass, especially Preferably, it is 0.7 mass part - 10 mass parts.

When the polyfunctional cyanoacrylate contains at least one of a dicyanoacrylate compound and a cyanoacrylate compound, from the viewpoint of the increase rate of the peel adhesion strength of the hardened product to rubber such as EPDM and the elongation recovery rate of the hardened product See, relative to the total mass of the multifunctional cyanoacrylate contained in the 2-cyanoacrylate adhesive composition, the sum of the content of the dicyanoacrylate compound and the cyanoacrylate compound is preferably 70%. % by mass or more, more preferably at least 80% by mass, still more preferably at least 90% by mass, particularly preferably at least 95% by mass, and may be 100% by mass.

＜Other ingredients＞ The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain other components other than the specific 2-cyanoacrylate compound and the polyfunctional cyanoacrylate compound within the range not impairing its properties. Examples of other components include: 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds, stabilizers, hardening accelerators, plasticizers, thickeners, particles, colorants, fragrances, solvents, strength Elevator etc.

Examples of 2-cyanoacrylate compounds other than specific 2-cyanoacrylate compounds include the following esters of 2-cyanoacrylate: methyl ester, ethyl ester, ethyl chloride, n-propyl ester, isopropyl ester, Propyl ester, propargyl ester, n-butyl ester, isobutyl ester, n-pentyl ester, n-hexyl ester, cyclohexyl ester, phenyl ester, tetrahydrofuryl methyl ester, heptyl ester, 2-ethylhexyl ester, n-octyl ester, 2-octyl ester Esters, n-nonyl esters, side oxonyl esters, n-decyl esters, n-dodecyl esters, methoxyethyl esters, methoxypropyl esters, methoxyisopropyl esters, methoxybutyl esters, ethoxyethyl esters Ester, Ethoxypropyl, Ethoxyisopropyl, Propoxymethyl, Propoxyethyl, Isopropoxyethyl, Propoxypropyl, Butoxymethyl, Butoxyethyl ester, butoxypropyl ester, butoxyisopropyl ester, butoxybutyl ester, 2,2,2-trifluoroethyl ester, hexafluoroisopropyl ester, etc. These 2-cyanoacrylate compounds may use only 1 type, and may use 2 or more types together.

Examples of stabilizers include (1) aliphatic sulfonic acids such as sulfur dioxide and methanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, trifluorinated methanol such as boron trifluoride methanol, and boron trifluoride diethyl ether. Anionic polymerization inhibitors such as boron complexes, HBF ₄ , and trialkyl borates; (2) Free radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tertiary butylcatechol, catechol, and gallicol agent etc. These stabilizers may be used alone or in combination of two or more.

As the curing accelerator, any thing can be used as long as it can accelerate the anionic polymerization of the 2-cyanoacrylate compound-based adhesive composition. Examples of the curing accelerator include polyether compounds, calixarenes, thiacalixarenes, pyrogallolarenes, and onium salts. These curing accelerators may be used alone or in combination of two or more.

In addition, examples of plasticizers include acetyl triethyl citrate, acetyl tributyl citrate, dimethyl adipate, diethyl adipate, dimethyl sebacate, ortho Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, dihexyl phthalate, diheptyl phthalate, phthalate Dioctyl dicarboxylate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, di(isotridecyl) phthalate, bis(pentadecanyl) phthalate Alkyl ester), dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis(2-ethylhexyl camphorate), 2-ethylhexyl cyclohexanecarboxylate, rich Diisobutyl maleate, diisobutyl maleate, glyceryl tricaproate, 2-ethylhexyl benzoate, dipropylene glycol dibenzoate, etc. Among them, acetyl tributyl limonate, dimethyl adipate, and phthalic acid are preferred from the viewpoint of good compatibility with 2-cyanoacrylate compounds and high plasticizing efficiency. Dimethyl ester, 2-ethylhexyl benzoate, or dipropylene glycol dibenzoate. These plasticizers may use only 1 type, and may use 2 or more types together.

