JP2009051944A - Radical-curable adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radical-curable adhesive composition capable of bonding various kinds of adherends through strong adhesive force without causing curing defects by air. <P>SOLUTION: The radical-curable adhesive composition comprises a chlorosulfonated polyethylene, styrene and/or an acrylic monomer, a transition metal compound, and a polyamine compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a radical curable adhesive composition.

  As is known for “Niwa” etc., adhesives have been familiar since ancient times. Adhesives, such as polyvinyl acetate adhesives and rubber glues, exhibit adhesive function by evaporating the solvent, mix the main agent and curing agent like epoxy resin adhesives, There are also those that exhibit tougher adhesive strength, heat resistance, and chemical resistance by causing primary crosslinking.

  In recent years, attempts have been made to perform bonding at a lower temperature in a shorter time. This adhesive is a radical curable adhesive using a redox polymerization initiator, and is widely known as a second generation adhesive (SGA).

  In SGA, a rubber polymer such as chlorinated polyethylene is usually dispersed or dissolved in an acrylic monomer such as methyl methacrylate, and a crosslinkable monomer such as ethylene glycol dimethacrylate is added, followed by curing with a redox polymerization initiator. . Examples of the redox polymerization initiator include a combination of an organic peroxide (oxidizing agent) such as benzoyl peroxide / N, N-dimethyl-p-toluidine and an amine compound (reducing agent), cumene hydroperoxide / cobalt octylate, and the like. A combination of a hydroperoxide compound (oxidant) and a metal soap (reducing agent) is well known, and is generally known as a curing system that initiates a radical curing reaction at room temperature to 100 ° C.

  SGA is widely recognized as a structural adhesive for use in aircraft and the like because it exhibits relatively good adhesive strength at low temperature and short time curing. Disadvantages include strong odor peculiar to acrylic monomers, large shrinkage during curing, large calorific value, and the presence of defects on the surface due to sinks when applied to plastics, inhibition of curing by oxygen In some cases, it is easy to be affected by the above-mentioned, sometimes causing insufficient curing and adhesion failure.

An adhesive composition comprising an acrylic polymer having —OC (O) C (R) ═CH ₂ in the molecule and a redox polymerization initiator is shown (see Patent Document 1). The technique proposed in Patent Document 1 relates to atom transfer radical polymerization of an acrylic monomer, and an adhesive composition is shown as its application.

  A flexible acrylic polymer as shown in the technique proposed in Patent Document 1 has a polymer cohesive force smaller than that of a polymer having rubber elasticity such as polyethylene, polybutadiene, and polyisoprene. Therefore, an adhesive mainly composed of a flexible acrylic polymer has a low stress only by gently stretching in a tensile test, for example. That is, the mechanical strength of the adhesive is insufficient.

  Examples of the technique proposed in Patent Document 1 show the results of an aluminum alloy-aluminum alloy single wrap adhesion test that is often performed as an adhesive strength evaluation of an adhesive. As seen in the examples, no shear adhesive force exceeding 10 MPa (the maximum value of the shear adhesive force is 6.65 MPa) is found, and the shear adhesive force is small as a structural adhesive.

An introduction of a redox curing system replacing the benzoyl peroxide / amine system has been made (see Non-Patent Document 1). The introduced technology uses cuprous chloride (Cu (I) Cl) as the oxidizing agent and 1,3,5-trimethylbarbituric acid as the reducing agent. In this combination, the polymerization is greatly inhibited by oxygen, and the curing is liable to occur. In addition, this starting system has poor curability.
JP 2006-299257 A Shigeru Hirabayashi, Yasuyo Nasu, Goro Harashima, Tadashi Hirasawa, “Study on Dental Methacrylic Resin; (9) Composition of Heat Resin, Heat Shock Resin, Pour Resin, and Room Temperature Polymer Resin”, Dental Materials (Journal of the Japanese Society for Dental Materials and Devices), Vol13. No. 3 (19840525), pp338-349.

