JPH0588278B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel composition having an acrylate group or a methacrylate group, which is suitably used as an adhesive. In particular, the present invention provides novel acrylate or methacrylate groups containing relatively effective amounts of chlorosulfonated polyethylene and graft copolymers to significantly improve the overall adhesive performance of the composition. A composition having the following. Various patents (e.g. U.S. Pat. No. 3,890,407;
No. 4112013, No. 4118436, No. 4126504, No.
No. 4127699, No. 4182644, No. 4223115, No.
4226954, 4263419, 4293665),
It has been shown that adhesives having acrylate or methacrylate groups can be obtained from mixtures containing effective amounts of chlorosulfonated polyethylene. In the above-mentioned patents, the physical properties of adhesive adhesion are stated in terms of lap shear strength or T-peel strength, or both. Additionally, some of these patents claim that the inclusion of chlorosulfonated polyethylene provides other benefits, such as no premixing of the ingredients prior to use, relatively rapid curing, and Formation of durable strong bonds or adhesion to oily metal surfaces). As the following terms are used throughout this application, adhesives with acrylate groups are defined as:

[Formula] Adhesives with methacrylate groups are based on the chemical structure below.

[Formula] For example, when R is hydrogen, the former is acrylic acid and the latter is methacrylic acid, or when R is a methyl group, they are methyl acrylate and methyl methacrylate, respectively. Graft Copolymer A polymer having relatively long chains or chains of at least two different monomers or monomer units, such that the chains are joined together in a "block" or "graft" arrangement. It's okay. The block arrangement is linear and formed by at least two alternating monomer units. Moreover, the block arrangement may be formed by chains of monomer units alternating (or repeating) either in an ordered or random manner). See US Pat. No. 4,332,858. Block or graft polymers are often referred to as copolymers, trimers or multicomponent polymers. In a grafted configuration, one or more of the chains are
Furthermore, the graft is grafted to the main chain of another chain, and the graft is
Typically, this is done at each one of a plurality of grafting locations on the backbone. See, for example, pages 350-351 of "Textbook of Polymer Science" by F. W. Bill Meyer, 2nd edition, published by John Willy & Sons, Willy Interscience Division (1971). In graft copolymer technology, when the backbone is a rubber or rubber-like material and the backbone grafted is a monomer of vinyl or acrylate or methacrylate groups, the backbone is Often referred to as the "core". The grafted chains to the core form a "shell" around it. The graft copolymers, often referred to as resins, are often in the form of a plurality of relatively small particles, especially when the rubber or rubber-like material or the graft moiety or both are crosslinked. However, not all graft copolymer resins have the core and shell shape. For example, some have a more continuous (ie, homogeneous) microstructure, which very often takes the form of an interpenetrating polymer network. Graft copolymer resins with core and shell configurations are currently primarily used as modifiers in certain polymer systems. For example, certain ABS
(Acrylonitrile-butadiene-styrene) resin or MBS (methacrylate-butadiene-styrene) resin has good impact resistance or processability when added to PVC (polyvinyl chloride). Graft copolymers themselves are generally not added to adhesive compositions to enhance or improve adhesive properties. For example, U.S. Pat.
No. 3870675 indicates that adhesive compositions having acrylate groups or methacrylate groups can contain ABS resin (column 2, lines 6 to 6).
In line 27), the ABS resin is included primarily for its rubbery properties. Moreover, certain types of ABS resins are known to be rubber-like materials and are therefore often used in place of other rubber-like materials. Moreover, this type of ABS resin is, as is known, a two-phase system, containing a rubber or rubbery phase within a matrix, a continuous, glassy phase. It is further well known that obtaining suitable rubbery properties for ABS resins of this type requires selective grafting between a continuous phase and a rubber or rubbery phase. See, for example, page 408 of the above-mentioned "Textbook of Polymer Science."