Examples of thickeners include polymethyl methacrylate, copolymers of methyl methacrylate and acrylate, copolymers of methyl methacrylate and other methacrylates, acrylic rubber, polyvinyl acetate ester, polyvinyl chloride, polyurethane resin, polyamide resin, polystyrene, cellulose ester, polyalkylene cyanoacrylate, ethylene-vinyl acetate copolymer, etc. These thickeners may be used alone or in combination of two or more.

The 2-cyanoacrylate-based adhesive composition of the present disclosure may contain particles within the range not impairing its characteristics, whereby the adhesion formed by using the 2-cyanoacrylate-based adhesive composition can be adjusted The thickness of the agent layer. The average particle diameter of the particles is preferably from 10 μm to 200 μm, more preferably from 15 μm to 200 μm, even more preferably from 15 μm to 150 μm. The particle material is not particularly limited as long as it is insoluble in the 2-cyanoacrylate compound used and does not cause deterioration such as polymerization. Examples of particles include polyethylene, polypropylene, polymethylpentene, acrylic resin, polyvinyl chloride, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, Polypropylene, polyphenylene ether and other thermoplastic resins; unsaturated polyester, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-(meth)acrylate copolymer, phthalic acid Cross-linked resins such as diallyl ester polymers; inorganic compounds such as spherical silica, glass beads, and glass fibers; silicon oxide compounds; organic-inorganic composite particles composed of organic polymer skeletons and polysiloxane skeletons, etc. In addition, the content of the particles is not particularly limited. From the viewpoint of the curing speed and adhesive strength, when the content of the 2-cyanoacrylate compound contained in the 2-cyanoacrylate adhesive composition of the present disclosure is 100 Parts by mass, the content of particles is preferably from 0.1 parts by mass to 10 parts by mass, more preferably from 1 part by mass to 5 parts by mass, further preferably from 1 part by mass to 3 parts by mass. Furthermore, in the present disclosure, the average particle diameter of the particles is the average value based on the volume measured by a laser diffraction particle size distribution measuring device.

<Elongation recovery rate of the 2-cyanoacrylate-based adhesive composition disclosed herein> The hardened product obtained by curing the above-mentioned 2-cyanoacrylate adhesive composition disclosed in the present disclosure and having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm was fixed to the On the tensile testing machine, mark the fixed position of the clamps, stretch at a tensile speed of 20mm/min until the distance between the clamps becomes 40mm (L1), release the fixation of the clamps, and measure the length between the marks after 1 minute (L2 ), the elongation recovery rate (%) obtained by the following calculation formula is preferably more than 70%, more preferably more than 80%, more preferably more than 90%, and most preferably more than 95%. Furthermore, the measurement of the elongation recovery rate is carried out in an environment with a temperature of 25° C. and a relative humidity of 50%. Elongation recovery rate (%): {(L1－L2)/(L1－L0)}×100

The hardened product obtained by curing the above-mentioned 2-cyanoacrylate adhesive composition disclosed in the present disclosure and having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm was fixed to the On the tensile testing machine, mark the fixed position of the clamps, stretch at a tensile speed of 20mm/min until the distance between the clamps becomes 40mm (L1), release the fixation of the clamps, and measure the length between the marks after 5 minutes (L3 ), the elongation recovery rate (%) obtained by the following calculation formula is preferably more than 80%, more preferably more than 90%, more preferably more than 95%, and most preferably more than 97%. Furthermore, the measurement of the elongation recovery rate is carried out in an environment with a temperature of 25° C. and a relative humidity of 50%. Elongation recovery rate (%): {(L1－L3)/(L1－L0)}×100