  The radical curable adhesive composition of the present invention is cured by a radical reaction. The radical reaction is susceptible to polymerization inhibition by oxygen contained in the air, and tends to cause poor curing and poor adhesion based on this.

  The problem to be solved by the present invention is to provide a radical curable adhesive composition that joins various adherends with tough adhesive force without causing poor curing by air.

  The present invention is a radical curable adhesive composition comprising chlorosulfonated polyethylene, styrene and / or acrylic monomer, a transition metal compound, and a polyamine compound.

  The radically curable adhesive composition of the present invention joins various adherends with a strong adhesive force without causing poor curing by air.

  The radical curable adhesive composition of the present invention is made of metal-metal such as iron-iron, iron-aluminum, aluminum-aluminum, iron-copper, copper-copper, titanium alloy-titanium alloy, iron-plastic, aluminum-plastic, etc. It is suitable as an adhesive between metal, plastic, between metal and thermosetting resin, and between plastic and plastic. In particular, it exhibits strong adhesive strength as an adhesive suitable for polyphenylene oxide (PPS), polypropylene (PP), aromatic nylon (NY), and the like, which are difficult to adhere as plastics.

  Further, the radical curable adhesive composition of the present invention includes adhesion between high tensile steel (High Tensile Steel), adhesion between high tensile steel and carbon fiber or glass fiber reinforced plastic (CFRP, GFRP), aluminum alloy Adhesive strength between carbon steel and carbon fiber or glass fiber reinforced plastic (CFRP, GFRP) as a suitable adhesive.

  The adhesive composition of the present invention is excellent in mechanical strength and has necessary and sufficient performance as a structural adhesive.

  The present invention is a radical curable adhesive composition containing chlorosulfonated polyethylene, styrene and / or acrylic monomer, transition metal compound, and polyamine compound.

The chlorosulfonated polyethylene used in the radical curable adhesive composition of the present invention includes “TOSO-CSM TS-430”, “TOSO-CSM TS-530”, “TOSO-CSM TS-830”, “TOSO”. -CSM TS-930 "," TOSO-CSM TS-320 "," TOSO-CSM TS-340 "," TOSO-CSM TS-1500 "," extos ET-8010 "," extos ET-8510 " Products of Tosoh Corp.), “Hypalon 20”, “Hypalon 30”, “Hypalon 40s”, “Hypalon 40”, “Hypalon 4085”, “Hypalon 45”, “Hypalon 48” (above, DuPont Elastomer (stock) ) Products) and the like.
These chlorosulfonated polyethylenes may be used alone or as a mixture of two or more.

  In the radical curable adhesive composition of the present invention, a chlorosulfonated polyethylene having a viscosity of 200 to 2000 mPa · s in a 25 wt% toluene solution at 23 ° C. is recommended as the chlorosulfonated polyethylene.

  As the chlorosulfonated polyethylene having a 25 wt% toluene solution viscosity at 23 ° C. of 200 to 2000 mPa · s preferably used in the present invention, “TOSO-CSM TS-340” (25 wt% toluene solution viscosity at 23 ° C. 350 mPa · s) is used. s), “TOSO-CSM CN-1500” (25 wt% toluene solution viscosity at 1400 mPa · s at 23 ° C.) (above, product of Tosoh Corporation), “Hypalon 20” (25 wt% toluene solution viscosity at 23 ° C.) 1300 mPa · s), “Hypalon 30” (25% by weight toluene solution viscosity at 23 ° C. 400 mPa · s) (product of DuPont Elastomer Co., Ltd.), and the like.

  In the radical curable adhesive composition of the present invention, the chlorosulfonated polyethylene having a 25 wt% toluene solution viscosity at 23 ° C. of 200 to 2000 mPa · s can be used alone or as a mixture of two or more. Also good.