Accordingly, Patent No. 3,870,675 further describes other compositions in which other rubbers or rubber-like materials are substituted for ABS (in that patent, in column 3, lines 42 to 45 and column 6, table 3). Related to this, column 2, lines 15 to 15
Please refer to line 19. ). The adhesive composition of the patent has adhesive properties (e.g., tensile strength after contact, shear strength and impact strength). Further, U.S. Pat. No. 4,287,106 discloses adhesive compositions having acrylate or methacrylate groups (see column 2, lines 33-48) containing ABS polymers, but in particular chlorosulfonated polyethylene. The content of (column 1, lines 57 to 68, column 2, lines 1 to 32, column 8,
1st column, lines 14 to 34 related to lines 41 to 56 and column 9, lines 50 to 64). In particular, the patent teaches that chlorosulfonated amides or imides in place of chlorosulfonated polyethylene result in adhesive compositions having certain desirable adhesive qualities or properties. Moreover, to date, the addition of rubber or rubbery polymers such as ABS to adhesive compositions having acrylate or methacrylate groups has improved the first class (or group) adhesive properties of the composition. but the further addition (or inclusion) of additional ingredients such as chlorosulfonated polyethylene (to improve the adhesive properties of the second class or group of compositions)
It was believed that this would probably make the adhesive properties of the first group relatively less effective, or otherwise adversely affect the overall adhesive performance of the composition. Therefore, the above-mentioned U.S. Pat. No. 4,287,106
The combined inclusion of ABS polymer and chlorosulfonated polyethylene in adhesive compositions having acrylate or methacrylate groups is not indicated. OBJECTS AND SUMMARY OF THE INVENTION The first object of the invention is to provide adhesive compositions having novel acrylate or methacrylate groups. Another object of the present invention is to provide a composition containing an effective amount of a chlorosulfonated polyethylene resin and a graft copolymer so as to improve the overall quality or properties of the adhesive composition. be. Still other objectives are to provide relatively high compressive shear strength (i.e., to provide a relatively strong adhesive bond between, e.g., most plastic materials) and lap shear strength (i.e., to provide a relatively strong adhesive bond, e.g., between most metal materials). It is an object of the present invention to provide an adhesive composition having adhesive bonding properties), peel strength, and impact strength. In summary, for the above-mentioned purposes, the novel acrylate or methacrylate group-containing adhesive compositions of the present invention contain ester monomers having acrylate or methacrylate groups, so as to considerably improve the overall adhesive quality or properties thereof. a catalyst, and relatively effective amounts of a chlorinated or chlorosulfonated polyethylene polymer resin and a graft copolymer resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The compositions of the present invention may include acrylate-based ester monomers. However, preferably the composition includes methacrylate ester monomer. The methacrylate ester monomer is preferably selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and tetrahydrofurfuryl methacrylate. Even more preferably, the methacrylate ester monomer is selected from the group consisting of methyl methacrylate and ethyl methacrylate. Most preferably the methacrylate ester monomer is methyl methacrylate. In certain cases, it may be desirable for the methacrylate ester monomer to contain an effective amount of an inhibitor to inhibit or otherwise inhibit its polymerization. For example, the following examples of compositions of the invention that include methacrylic acid methyl ester monomers typically include:
The ester monomer contains from about 50 parts per million (ppm) to about 90 parts per million (ppm) of hydroquinone as the inhibitor. Throughout this application, ppm is based on the total weight of the named materials. In this sense, the expression ranges from about 50 to about 50 pounds per million pounds of ester monomer.
Equivalent to a content of 90 pounds of hydroquinone, the weight of the monomer is the combined amount of hydroquinone and methyl methacrylate. The composition may further include an acid monomer having an acrylate group, such as acrylic acid. See, for example, the discussion below regarding illustrative illustrations. However, in some cases, it may be preferable to further include methacrylic acid. On top of that,
The methacrylic acid can be used in the following examples (of the composition of the invention):
In this case, acid monomers having arylate groups are usually used as inhibitors for the reasons explained immediately above.