The hardened product obtained by curing the above-mentioned 2-cyanoacrylate adhesive composition disclosed in the present disclosure and having a width of 5 mm, a length of 50 mm, and a thickness of 1 mm was fixed to the On the tensile testing machine, mark the fixed position of the clamps, stretch at a tensile speed of 20mm/min until the distance between the clamps becomes 40mm (L1), release the fixation of the clamps, and determine the length between the marks after 30 minutes ( L4), the elongation recovery rate (%) obtained by the following calculation formula is preferably 95% or more, more preferably 97% or more, and more preferably 99% or more. Furthermore, the measurement of the elongation recovery rate is carried out in an environment with a temperature of 25° C. and a relative humidity of 50%. Elongation recovery rate (%): {(L1－L4)/(L1－L0)}×100

In addition, as the tensile tester used for the measurement of the above-mentioned elongation recovery rate, Toyo Seiki Co., Ltd.'s STROGRAPH V20-C (trade name) or an equivalent device can be used. In addition, the hardened|cured material used for the measurement of the above-mentioned elongation recovery rate was manufactured as follows. First, a silicone rubber mold frame (mold frame) with a thickness of 1 mm was placed on a release polyethylene terephthalate (PET) film. Next, 1 μL of triethanolamine was added to 1 g of the 2-cyanoacrylate-based adhesive composition disclosed herein, stirred, and then poured into the above-mentioned mold frame. After pouring the 2-cyanoacrylate-based adhesive composition, cover the mold frame and the adhesive composition with the above-mentioned release PET mold that was separately prepared, clamp it with a glass plate, and place it at 25°C, 50% Let stand in relative humidity for 24 hours to fully harden. After curing, the frame and the release PET film were removed to obtain a cured product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm.

<Peel Adhesive Strength of the 2-Cyanoacrylate Adhesive Composition of the Present Disclosure> Let the peel adhesion strength (N/cm) of the disclosed 2-cyanoacrylate adhesive composition to the ethylene propylene diene rubber (EPDM) substrate measured in accordance with JIS K 6854-3:1999 be As1 , and the peel adhesive strength of the 2-cyanoacrylate adhesive composition after removing the multifunctional cyanoacrylate compound from the above-mentioned 2-cyanoacrylate adhesive composition after measuring the peel adhesive strength As1 ( When N/cm) is As2, it preferably satisfies the following formula (A), more preferably satisfies the following formula (B), and still more preferably satisfies the following formula (C). In addition, the increase rate of the peeling adhesive strength can be calculated|required from following formula (A) - (C). (As1－As2／As2)×100≧150% (A) (As1－As2／As2)×100≧200% (B) (As1－As2／As2)×100≧250% (C)

More specifically, the measurement of the above-mentioned peeling adhesive strength was carried out as follows. First, 1 g of the disclosed 2-cyanoacrylate-based adhesive composition was coated on an EPDM substrate, and left to stand for 7 days at a temperature of 23° C. and a relative humidity of 50% to completely harden it. After hardening, T-peel adhesive strength (N/cm) was measured based on JISK6854-3:1999 using a tensile tester. In addition, the stretching speed was set to 100 mm/min. Furthermore, the measurement of the T-peel adhesive strength is carried out in an environment with a temperature of 25° C. and a relative humidity of 50%. As the tensile tester, the same tensile tester as that used for the measurement of the above-mentioned elongation recovery rate can be used.