  In the radical curable adhesive composition of the present invention, the viscosity of a 25 wt% toluene solution of chlorosulfonated polyethylene at 23 ° C. is preferably 200 to 2000 mPa · s, more preferably 300 to 2000 mPa · s, and still more preferably. 300 to 1800 mPa · s is desirable. When the viscosity of a 25% by weight toluene solution of chlorosulfonated polyethylene at 23 ° C. is less than 200 mPa · s, the degree of polymerization of the chlorosulfonated polyethylene is small, and the toughness of the adhesive is lost and a tendency to become brittle is observed. When the viscosity of a 25% by weight toluene solution of chlorosulfonated polyethylene at 23 ° C. exceeds 2000 mPa · s, the viscosity of the adhesive becomes too high, and the amount of styrene and / or acrylic monomer used as a diluent is too high. In some cases, the shrinkage rate and heat generation at the time of curing increase and it becomes impossible to design good adhesion.

  Here, in the present invention, the viscosity of a 25 wt% toluene solution at 23 ° C. is measured using a Brookfield viscometer after dissolving chlorosulfonated polyethylene in toluene so that the concentration of chlorosulfonated polyethylene is 25 wt%. And measured at 23 ° C.

  The radical curable adhesive composition of the present invention is for improving the adhesive application workability and increasing the adhesive strength corresponding to various adherends. Styrene and / or acrylic monomers are used.

  Styrene used in the radical curable adhesive composition of the present invention acts as a good solvent for chlorosulfonated polyethylene, and provides a flexible and impact-resistant adhesive.

  Examples of the acrylic monomer used in the radical curable adhesive composition of the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, i-butyl acrylate, and cyclohexyl acrylate. 2-ethylhexyl acrylate, lauryl acrylate, isobornyl acrylate, dicyclopentenyloxy acrylate, dicyclopentanyloxy acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyloxyethyl acrylate, acrylic acid, acrylic acid 2- Hydroxyethyl, 4-hydroxybutyl acrylate, acrylamide, N, N-dimethylacrylamide, ethyl ethylene urea, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacryl t-butyl, i-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, dicyclopentenyloxy methacrylate, dicyclopentanyloxy methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclo Pentanyloxyethyl methacrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, methacrylamide, N, N-dimethylmethacrylamide, ethyl ethylene urea methacrylate, tetrahydrofurfuryl methacrylate, N, N- Examples include dimethylaminoethyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, and glycidyl methacrylate. In the radical curable adhesive composition of the present invention, the acrylic monomer may be used alone or as a mixture of two or more.

  In the radical curable adhesive composition of the present invention, the acrylic monomer is preferably one that can dissolve, swell, or disperse chlorosulfonated polyethylene, or one that is compatible, such as methyl methacrylate, ethyl methacrylate, methacrylic monomer. Methacrylic acid esters such as benzyl acid, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate are recommended as suitable acrylic monomers. 2-Hydroxyethyl methacrylate improves adhesion to metals such as iron and aluminum, and tetrahydrofurfuryl methacrylate facilitates adjustment of the viscosity of the adhesive and improves application workability, such as metals such as iron and aluminum, and It is expected to improve adhesion to plastics such as FPR. In addition, acrylic monomers such as methacrylic acid, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, acrylamide, methacrylamide, and N, N-dimethylacrylamide increase the cohesive strength of the adhesive and increase the shear adhesive strength. The tendency to improve is seen and preferable.

  Furthermore, in the present invention, in order to avoid evaporation of the acrylic monomer due to the heat of polymerization when the adhesive is cured and foaming due to this, and to avoid a decrease in strength and adhesive strength of the adhesive due to foaming, As the monomer, the boiling point at 1013 hPa (normal pressure) is preferably 100 ° C. or higher.

  In the radical curable adhesive composition of the present invention, preferably, the acrylic monomer is methyl methacrylate (boiling point = 100.8 ° C./1013 hPa) and / or tetrahydrofurfuryl methacrylate (boiling point = 75 ° C./4 hPa). It is recommended to contain. When the acrylic monomer contains methyl methacrylate and / or tetrahydrofurfuryl methacrylate, the curability of the adhesive is improved, and it becomes easier to avoid the inhibition of curing by oxygen, and the mechanical strength and adhesion of the adhesive. There is a tendency to balance the power at a high level.