Contains 250ppm hydroquinone. The composition of the invention further comprises a catalyst. "catalyst"
means a free radical generator. As explained in column 2, lines 23 and 24 of US Pat. No. 4,112,013, examples of the free radical generator include organic peroxides, organic hydroperoxides, peresters, and peracids. As is well known in the art of compositions having acrylate and methacrylate groups, the catalyst is used to initiate the polymerization of monomers having acrylate and methacrylate groups. A preferred catalyst is cumene hydroperoxide, as shown in the Examples below. The compositions of the present invention further include a chlorinated or chlorosulfonated polyethylene polymer resin. In the case mentioned above (see e.g. U.S. Pat. No. 3,890,407),
It has been found that chlorinated polyethylene can be substituted for chlorosulfonated polyethylene. However, when the chlorinated polyethylene is replaced, an organic chlorinated sulfonation is preferably further included. That is, the compositions of the present invention include a chlorosulfonated polyethylene polymer, the resin preferably containing from about 25% to about 70% by weight of chlorine;
from about 3 mmol to about 160 mmol sulfonyl chloride moieties per 100 grams. The polymer resin is disclosed in U.S. Patent Nos. 3890407, 4112013, and
It is described in detail in No. 4182644. A brief note from the patent is that the polyethylene from which the chlorosulfonated polyethylene is prepared must have a melt index of about 4 to about 500. Suitable chlorosulfonated polyethylene polymer resins are prepared from branched polyethylene and have a chemical structure similar to that shown below.

One suitable chlorosulfonated polyethylene polymer resin commercially available under the trademark "HYPALON 30" is currently available from E.T. Dupont Unnemore & Co., 19898 Wilmington, Delaware. Commercially available. In particular, the chlorosulfonated polyethylene polymer resin under the trademark "Hypalon 30" is approximately 43% by weight.
of chlorine and about 34 mmoles of sulfonyl chloride moieties per 100 grams of polymeric resin, and is known to be made from branched polyethylene having a melt index of about 100, as given below. It is known to have certain other physical properties as outlined in Table 1 below. See also, eg, US Pat. No. 4,226,954, incorporated herein by reference. Table 1A below also shows other suitable types of chlorosulfonated polyethylene (CSPE). These varieties, sold under the trademark "Hypalon", are currently available commercially from EI DuPont de Nemois and Company. The use of these other types of chlorosulfonated polyethylene is given below in connection with illustrative examples. However, the preferred type of chlorosulfonated polyethylene Hypalon 30 provided herein is
is of the most preferred type.

[Table] The composition preferably also contains a catalyst activator (or reaction initiator). In this specification,
The terms "activator" and "initiator" are used interchangeably and usually mean an aldehyde-amine condensate, an organic sulfonyl chloride, or a mixture thereof. For example, the condensate may be made from a primary amine and butyraldehyde, where the amine is, for example, aniline or butylamine. On the other hand, certain well-known catalysts (e.g. thermally activatable peroxides or azodiisobutyronitrile) catalyze (preferably) when heated above room temperature to induce their decomposition. It is known that this results in the polymerization of monomers without the presence of a catalyst activator (or reaction initiator), and therefore the content (of the composition) of catalyst activator (or reaction initiator) is Not the point. However, certain well-known cocatalysts (eg, cobalt, copper, and other transition element compounds) are often added to aid thermally induced peroxide decomposition. Additionally, ultraviolet light and other forms of radiant energy may be used in place of heat to induce polymerization in the absence of a suitable activator. For example, pages 12 to 14 of "The Chemistry of Organic Film Formers" by D. H. Solomon, published by Robert E. Kriega Publishers (1977), and by John Willyend Sands. (1982
See pages 604 to 605 of ``Resin Polymers and Science and Technology'' edited by MD Vizial. Further, as the active agent contained in the composition of the present invention, a condensation product of an aliphatic aldehyde with an aliphatic or aromatic amine is used. In the absence of such condensates, organic materials with sulfonyl chloride moieties are preferred. However, reaction initiators (reaction activators) also include condensates of butyraldehyde and aniline.
One such butyraldehyde-aniline condensate sold under the trademark "VANAX 808" is currently available commercially from RT Vanderbilt, Inc., 230 Park Street, New York, NY 10017. Also, the tertiary amines described in the above-mentioned U.S. Pat. , can be used as a catalytic reaction initiator. The chlorosulfonated polyethylene polymer resin used contains sulfonyl chloride moieties that act as catalyst activators (or reaction initiators).