<Applications of the 2-cyanoacrylate-based adhesive composition disclosed herein> The 2-cyanoacrylate-based adhesive composition disclosed herein can be used in various applications such as construction applications, automobile-related applications, and electrical/electronic material applications. Examples of construction uses include elastic adhesives for construction, adhesives for laminated glass, adhesives for artificial marble, and the like. In addition, examples of electrical/electronic material applications include resins for sealing semiconductors, insulating materials for printed circuit boards, insulating coating materials for electric wires/cables, coating agents for electronic parts, adhesives for electronic parts, and sealing agents for electrical devices. In addition, the 2-cyanoacrylate-based adhesive composition of the present disclosure can also be used for packing, O-rings, and the like. Specifically, waterproof seals, insect-proof seals, vibration-proof/sound-absorbing and airtight materials for cleaners, drip-proof covers for electric water heaters, waterproof seals, heater seals, electrode seals, safety Valve diaphragms, solenoid valves, waterproof seals for steam ovens and cooking pots, water supply tank seals, water suction valves, water connection seals, thermal insulation heater parts seals, steam outlet seals, etc. for combustion machines Oil plugs, O-rings, drain plugs, supply/suction plugs, anti-vibration rubber, oil supply port plugs, oil gauge plugs, diaphragm valves, speaker gaskets for audio equipment, speaker edges End and so on. In addition, for automobile-related applications, it can be used as an adhesive seal material for maintaining airtightness, a vibration-proof material for glass, a vibration-proof material for vehicle body parts, especially windshield gaskets, and gaskets for door glass as body parts. film etc. As an engine part, it can be used as an adhesive sealant for engine oil, etc. Furthermore, the adhesive composition of the present invention can also be used in a gasket method [in-situ molded gaskets] in which a liquid sealing material is automatically applied and a sealing material is applied on an assembly line of electric/electronic parts and automobile parts by a robot or the like. Sheet (Mold In Place Gasket, MIPG), Field Formed Gasket (Formed In Place Gasket, FIPG), Field Cured Gasket (Cured In Place Gasket, CIPG)].

In addition, the 2-cyanoacrylate adhesive composition disclosed in the present disclosure can also be suitably used for resin or metal as an adherend, can be more suitably used for rubber, and can be particularly suitably used for EPDM. [Example]

Hereinafter, although the said embodiment is demonstrated concretely using an Example, the said embodiment is not limited to these Examples. In addition, unless otherwise specified, "part" hereinafter means "parts by mass".

Various physical property values were measured in the following manner.

<Storage elastic modulus at 25°C of a hardened product obtained by homopolymerizing 2-cyanoacrylate compound> After the 2-cyanoacrylate compound was injected between the clamps of the dynamic viscoelasticity measuring device coated with triethanolamine, the dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301") was used to perform the test at a frequency of 1 Hz and a temperature of The storage elastic modulus was measured at 25° C. and a thickness of 300 μm. It was confirmed that the storage elastic modulus of the 2-cyanoacrylate compound did not change, and this was made into a cured product of the 2-cyanoacrylate compound. Using the above cured product, measure the storage elastic modulus of the cured product caused by shearing in the range of -50°C to 150°C under the conditions of a frequency of 1 Hz, a heating rate of 2°C/min, and a relative humidity of 50%. , Obtain the storage elastic modulus of the cured product at 25°C. The storage elastic modulus at 25°C of the hardened product obtained by homopolymerizing the 2-cyanoacrylate compound used in each example and each comparative example (the storage elasticity of the 2-cyanoacrylate compound is described in the table Modulus) are summarized in Table 1.

<Temperature showing the maximum loss tangent (tanδ(max)) of 2-cyanoacrylate compounds> After the 2-cyanoacrylate compound was injected between the clamps of the dynamic viscoelasticity measuring device coated with triethanolamine, the dynamic viscoelasticity measuring device (manufactured by Anton Paar, product name "MCR301") was used to perform the test at a frequency of 1 Hz and a temperature of The storage elastic modulus was measured at 25° C. and a thickness of 300 μm. It was confirmed that the storage elastic modulus of the 2-cyanoacrylate compound did not change, and this was made into a cured product of the 2-cyanoacrylate compound. Using the above-mentioned cured product, under the condition of frequency of 1Hz and heating rate of 2°C/min, the dynamic viscoelasticity spectrum is obtained in the range of -50°C to 150°C, and the temperature at which the loss tangent (tanδ) becomes the maximum value is measured. . When two or more peaks are observed, the loss tangent (tan δ) which becomes the largest peak is made the maximum value.