  The transition metal complex used in the radical curable adhesive composition of the present invention is a metal complex compound composed of a transition metal of Group 7, 8, 9, 10, or 11 of the periodic table. Examples of the transition metal elements of Groups 7, 8, 9, 10, or 11 of the periodic table include copper, nickel, ruthenium, and iron.

  Examples of the transition metal complex used in the radical curable adhesive composition of the present invention include a zerovalent copper complex, a monovalent copper complex, a divalent copper complex, a divalent iron complex, a divalent nickel complex, and the like. Is exemplified. In the radical curable adhesive composition of the present invention, these transition metal complexes may be used alone or in a mixture of two or more.

  In the radical curable adhesive composition of the present invention, preferably, a zero-valent copper complex, a monovalent copper complex, a divalent copper complex, and a divalent iron complex are recommended, and more preferably a monovalent copper Complexes are recommended.

  Examples of the monovalent copper compound preferably used in the radical curable adhesive composition of the present invention include cuprous chloride, cuprous bromide, cuprous iodide.

  In the radical curable adhesive composition of the present invention, the transition metal complex is an essential component for initiating the curing reaction of the adhesive and realizing low temperature and short time curing.

  Polyamine compounds used in the radical curable adhesive composition of the present invention include 2,2'-bipyridyl, 1,10-phenantrone, tetraethylethylenediamine, pentamethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-amino Examples include ethyl) amine and the like. In the radical curable adhesive composition of the present invention, these polyamine compounds may be used alone or as a mixture of two or more.

  In the radical curable adhesive composition of the present invention, a polyamine compound represented by the following structural formula is recommended as the polyamine compound.

(Here, R1, R2, R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
As a polyamine compound represented by the following structural formula,

(Here, R1, R2, R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Examples thereof include N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentaisopropyldiethylenetriamine and the like. These polyamine compounds may be used alone or in a mixture of two or more.

  In the radical curable adhesive composition of the present invention, styrene and / or chlorosulfonated polyethylene is used as a polymerization initiator by the interaction between the transition metal compound used and a ligand compound capable of forming a complex with the transition metal compound. Alternatively, it is presumed that radical polymerization of the acrylic monomer is initiated and the radical polymerization reaction proceeds by a living radical mechanism.

  In the present invention, the adhesive becomes tough and the adhesive strength is improved. Further, the curing rate of the adhesive is accelerated, and it becomes difficult for unreacted monomers to remain after curing. That is, the unpleasant feeling that the residual monomer odor remains in the cured adhesive often observed with conventional adhesives is eliminated. This effect is that a zero-valent copper complex, a monovalent copper complex, or a divalent copper complex is used as the transition metal compound used in the present invention, and N, N, N ′, N ″ as the polyamine compound. When N, N ″ -pentamethyldiethylenetriamine is used, a more pronounced tendency is seen.

  In the present invention, preferably, when a hindered amine compound having the following structural formula is further used, the storage stability and curability of the adhesive are improved and improved.

(Here, R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
As the hindered amine compound of the following structural formula used in the radical curable adhesive composition of the present invention,

(Here, R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Examples include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-1,2,2,6,6-pentamethylpiperidine, and the like. These hindered amine compounds may be used alone or in a mixture of two or more.

  In the radical curable adhesive composition of the present invention, preferably, by using a hindered amine compound, the solubility of the transition metal compound in styrene and / or acrylic monomer is drastically improved. There is a tendency that the initiation reaction of the adhesive composition occurs smoothly, the curing rate increases, and an adhesive having higher toughness and excellent adhesive strength can be obtained.