For certain adhesive compositions described below that do not contain chlorosulfonated polyethylene polymer resins, certain organic sulfonyl chloride derivatives, such as propane sulfonyl chloride or paratoluene sulfonyl chloride, may be added to compensate for the lack of a sulfonyl chloride moiety. is added to the adhesive composition. Moreover, the adhesive composition of the present invention further contains a graft copolymer resin. Generally speaking, the graft copolymer resins of the present invention include rubber particles or a rubbery core or network surrounded by a relatively hard shell, which may even be entrapped. Additionally, the graft copolymer resins have been found to be useful as modifiers of the physical properties of PVC or other normally rigid resins in general, as briefly discussed above. See US Pat. No. 3,845,164.
Additionally, the physical property modifiers have been found to increase the flexibility and impact resistance of many normally rigid plastics. In this method of use, the graft copolymer is generally in relatively small particles;
The particles can be dispersed throughout the normally rigid plastics prior to injection molding, for example. Moreover, when dispersed in this manner throughout the plastics, particles of graft copolymer resins are generally not known to swell or react with the plastics. However, in the examples disclosed below, suitable graft copolymer particles are observed to "swell" in size and react or otherwise interact with the monomer component to be polymerized of the composition. It seems so. On the other hand, most ABS resins included in injection moldable plastics compositions do not appear to swell (for reasons outlined above) but rather dissolve in the compositions. However, in the present invention, when particles of a suitable graft copolymer resin are included in an adhesive composition, the particles of a suitable graft copolymer typically expand in size and become relatively gel-like; It has been found to improve the spreadability and flow properties of uncured adhesive compositions (described below). Highly desirable in the use of the improved flow adhesives described above. For example, when an adhesive is applied to an article by a dropper applicator, many commercially available adhesives typically move from a first point on the article (once the adhesive is applied) to It exhibits an undesirable tendency to form adhesive "streaks" that extend from one point to a second point (the next location on the applicator).
On the other hand, when the adhesive of the present invention was simultaneously tested, it was sufficient to apply relatively small droplets locally to the area of the article to be bonded. That is, the adhesive of the present invention is also effective for use in the field of bonding relatively small parts (for example, electronic parts). During testing of adhesive performance with a dropper applicator, it was observed that graft copolymer resins (eg, molding grade ABS resins) were also soluble in methacrylate ester monomers. In the present invention, methacrylate ester and methacrylate acid monomers polymerize and attach themselves to particles of chlorosulfonated polyethylene polymer resin. The mechanism of the adhesion and polymerization is currently unknown.
Details are not completely known. For example, it is not known to what extent deposition or polymerization occurs, nor is the order (of deposition and polymerization). However, it is believed that at least some of these monomers become attached during the initial stages of the polymerization reaction. Moreover, the ester and acid monomers are currently believed to enter the shell of the individual particles of the graft copolymer resin and polymerize into the particles, thereby expanding the dimensions of the shell or the core or both. However, theories aside, adhesive compositions having resin particles of chlorosulfonated polyethylene polymers and graft copolymers contained therein contain acrylate group (and even methacrylate group) ester and acid monomers. It is surprising that this greatly improves the adhesion and flow physical properties of the adhesive. Suitable graft copolymer resins include acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS), methacrylate-acrylonitrile-butadiene-styrene (MABS), acrylate-styrene-acrylonitrile (ASA), and all-acrylic resins. , ethylene-propylene-diene-monomer elastomeric backbone grafted with styrene-acrylonitrile (SAEPDM), and methacrylic-acrylic rubber-styrene (MAS). More preferred graft copolymer resins are selected from the group consisting of MABS, ASA, all-acrylic resins, and MBS. The most preferred graft copolymer resins are selected from the group consisting of MABS and ASA. The ABS graft copolymer resin preferably has a styrene-butadiene rubber core and a styrene-acrylonitrile shell. The MBS graft copolymer resin preferably has a styrene-butadiene rubber core and an acrylic polymer or copolymer shell. The MAS graft copolymer resin preferably has a styrene-butadiene rubber core and a methacrylate-acrylonitrile copolymer shell. More preferably, the MABS graft copolymer resin is about 75% by weight of its total weight and about 50:
It has a core of butadiene and styrene in a weight ratio of 25 and a shell of methyl methacrylate and acrylonitrile in a weight ratio of approximately 20:5. Suitable ASA graft copolymer resins are substantially as disclosed in US Pat. No. 3,944,631, incorporated herein by reference. That is, unlike the rest of the graft copolymer resins described above, the preferred ASA graft copolymer resins contain relatively small grafts (column 8, lines 9 through 45 and column 9, lines 1 through 1). Column 1, lines 31 to 32 in relation to line 20).