(Example 1 to Example 14) In 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 was blended so that the content described in Table 1 became, and it stirred until it became uniform, and produced A 2-cyanoacrylate-based adhesive composition.

(comparative example 1) The 2-cyanoacrylate compound described in Table 1 was used as an adhesive composition.

(Comparative Example 2 to Comparative Example 5) In 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 was blended so that the content described in Table 1 became, and it stirred until it became uniform, and produced Adhesive composition.

(comparative example 6) The 2-cyanoacrylate compound described in Table 1 was used as an adhesive composition.

(Comparative Example 7 to Comparative Example 10) In 100 parts of the 2-cyanoacrylate compound described in Table 1, the polyfunctional cyanoacrylate compound described in Table 1 was blended so that the content described in Table 1 became, and it stirred until it became uniform, and produced Adhesive composition.

(Comparative Example 11 and Comparative Example 12) The 2-cyanoacrylate compound described in Table 1 was used as an adhesive composition.

The details of the codes of the polyfunctional cyanoacrylates in Table 1 are as follows. ･HBCA: Difunctional 2-cyanoacrylate compound (1,6-hexanediol-dicyanoacrylate), molecular weight: 276.29 ･DBCA: Difunctional 2-cyanoacrylate compound (1,10-decanediol-dicyanoacrylate), molecular weight: 332.40 ･PPG4000TCA: Trifunctional 2-cyanoacrylate compound (PPG(Mn4000)-paracyanoacrylate), Mn is 4640 ･PPG10000BCA: Difunctional 2-cyanoacrylate compound (PPG(Mn10000)-biscyanoacrylate), Mn is 19700

In addition, HBCA was synthesized according to the following method. 4.80 g (41.6 millimoles) of cyanoacryloyl chloride and 270 mL of benzene were put into a 500-mL flask equipped with a stirrer, a thermometer, a Lippie condenser, a nitrogen blowing tube, and a dropping funnel. Then, the temperature of the reaction system was raised to 60° C., and 5.22 g of 1,6-hexanediol (reagent) was added to a solution in which 5 mL of benzene was dissolved while blowing nitrogen gas through a nitrogen blowing tube. Then, the temperature was maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25°C, benzene was distilled off under reduced pressure, and recrystallization by cooling to -20°C in a pentane/hexane=7/4 mixed solution was repeated twice to obtain 5.02 g of a solid multifunctional cyanoacrylate (HBCA). In addition, dry benzene was used as benzene, and the glassware which fully heated and dried was used for glassware. The same applies to the following synthesis examples.

In addition, DBCA was synthesized according to the following method. 4.80 g (41.6 millimoles) of cyanoacryloyl chloride and 270 mL of benzene were put into a 500-mL flask equipped with a stirrer, a thermometer, a Lippie condenser, a nitrogen blowing tube, and a dropping funnel. Then, the temperature of the reaction system was raised to 60° C., and 10.2 g of 1,10-decanediol (reagent) was added to a solution in which 10 mL of benzene was dissolved while blowing nitrogen gas through a nitrogen gas blowing tube. Then, the temperature was maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25°C, benzene was distilled off under reduced pressure, and recrystallization by cooling to -20°C in a mixed solution of pentane/hexane=7/4 was repeated twice to obtain 8.00 g of a solid. multifunctional cyanoacrylate (DBCA).

In addition, PPG4000TCA was synthesized according to the following method. 2.40 g (20.8 millimoles) of cyanoacryloyl chloride and 135 mL of benzene were charged into a 500-mL flask equipped with a stirrer, a thermometer, a Lippie condenser, a nitrogen blowing tube, and a dropping funnel. Then, the temperature of the reaction system was raised to 60° C., while nitrogen gas was blown into the nitrogen gas blowing tube, 25.2 g of polyoxypropylene glycol [number average molecular weight: 4000 (catalogue value), polyether triol type, manufactured by ADEKA Corporation, trade name "ADEKA POLYETHER G-4000"] was added to a solution in which 16 mL of benzene was dissolved. Then, the temperature was maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25 degreeC, benzene was distilled off under reduced pressure, and 28.1 g of colorless and viscous oily polyfunctional cyanoacrylates (PPG4000TCA) were obtained.