  By using the hindered amine compound, the radical curable adhesive composition of the present invention exhibits sufficient adhesive strength at a low temperature of about room temperature to 80 ° C. and for a short time of about 5 minutes to 60 minutes. At the same time, the storage stability of the adhesive is improved. Furthermore, the adhesives exhibit good mechanical strength, and are designed from high strength with a breaking stress of 30 MPa or more to flexible with a breaking elongation of 300% or more (tensile strength test; ASTM D 638). Is possible. At the same time, the lap shear strength (tensile shear strength test; ASTM D 1002) of aluminum alloy-aluminum alloy also exhibits a high tensile shear strength of 10 MPa or more.

  In the radical curable adhesive composition of the present invention, the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer is 100% by weight, and chlorosulfonated polyethylene is preferably 3 to 60% by weight. More preferably, it is 5 to 60% by weight, and still more preferably 8 to 45% by weight. When the content of the chlorosulfonated polyethylene is less than 3% by weight, the flexibility of the adhesive is reduced, and the impact resistance and adhesiveness may be reduced. When the content of chlorosulfonated polyethylene exceeds 60% by weight, the mechanical strength of the adhesive is lowered, and there are cases where sufficient adhesive strength is not exhibited. When the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer is 100% by weight, and the chlorosulfonated polyethylene is 3 to 60% by weight, the mechanical strength, adhesive strength, and There is a tendency to balance the environmental suitability of the adhesive (moisture and heat resistance, heat resistance, etc.) and to exhibit excellent performance.

  In the radical curable adhesive composition of the present invention, the chlorosulfonated polyethylene is used in an amount of 12 to 42% by weight, where the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer is 100% by weight. Most preferably.

  In the radical curable adhesive composition of the present invention, the transition metal compound is preferably 0.5 to 10 weights with respect to 100 weight parts of the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer. Parts, more preferably 0.5 to 8 parts by weight, still more preferably 0.5 to 5 parts by weight. When the amount of the transition metal compound used is less than 0.5 parts by weight, the curability of the adhesive deteriorates, and there are cases where sufficient adhesive strength is not exhibited. When the amount of the transition metal compound used exceeds 10% by weight, the pot life of the adhesive tends to be too short, and the adhesive workability tends to deteriorate.

  In the radical curable adhesive composition of the present invention, the polyamine compound is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer. More preferably, 0.2 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight are used. When the usage-amount of a polyamine compound is less than 0.01 weight part, the sclerosis | hardenability of an adhesive agent deteriorates and the case where it cannot show sufficient adhesive strength is seen. When the usage-amount of a polyamine compound exceeds 5 weight%, the tendency for the pot life of an adhesive agent to become too short is seen, and the tendency for adhesion workability to deteriorate is seen.

  In the radical curable adhesive composition of the present invention, the hindered amine compound of the following structural formula is

(Here, R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Preferably, 0.005 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, more preferably 100 parts by weight of the total amount of chlorosulfonated polyethylene and styrene and / or acrylic monomer. 0.1 to 5 parts by weight is preferably used. When the amount of the hindered amine compound used is 0.005 to 10 parts by weight, the adhesive has good curability, exhibits sufficient adhesive strength, and does not cause poor curing.

  The radical curable adhesive composition of the present invention can be produced, for example, as follows.

  After a predetermined amount of chlorosulfonated polyethylene is dissolved or swelled and dispersed in a styrene and / or acrylic monomer, a predetermined amount of polyamine compound, and if necessary, a hindered amine compound is added and dissolved to dissolve the main agent. To manufacture. Before performing the bonding operation, a transition metal compound that is a curing agent is added and mixed well to obtain a radical curable adhesive composition.

  In the radical curable adhesive composition of the present invention, the adhesive is applied to an adherend such as metal or plastic so that the film thickness is about 50 μm to 5 mm, and then adhered at room temperature to about 80 ° C. for about 5 to 60 minutes. By curing the agent, a good adhesive member can be produced.

  In the radical curable adhesive composition of the present invention, a radical polymerizable oligomer having two or more (meth) acryloyl groups in one molecule can be preferably used. A radically polymerizable oligomer having two or more (meth) acryloyl groups in one molecule imparts an appropriate cross-linked structure to the adhesive, improves the toughness of the adhesive, and improves heat resistance.

