JPS59159866A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. exhibiting excellent grab even on an oil-stained surface on which a rust preventing oil or a process oil is left behind, consisting of a polar group-contg. polymer, an epoxy acrylate resin, a (meth) acrylic monomer, an org. peroxide and an amino compd. CONSTITUTION:A compsn. consists of (1) a polar group-contg. polymer selected from an acrylonitrile/butadiene copolymer, an acrylonitrile/butadiene copolymer contg. carboxyl groups, an acrylic rubber, a urethane rubber, chloroprene rubber, chlorosulfonated polyethylene, an ethylene/vinyl acetate copolymer, an ethylene/ acrylic acid copolymer, a thermoplastic polyester and nylon or a mixture thereof, (2) an epoxy acrylate, (3) an acrylic or methacrylic monomer having at least two different functional groups, (4) an org. peroxide and (5) imidazole or an amine compd. contg. a tert. amino group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive composition used for bonding metals, paper, plastics, inorganic materials, etc., and particularly for adhesive compositions in which rust preventive oil or processing oil remains. The present invention relates to a structural adhesive that has excellent adhesion properties even on curved surfaces, has high adhesion even after heat curing, and further suppresses the occurrence of 115 after adhesion.

Traditionally known structural adhesives include epoxy resin, polyurethane, structural acrylic, and anaerobic structural adhesives, and oil-absorbing adhesives that can adhere to metal surfaces with oil still attached to them. Talolobrene-based mastic type (non-volatile content of 67% or more) and vinyl chloride-based mastic type (non-volatile content of 92% or more) are used. These adhesives are used as structural adhesives, or the adhesion force decreases on oily surfaces, or although they adhere to curved surfaces, their strength as structural adhesives (nose) feet etc. It's not about strength. In addition, polyurethane type and structural acrylic type,
Adhesives for anaerobic structures may be fixed on the surface of a porous body or cured while being held vertically after fixing, or scratches may occur due to plasticization of marks or vibration. yl C
The disadvantage was that spot welding or clipping was required. A type that cures even at high temperatures has been reported, for example, in JP-A No. OC50-15862A, using a liquid containing epoxy resin and a polyamide resin, and at least one of these liquids contains =1-silene resin (both liquids)
Although the adhesive composition obtained by kneading is shown in Ii'l,
This product has the disadvantage that the adhesive strength is inferior to 1σ at a temperature of 11%.
, °1 was there. Polyurethane adhesives are mainly C
Is it effective for bonding 11 such as mortar, slay 1, and ash? Is it effective for adhesion between metals? Because it is easy to do, and there is no (11) no to smoke,] Concubine'4:]
The degree of tsuji is decreasing. Also, regarding cyanoacrylate-1 to Ct) Zento 1 or '390'C, the fragrance power decreases or is not too great, but as soon as you exceed that point, it suddenly drops to I1 (Ct) or '390'C. It had the drawbacks of poor peeling power and lack of versatility due to high cost.

The present invention was made to solve the drawbacks of the conventional techniques 1, 1, and i. The purpose of the present invention is to provide a structural adhesive composition that exhibits excellent adhesion properties and high adhesive strength after curing, and also prevents rust from forming on the adhesive surface, and is suitable for use in automobiles. It is used in assembly lines, electric refrigerators, washing machines, other electric accessories, architecture, civil engineering structures, etc.

This object of the invention is accomplished by the following adhesive composition.

That is, the present invention provides (1) an acryloni-1-lylubutadiene copolymer, an acryloni-1-lylubutadiene copolymer in which the carboxyl group is
Relubutacyenno (polymer, acrylic rubber, urethane rubber, chloroprene rubber, chlorosulfonated polyethylene, direzyvinyl acetate copolymer, ethylene-acrylic copolymer, ) plastic polyurethane, saturated polynisdel, nylon (2) Epoxy acrylate-1 to resin alone or a mixture of two or more of them; The above acrylic or methacrylic monomers, (4) organic oxides, (5) imitazoles or amine compounds containing at least one tertiary amine, etc. compound, or (in addition to (6) mono(2-methacryloyl)-1xystyl)acid phosphe-1, mono(2-acryloy[]oxydyl)acin 1 small sulfate, impugned. Motono l Kurire-1
- or methacrylate (- alone or in combination)
, Is it possible to combine tT? ), and these adhesive compositions are heat-cured and used as adhesive agent -C,
The polymer of the component (1) in the present invention is relatively highly polar, and the components (2), (3), and (6) have a high adhesiveness.
Component C is a polymer that is compatible with the reactive oligomer or monomer used and has a certain degree of oil resistance, that is, it does not swell significantly even with oil.
Therefore, acryloni-1-lyl-butadiene copolymers and other highly polar polymers mentioned above are suitable. Further, in order to impart tenacity during adhesion after curing, a polymer with rubber-like elasticity is selected, and a polymer with elongation even after curing is selected. These polymers can be used alone or in a blend with other polymers to improve appropriate modulus and compatibility, and to exhibit balance as a whole system.