In addition, PPG10000BCA was synthesized according to the following method. 2.40 g (20.8 millimoles) of cyanoacryloyl chloride and 135 mL of benzene were charged into a 500-mL flask equipped with a stirrer, a thermometer, a Lippie condenser, a nitrogen blowing tube, and a dropping funnel. Then, the temperature of the reaction system was raised to 60° C., and nitrogen gas was blown in from a nitrogen gas blowing tube while 94.5 g of polyoxypropylene glycol [number average molecular weight: 10000 (catalogue value), both terminal hydroxyl type, manufactured by AGC Corporation, trade name “ PREMINOL S-4011”] was added to the solution dissolved in 60mL of benzene. Then, the temperature was maintained at 60° C. and stirred for 30 minutes. Then, after cooling to 25 degreeC, benzene was distilled off under reduced pressure, and 97.8 g of colorless and viscous oily polyfunctional cyanoacrylates (PPG10000BCA) were obtained.

＜Evaluation of Peel Adhesion Strength＞ On an ethylene propylene diene rubber (EPDM) base material (EPDM-5065 manufactured by Iramagawa Rubber Co., Ltd.), 1 g of the adhesive composition produced in the above-mentioned Examples and Comparative Examples was coated, and statically placed at 23°C and a relative humidity of 50%. Leave for 7 days to fully harden. After hardening, T-peel adhesive strength (N/cm) was measured based on JISK6854-3:1999 using the said tensile tester. Furthermore, the measurement of the T-peel adhesive strength was carried out in an environment with a temperature of 25° C. and a relative humidity of 50%, and the tensile speed was set at 100 mm/min. The measurement results are shown in Table 1.

The peel adhesion strength (As1a) of the 2-cyanoacrylate adhesive composition produced in Example 1 to the EPDM substrate, and the peel adhesion strength of the adhesive composition produced in Comparative Example 11 to the EPDM substrate ( As2a) The increase rate ((As1a-As2a/As2a)×100) of the peeling adhesive strength was calculated and found to be 270%. In the same manner as above, the peel adhesion strength of the 2-cyanoacrylate-based adhesive compositions produced in Examples 2 to 7 to EPDM substrates, and the adhesive composition produced in Comparative Example 11 to EPDM substrates According to the peeling adhesion strength, the increasing rate of the peeling adhesion strength was obtained, and the results were 242%, 247%, 201%, 278%, 163%, and 156%, respectively. In addition, the peel adhesion strength (As1b) of the 2-cyanoacrylate adhesive composition produced in Example 8 to the EPDM substrate, and the peel adhesion of the adhesive composition produced in Comparative Example 12 to the EPDM substrate The strength (As2b) obtained the increase rate of the peeling adhesive strength ((As1b-As2b/As2b)×100), and the result was 372%. In the same manner as above, the peel adhesion strength of the 2-cyanoacrylate-based adhesive compositions produced in Examples 9 to 14 to EPDM substrates, and the adhesive composition produced in Comparative Example 12 to EPDM substrates The peeling adhesion strength was obtained to obtain the increase rate of the peeling adhesion strength, and the results were 432%, 440%, 410%, 521%, 270%, and 206%, respectively. In addition, the peeling strength (As1c) of the adhesive composition produced in Comparative Example 1 to the EPDM substrate and the peeling adhesion strength (As2c) of the adhesive composition produced in Comparative Example 2 to the EPDM substrate were obtained. The increase rate of adhesive strength ((As1c-As2c/As2c)×100) was 2%. The increase in the peeling adhesive strength was obtained from the peeling adhesive strength of the adhesive composition produced in Comparative Example 3 to the EPDM substrate and the peeling adhesive strength of the adhesive composition produced in Comparative Example 1 to the EPDM substrate in the same manner as above. rate, the result was 8%. In addition, the peeling strength (As1D) of the adhesive composition produced in Comparative Example 7 to the EPDM substrate and the peeling adhesion strength (As2D) of the adhesive composition produced in Comparative Example 6 to the EPDM substrate were obtained. The increase rate of the adhesive strength ((As1D-As2D/As2D)×100) was 137%. In the same manner as above, the peeling strength was obtained from the peeling strength of the adhesive composition produced in Comparative Examples 8 to 10 to the EPDM substrate and the peeling strength of the adhesive composition produced in Comparative Example 6 to the EPDM substrate. The increase rate of adhesive strength was 144%, 94%, and 81%, respectively.