  In the radical curable adhesive composition of the present invention, the radical polymerizable oligomer having two or more (meth) acryloyl groups in one molecule includes ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and trimethylol. Examples include propane triacrylate, trimethylolpropane trimethacrylate, diacrylate of bisphenol A diglycidyl ether, dimethacrylate of bisphenol A diglycidyl ether, polyester acrylate, polyurethane acrylate, and the like. Examples of epoxy di (meth) acrylates such as diacrylate of bisphenol A diglycidyl ether and dimethacrylate of bisphenol A diglycidyl ether include “NK ester BPE-100” and “NK ester BPE-200” (above, Shin Nakamura Chemical). As examples of products from Kogyo Co., Ltd., polyester acrylate, polyurethane acrylate, etc., “Aronix M-5700”, “Aronix M-7100” (above, products from Toagosei Co., Ltd.) and the like are exemplified. In the radical curable adhesive composition of the present invention, the radical polymerizable oligomer having two or more (meth) acryloyl groups in one molecule may be used alone or as a mixture of two or more kinds. Good.

  In the radical curable adhesive composition of the present invention, the radical polymerizable oligomer having two or more (meth) acryloyl groups in one molecule is preferably 0.2 to 50% by weight in 100% by weight of the acrylic monomer. %, More preferably 0.5 to 30% by weight, and still more preferably 2.0 to 25% by weight. When the amount of the radical polymerizable oligomer used is 0.2 to 50% by weight, the toughness of the adhesive is improved, the heat resistance is also improved, the storage stability of the adhesive is good, and the impact resistance is good.

  Furthermore, in the radical curable adhesive composition of the present invention, paint additives such as a wetting agent and a penetrating / wetting agent are preferably used.

  In the radical curable adhesive composition of the present invention, as a slipping agent, a non-fluorine compound, preferably a 0.1% aqueous solution having a surface tension of 20 to 40 mN / m, more preferably a non-fluorine compound. A compound having a surface tension of 20 to 38 mN / m of a 0.1% aqueous solution, more preferably a non-fluorine compound having a surface tension of 20 to 35 mN / m of a 0.1% aqueous solution. It is recommended. In the present invention, when the wet agent is a non-fluorine compound and the surface tension of the 0.1% aqueous solution is 20 to 40 mN / m, the wettability and permeability of the adhesive to the adherend tend to be improved. In many cases, stronger adhesion is exhibited.

  Examples of the uretic agent preferably used in the radical curable adhesive composition of the present invention and having a surface tension of 20 to 40 mN / m of a 0.1% aqueous solution as a non-fluorine compound include “Surfinol 104E”. , "Surfinol 104H", "Surfinol 104A", "Surfinol 104DPM", "Surfinol 420", "Surfinol 440", "Dinol 604" (above, products of Air Products and Chemicals) Illustrated. In the radical curable adhesive composition of the present invention, these non-fluorine compounds having a 0.1% aqueous solution with a surface tension of 20 to 40 mN / m may be used alone or in combination of two or more. May be used as

  The radical curable adhesive composition of the present invention further includes various fillers such as silica, carbon black, montmorillonite, glass fiber, liquid polybutadiene, etc. for viscosity adjustment (rheology control), strength improvement and other purposes of the adhesive. It is also possible to add polymers and oligomers such as both-end acrylated liquid polybutadiene, liquid acrylonitrile-butadiene resin, liquid both-end acrylated acrylonitrile-butadiene resin, and MBS resin.

  Hereinafter, an example of the present invention will be described with reference to examples. In the examples described below, the tensile strength test of the adhesive was performed at 23 ° C. and 80 ° C. according to ASTM D638. Further, the tensile shear strength test was performed at 23 ° C. according to ASTM D1002, with the adhesive thickness set to 500 μm. An aluminum alloy (JIS A-2017P) was used as the adherend. In any test, the curing conditions for the adhesive were a curing temperature of 60 ° C. and a curing time of 30 minutes.