The (2) component epoxy acrylate-1~resin is as follows:
Various epoxy resins, such as hisphenol A type, bisphenol F type, polyphenol type, halogenated hisphenol type, polyglycidyl ester type, peracetic acid flu
It is an acrylic or methacrylic modified F2 type, etc., and has an acrylic or methacrylic group at the end. This epoxy acrylate resin has a suitable hardness at the highest temperatures, prevents dripping on the adhesive surface, and has a suitable tank and reactivity when heated. For molecules, the amount is 200 to 4,000, and for compounding, it is 20 to 200 parts by weight per 100 parts by weight of the polar porin, which is the component (1).

The (3) component of the present invention is a methacrylic monomer (a methacrylic monomer).
Increasing the crosslinking density of the adhesive, increasing the modulus, and increasing the wetting of the adhesive interface, especially the solubility in various surface conditions, various rust preventive oils, mechanical oils, hydraulic oils, crushed oils, etc. First time to dissolve and disperse and improve the tack of the system! It has an effect on the adhesive strength of "I". The acrylic or methacrylic monomers used here are nib-lene glycol (meth)acrylate, di-I-dilene glycol (meth)acrylate-1 to 1, and di-L-dilene glycol (meth)acrylate-1-11. , 3 ethylene glycol di (meth)acryle-1, 1.4 hexane glycol di (meth)acryle-1~, 1.6 hexane glycol di (meth)acryle-1~, neopendel glycol di (meth)acryle) Hey, Te1-
lamedilol methane tri7-acryle i~, tetramethylol methane tetraacryle-1, glycidyl (meth)acrylate-1~, 2-1-loxy]nityl (meth)
Acrylate or the like is used, and the appropriate blending ratio is 5 to 70 parts by weight per 100 parts by weight of the (1) elastomer. If more than 70% is added, it becomes too hard, resulting in poor toughness, poor bending strength, peel strength and impact strength. Moreover, if it is less than 5 parts by weight, the modulus will be poor, and the adhesive strength and heat resistance will also decrease.

In the present invention, the phosphorus-containing (meth)acrylate and/or nitrogen-containing (meth)acrylate, which is the component (6), has excellent adhesion to metal surfaces or rust prevention effects after adhesion.
This is remarkable, and these monomers are incorporated into the 74<tb> due to the heating effect, allowing the antirust effect to be maintained for a long time. If such a monomer -C is mono(
2-Methachloroyloxyedyl) acin 1 hebosuf 1-1
to, mono(2-acryloylothyl diethyl)acid phosph t-1~, dimedylaminoedyl (meth)acrylate-1~, cy:L delaminoethyl (meth)acrylate, 2-amino 1 thylhinyl ether, sh- Preferred examples include butylaminonibyl acrylate-1 and self-A linoethyl (meth)acrylate. This 6th component is not necessarily an essential component in the present invention, but it is preferable to include it from the viewpoint of improving the adhesion to metal surfaces and the rust prevention effect after adhesion, and the amount of addition is 1st (1st
) 10 parts by weight or less, preferably 1 to 10 parts by weight, per 100 parts by weight of the polymer, which is a component. Even if more than 10 parts by weight is blended, the blending effect will not improve much and it will not copolymerize with other monomers. C modulus increases, elongation decreases, and adhesive strength does not improve.

Acrylic monomer or methacrylic monomer, which is added as an optional component in J'3 in the present invention, increases the molecular weight by polymerizing, but it does not have the function of simply polymerizing, but has the same function as the above-mentioned component (3) (adhesive). iIm leakage to the interface, especially the solubility of J5 in various surface conditions and various rust preventive oils,
Dissolving and dispersing machine oil, hydraulic oil, lubricating oil, etc.
Improve the tack of the system, and the effect will be effective on the initial adhesion. I
-I L/If there is a process that causes high levels of hardness,
and low atmospheric pressure 1. ) monomer is used. For example, when passing the firing process at 200"C, it was found that if the vapor pressure at that time was not less than 10On+mH (l), foaming would occur at the same rate as 70". Foaming is undesirable as it reduces adhesive strength.The methacrylate monomer used here has the following general formula: 1-t, C=C-C00R2 (R+ is 1" or CI-h, R2 is 1 prime number 1~1
8 alkyl group) C, specifically 1 to C 4 alkoxyconityl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxy 1del(meth)acrylate, ) Lancrylate, Detracht L1 furfuryl acrylate-1 or more may be used alone or as a mixture of two or more of them.
3 to 20 medium suspension for 00 weight tn part? ``J1 (is suitable (
-Yes.

Furthermore, the 41st (2>(3)(6)
Ingredients: 15 Yohino 1 Acrylic S1: (J methacrylic monomer is mixed with a polar polymer, which is the first component, and added with an organic peroxide, which is the fourth component, and heated in a heating oven. The organic peroxide to be used is selected according to the heating conditions.The organic peroxides used here include ketone-based baroxazine 1~, shea silver 1, hydroperoxide, dialkyl peroxide → noid, peroxyphthal, alkyl perester, bar carbonate 1-
1. Other peroxides containing silane are used. In addition, when adding the above-mentioned par 711 = lytes, the imidazole group 1 of component (!) in J3 of the present invention ((S))
Or an amine compound containing at least one tertiary amine,
Examples are imidazole 211'iM7, imidazole C1
7/, ToMP-30, DMP-10, DBtJ, l
It is advisable to add a small amount of -lyethylene di)nomine, detramedi-1 nonpentamine, etc. (about 1/3 to 1/20 of -ide mono). Of course, an inorganic filler may be added.