From the above, it can be seen that the 2-cyanoacrylate-based adhesive composition produced in the examples is excellent in the increase rate of the peeling adhesive strength to rubber such as EPDM. Table 1 puts together the increase rate of the peeling adhesive strength of each Example and a comparative example. In addition, about the comparative example 1, the comparative example 6, the comparative example 11, and the comparative example 12 which are the reference|standard of peeling adhesive strength, it describes as "1" in Table 1. In addition, about Comparative Example 4 and Comparative Example 5, since the increase rate of the peeling adhesive strength was not observed, it described as "-" in Table 1.

＜Evaluation of elongation recovery rate＞ A silicone rubber mold frame with a thickness of 1 mm was placed on a release polyethylene terephthalate (PET) film (manufactured by TEIJIN FILM SOLUTIONS Co., Ltd., product name "PUREX (registered trademark) A31"). 1 μL of triethanolamine was added to 1 g of the adhesive composition produced in the above-mentioned Examples and Comparative Examples, stirred, and then poured into the above-mentioned mold frame. After pouring the adhesive composition, cover the mold frame and the adhesive composition with the above-mentioned release PET mold prepared separately, clamp it with a glass plate, and let it stand at 25°C and 50% relative humidity for 24 hours , to fully harden. After curing, the mold frame and the release PET film were removed to obtain a cured product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm.

Using a tensile testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "STROGRAPH V20-C"), set the distance between the clamps to 20mm (L ₀ ) and mark the hardened product at the clamp fixing position , stretched at a stretching speed of 20 mm/min until the distance between clips becomes 40 mm (L ₁ ). After releasing the fixation of the jig, the length (L ₂ ) between the marks was measured at 1 minute, 5 minutes, and 30 minutes, and the elongation recovery rate (%) was calculated according to the following calculation formula. The calculation results are shown in Table 1. Elongation recovery rate (%): {(L ₁ -L ₂ )/(L ₁ -L ₀ )}×100

[Table 1]

As can be seen from Table 1, the 2-cyanoacrylate-based adhesive composition prepared in the examples is superior in the peel adhesion strength and the increase rate of the peel adhesion strength to rubber such as EPDM, compared with the adhesive composition prepared in the comparative example. . In addition, it can be seen that the cured product of the 2-cyanoacrylate-based adhesive composition produced in the examples is superior in the elongation recovery rate compared to the adhesive composition produced in the comparative example.

The disclosure of Japanese Patent Application No. 2021-115346 filed on July 12, 2021 is incorporated herein by reference in its entirety. All documents, patent applications, and technical specifications described in this specification are specifically incorporated by reference in this specification to the same extent as if each document, patent application, and technical specification were separately described.