Example 1
Chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation) (25% weight toluene solution viscosity at 23 ° C. is 350 mPa · s) (hereinafter also referred to as “TS-340”) 35 g, styrene ( Hereinafter, 0.05 g of t-butylcatechol (hereinafter also referred to as TBC) which is a polymerization inhibitor of St) is dissolved in 52 g of styrene (St), and then an epoxy dimethacrylate oligomer “BPE-200” (Shin Nakamura Chemical). A product of Kogyo Co., Ltd., 5 g of 2,2′-bis [4- (methacryloxydiethoxy) phenyl] propane), 8 g of 2-hydroxyethyl methacrylate (hereinafter also referred to as HEMA) are added, .3 "(product of Kao Corporation, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine) 1 g (hereinafter also referred to as PMDEA) was added to produce an adhesive main agent (1).

  Radical curable adhesive (1) was produced by mixing 101.05 g of adhesive main agent (1) with 1 g of cuprous chloride (Cu (I) Cl) as a curing agent.

Example 2
After dissolving 35 g of chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation) and 0.05 g of styrene polymerization inhibitor t-butylcatechol (TBC) in 52 g of styrene (St), 5 g of epoxy dimethacrylate oligomer “BPE-200” (product of Shin-Nakamura Chemical Co., Ltd.) and 8 g of 2-hydroxyethyl methacrylate (HEMA) were added, and “Sanol LS-744” (Sankyo Life Tech Co., Ltd.) As of July 2007, Ciba Specialty Chemicals Co., Ltd. product, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine) 1 g, “Kaorraiser No. 3” (PMDEA) (Kao Corporation ) Product) 1 g was added to produce an adhesive main agent (2).

  A radical curable adhesive (2) was produced by mixing 102.05 g of the adhesive main agent (2) with 1 g of cuprous chloride (Cu (I) Cl) as a curing agent.

  Example 3 30 g of chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation), p-methoxyphenol (hereinafter also referred to as MEHQ) which is a polymerization inhibitor of methyl methacrylate (hereinafter also referred to as MMA). Say) After dissolving 0.05 g in 57 g of methyl methacrylate (MMA), 5 g of epoxy dimethacrylate oligomer “BPE-200” (product of Shin-Nakamura Chemical Co., Ltd.), 8 g of 2-hydroxyethyl methacrylate (HEMA) In addition, 1 g of “Sanol LS-744” (product of Sankyo Lifetech Co., Ltd.) and 1 g of “Kaorraiser No. 3” (PMDEA) (product of Kao Co., Ltd.) were added. 3) was produced.

  A radical curable adhesive (3) was produced by mixing 102.05 g of the adhesive main agent (3) with 1 g of cuprous chloride (Cu (I) Cl) as a curing agent.

  Example 4 30 g of chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation), p-methoxyphenol (MEHQ) which is a polymerization inhibitor of tetrahydrofurfuryl methacrylate (hereinafter also referred to as THFMA) After dissolving 0.05 g in 57 g of tetrahydrofurfuryl methacrylate (THFMA), 5 g of epoxy dimethacrylate oligomer “BPE-200” (product of Shin-Nakamura Chemical Co., Ltd.), 8 g of 2-hydroxyethyl methacrylate (HEMA) In addition, 1 g of “Sanol LS-744” (product of Sankyo Lifetech Co., Ltd.) and 1 g of “Kaorraiser No. 3” (PMDEA) (product of Kao Co., Ltd.) were added. 4) was produced.

  A radical curable adhesive (4) was produced by mixing 102.05 g of the adhesive main agent (4) with 1 g of cuprous chloride (Cu (I) Cl) as a curing agent.

Example 5
10 g of chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation), 20 g of MBS resin “Toyolac Transparent Grade 900-335” (product of Toray Industries Inc.), p-methoxyphenol (MEHQ) 0 .05 g dissolved in 30 g of tetrahydrofurfuryl methacrylate (THFMA), 20 g of epoxy dimethacrylate oligomer “BPE-200” (product of Shin-Nakamura Chemical Co., Ltd.), 20 g of 2-hydroxyethyl methacrylate (HEMA), 1 g of “Sanol LS-744” (product of Sankyo Lifetech Co., Ltd.) and 1 g of “Kaorraiser No. 3” (PMDEA) (product of Kao Co., Ltd.) were added to produce an adhesive main agent (5). did.