The above components combine with each other to develop initial tackiness, and a curing reaction results in a three-dimensional structure, lP
N
Because it has a structure with a lymerN network (interpenetrating network structure), it is possible to obtain an adhesive with moderate toughness, moderate modicolus, and excellent rust prevention properties.

Further, the present invention will be explained in detail based on Examples and Comparative Examples. Note that all amounts in Tables 1 and 2 are parts by weight.

v Gold side 1 to 14 Mixture d3 shown in Tables 1 and 2 Mixture ωC1th (
/I) Presence of the component (peroxide and the (5) component imidazoles; L, the components except the amine compound containing the tertiary amine are mixed in a mill soil, and further added to this mixture!<4)
Ingredients No. 5> 7.11 L of the ingredients were mixed while cooling to form a sheet.

10,000, without any treatment, the steel plate was immersed in anti-rust oil (Metal Guard 831) and lifted vertically for 24 hours, with a thin layer of anti-rust oil remaining on the surface. 8m
A test piece was made by sandwiching sheets 1 to 1 of m between two metal sheets and pressing them together at a pressure of 11 yen.The curved surface fixing properties were examined, and the piece was placed vertically in an oven at 80°C for 30 minutes to heat it. The deviation was evaluated as Klli. Furthermore, this test piece was heated at 215°C for 30
After heating for minutes, the adhesive strength (tensile shear strength, T-peel strength, bending strength) was measured according to JIS K6850. The respective results are shown in Tables 1 and 2.

:l:i; Bisno 1. Nor△diglycidyl edel with 3゜t added to both ends (=j, *2:
l[1yl group added, :I:3: Shrimp-J
-1 to 834 with a methanoyl] coil group added to both ends, ``4:4: 1133 mm containing vinyl acetate!
%, :l: 5: Ester-based thermoplastic polyurethane (product name: Pandex D-5205), :i: 6: Product name: Hypalon 40, manufactured by Decobon Co., Ltd., :i: 7: W
Type: C8: Product name Byron, manufactured by Toyobo Co., Ltd.; i;
The adhesive compositions of Examples 1 to 1/'l containing component (5) or component (6) in addition to component (5) are all 1:! It exhibits good layer adhesion, good oil surface fixing properties, and scratches on heating II) of 41 to 4 cm.

The adhesive composition of the present invention, which contains the above-mentioned components (1) to (5), can be applied to 4j such as steel plates.
l C71, however, do not perform any cleaning treatment on the oil surface.
I4-Ne<t<"C"b, By sufficiently setting the stone and heat curing (, E, 11, 4 properties are expressed in the hard 1. Also, the component (6) is When further added, it not only improves the adhesion with metal but also has an excellent rust prevention effect after adhesion.Therefore, the adhesive composition 1 of the present invention can be used in assembly lines, electric refrigerators, washing machines, etc. It is widely used as an adhesive for other electrical appliances, architecture, Toki Koichi structures, etc.

Claims (1)

[Scope of Claims] +, l) Acryloni-1-lylubutadiene copolymer,
carboxyl group]? Acryloni-1 to lyru-rutathiene copolymer, acrylic rubber, urethane rubber, chloroprene rubber, chlorosulfonated poly]nidylene, superprene-vinyl acetate copolymer, edge-regid acrylic acid copolymer, thermoplastic polyurethane, saturated A single polymer or a mixture thereof selected from polyester and nylon having a polar group Pi, (22) Small oxyacrylate 1 to resin + p or a mixture of 2 or more, (3 different functional groups 2 (II, 1a consisting of acrylic or methacrylic U-1 (7'l) organic peroxide, and (!')) imidazole or an amine compound containing at least one 33-class amine; Adhesive composition. 2, C1) Acrylonitrile-butadiene copolymer, acrylonitrile-butadiene copolymer having a carboxyl group, acrylic rubber, urethane rubber, chloroprene rubber, chlorosulfonated polyethylene, edge-regid vinyl acetate copolymer, ethylene - A polymer having a polar group selected from acrylic acid copolymer, thermoplastic polyurethane, saturated polyester, and nylon alone or in a mixture thereof; (2) Epoxy acrylate resin alone or in combination;
(3) dissimilar functional groups or two or more acrylic or methacrylic monomers; (4) organic peroxides; (5) imidazoles; or amino compounds containing at least one tertiary amine. , J3yohi (6) mono(2-methacryloyl L1 xyethyl) acid phosphate, mono(2-acryloyloxyethyl) acid phosphate-1
Nitrogen-containing acrylate-1~Also (methacrylate-1~)
An adhesive composition comprising: five or more types of IP;