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Claims (12)

A 2-cyanoacrylate adhesive composition, which contains a 2-cyanoacrylate compound and a multifunctional cyanoacrylate compound, and the hardened product obtained by homopolymerizing the above-mentioned 2-cyanoacrylate compound in The storage elastic modulus at 25°C is 1.0×10 ⁷ Pa or less. The 2-cyanoacrylate-based adhesive composition according to claim 1, wherein the 2-cyanoacrylate-based adhesive composition is hardened so that the distance between jigs is 20 mm (L0). Fix the hardened product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm on the tensile testing machine, mark the fixed position of the clamps, and stretch at a tensile speed of 20 mm/min until the distance between the aforementioned clamps becomes 40 mm (L1 ), remove the fixation of the aforementioned clamps, determine the length (L2) between the aforementioned marks after 1 minute, and the elongation recovery rate (%) obtained by the following calculation formula is more than 70%: Elongation recovery rate (%): {(L1-L2)/(L1-L0)}×100. The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein the 2-cyanoacrylate-based adhesive composition is made so that the distance between the clamps is 20 mm (L0). Fix the hardened product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm on the tensile testing machine, mark the fixed position of the clamps, and stretch at a tensile speed of 20 mm/min until the distance between the aforementioned clamps becomes 40 mm. After (L1), remove the fixation of the aforementioned clamps, measure the length (L3) between the aforementioned marks after 5 minutes, and the elongation recovery rate (%) obtained by the following calculation formula is more than 80%: Elongation recovery rate (%): {(L1-L3)/(L1-L0)}×100. The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein the 2-cyanoacrylate-based adhesive composition is made so that the distance between the clamps is 20 mm (L0). Fix the hardened product with a width of 5 mm, a length of 50 mm, and a thickness of 1 mm on the tensile testing machine, mark the fixed position of the clamps, and stretch at a tensile speed of 20 mm/min until the distance between the aforementioned clamps becomes 40 mm. After (L1), release the fixation of the aforementioned clamps, measure the length (L4) between the aforementioned marks after 30 minutes, and the elongation recovery rate (%) obtained by the following calculation formula is 95% or more. Elongation recovery rate (%): {(L1－L4)/(L1－L0)}×100 The 2-cyanoacrylate adhesive composition as described in Claim 1 or 2, wherein, the aforementioned 2-cyanoacrylate adhesive composition measured in accordance with JIS K 6854-3:1999 is The peel adhesive strength (N/cm) of the propylene diene rubber (EPDM) base material was set to As1, and the aforementioned polyfunctional cyanide was removed from the aforementioned 2-cyanoacrylate adhesive composition after the peel adhesive strength As1 was measured. When the peel adhesive strength (N/cm) of the 2-cyanoacrylate-based adhesive composition after the acrylate compound is As2, the following formula is satisfied: (As1－As2/As2)×100≧150%. The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein, relative to 100 parts by mass of the aforementioned 2-cyanoacrylate compound, the 2-cyanoacrylate-based adhesive composition Containing 0.01 to 50 parts by mass of the aforementioned polyfunctional cyanoacrylate compound The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein the 2-cyanoacrylate compound has an ether bond. The 2-cyanoacrylate-based adhesive composition according to claim 7, wherein the 2-cyanoacrylate compound has two or more ether bonds. The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein the aforementioned 2-cyanoacrylate compound includes a compound represented by the following formula (1):

In formula (1), L ¹ each independently represents -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(R ¹ )CH ₂ - or -CH ₂ CH(R ¹ )-, R ¹ represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, R ² represents a straight-chain or branched chain alkyl group having 1 to 8 carbon atoms which may have a substituent, and p represents 1 to 5 an integer of . The 2-cyanoacrylate-based adhesive composition according to claim 1 or 2, wherein the hardened product obtained by homopolymerizing the 2-cyanoacrylate compound has a maximum loss tangent value (tanδ( max)) temperature is below 65°C. The 2-cyanoacrylate adhesive composition according to claim 1 or 2, wherein the multifunctional cyanoacrylate compound includes at least one of a dicyanoacrylate compound and a cyanoacrylate compound. The 2-cyanoacrylate adhesive composition according to claim 1 or 2, wherein the molecular weight or number average molecular weight of the aforementioned polyfunctional cyanoacrylate compound is 200-50,000.