  Curing agent cuprous chloride (Cu (I) Cl) 1 g was mixed with 102.05 g of the adhesive main agent (5) to produce a radical curable adhesive (5).

Comparative Example 1
In Example 1, a radical curable adhesive (6) was produced in the same manner as in Example 1 except that “Kao Raiser No. 3” (a product of Kao Corporation) was not blended.

Comparative Example 2
After dissolving 35 g of chlorosulfonated polyethylene “TOSO-CSM TS-340” (product of Tosoh Corporation) and 0.05 g of t-butylcatechol (TBC) in 52 g of styrene (St), the epoxy dimethacrylate oligomer “BPE- 200 ”(product of Shin-Nakamura Chemical Co., Ltd.), 8 g of 2-hydroxyethyl methacrylate (HEMA), and 2 g of N, N-dimethyl-p-toluidine (hereinafter also referred to as DMPT) are added. Thus, an adhesive main agent (7) was produced.

  A radical curable adhesive (7) was produced by mixing 100 g of the adhesive main agent (7) with 2 g of benzoyl peroxide (hereinafter also referred to as BPO) as a curing agent.

  The composition list of the radical curable adhesives of Examples and Comparative Examples is shown in Table 1, and the test results are shown in Table 2.

    Adhesives 1 and 2 showed large elongation because styrene having good compatibility with chlorosulfonated polyethylene was used. The adhesive strength (tensile shear strength) also cleared 10 MPa required as a structural adhesive. Moreover, since "Sanol LS-744" is used for the adhesive 2, the curability is improved and the adhesive strength (tensile shear strength) is large.

  As the adhesive 3, methyl methacrylate is used. Both tensile strength and adhesiveness were balanced.

  Adhesive 4 has good compatibility with chlorosulfonated polyethylene, and tetrahydrofurfuryl methacrylate having a microphase-separated structure after curing is used. The amount of chlorosulfonated polyethylene (rubber component) was large, and the tensile strength, elongation, and adhesive strength (tensile shear strength) were well balanced and showed large values.

  Adhesive 5 is low in chlorosulfonated polyethylene (rubber component) and contains a thermoplastic MBS resin. Moreover, the quantity of "BPE-200" and HEMA was increasing, and both the tensile stress and the adhesive force showed large values.

  Adhesive 6 did not cure. The adhesive 7 was affected by the inhibition of curing by air, and the test piece surface caused a curing failure, so that the tensile strength test could not be performed.

Claims (7)

A radical curable adhesive composition comprising chlorosulfonated polyethylene, styrene and / or acrylic monomer, a transition metal compound, and a polyamine compound. The radical curable adhesive composition according to claim 1, wherein the chlorosulfonated polyethylene has a 25 wt% toluene solution viscosity at 23 ° C of 200 to 2000 mPa · s. The radical curable adhesive composition according to claim 1 or 2, wherein the acrylic monomer contains methyl methacrylate and / or tetrahydrofurfuryl methacrylate. The radical curable adhesive composition according to any one of claims 1 to 3, wherein the transition metal compound contains at least one of a zero-valent copper complex, a monovalent copper complex, and a divalent copper complex. The polyamine compound has the following structural formula

(Here, R1, R2, R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
The radical curable adhesive composition according to any one of claims 1 to 4, which is represented by: The radical curable adhesive composition further comprises a hindered amine compound having the following structural formula

(Here, R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The radical curable adhesive composition according to claim 1, comprising: The radical curable adhesive composition according to any one of claims 1 to 5, wherein the radical curable adhesive composition further comprises a radical polymerizable oligomer having two or more (meth) acryloyl groups in one molecule. .