The most preferred ASA graft copolymer resin commercially available under the trademark "SCC1015" (see Table 2 below) is substantially as described in Patent No. 3944631 and is a cross-linked acrylate elastomer, cross-linked styrene - acrylonitrile copolymers and linear styrene-acrylonitrile copolymers. Moreover, the most preferred ASA graft copolymer resins will have a network of interpenetrating polymers. Suitable all-acrylic graft copolymer resins are as disclosed in Patent No. 3,985,703. Trademarks “KM323B” and “KM330” (see Table 2 below)
The most preferred acrylic graft copolymer resins commercially available under the trade name have a rubber-type core composed of about 75% of the total amount of butyl methacrylate type monomers and a shell of methyl methacrylate. Currently commercially available and marketed under various trademarks of well-known manufacturers, the preferred methods just described above,
Examples of more preferred and most preferred graft copolymer resins are shown in Table 2 below.

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Table: Experimental Procedures Unless otherwise noted, adhesive compositions were prepared by combining two mixtures containing methacrylic acid methyl ester monomers. One of the two monomer mixtures includes a chlorosulfonated polyethylene resin. The other includes a graft copolymer resin. The mixture is preferably mixed independently (i.e. using a "HOBART" mixer)
After being mixed (separately), they were compounded together, preferably using a "HOCKMEYER" high speed dispersion device, to produce the adhesive compositions shown below. The adhesive strength (i.e., compressive shear) of the bond between resin materials formed by the adhesive composition is:
Measured using a variation of the test outlined in ASTM D905-49. For example, to test compressive shear strength, adhesive bond test specimens are
25mm x according to the test method of ASTMD905-49
25mm× bonded to the second resin specimen of 50mm×6.3mm
It consisted of a first resin specimen measuring 50 mm x 6.3 mm. The area of each coupon to be bonded was coated with a well-known surfactant, for example the condensate of butyraldehyde and aniline mentioned above. This surfactant is currently commercially available under the trademark "VANAX 808" and contains approximately 0.1% by weight copper naphthenate.
Next, adhesive was applied to the part of one section to be joined, and the other section was pressed together onto it. A 0.25 mm metal shim washer was used to measure (or measure) the bond thickness. room temperature i.e.
After conditioning for 2 days at 25°C,
The coupons were tested in compressive shear using a crosshead speed of 1.27 mm/min (approximately
(as specified in ASTM D905-49). The adhesive shear strength of the adhesive bond formed between specimens of cold-rolled steel is 25 mm × 76 mm × 1.6 for a similar pair.
Tested according to the test method of ASTMD-1002-64 using mm specimens. The coupons were first cleaned and grit blasted with methyl ethyl ketone (MEK) and then recleaned with MEK prior to testing. The surface of the specimen had an area of approximately 12.5 mm x 25 mm and a surface area of approximately 0.2 mm after being coated with a surfactant (mentioned immediately above), which is a condensate of butyraldehyde and aniline.
The adhesive composition was applied substantially as described above, except that a mold was used to provide the specimen with an even joint having a thickness of . The bond was conditioned for two days at room temperature and then
A separation speed of 1.27 mm/min was tested. The peel strength of the adhesive composition is 25mm x 254mm x 0.5
Using a pair of similar cold-rolled steel specimens of mm
Tested according to ASTM D-1876-61T test method. The coupons were first cleaned with MEK, polished with sandpaper, and then recleaned with MEK. The length of one specimen is approximately 228.6mm (9″).
The ASTM D-1876-61T test method was used immediately, except that a 0.18 mm wire spacer was used to measure (or measure) the bond thickness when the specimens were pressed together by a weight. Approximately 228.6mm (9″) of the other specimen using the activation and painting techniques described above.
joined to length. After conditioning for two days at room temperature, the samples were tested in a 180° peel at a speed of 254 mm/min. The impact strength of the adhesive composition shown below is:
12.7 mm (in diameter) steel bars with lengths of 76.2 mm and 9.5 mm, respectively, meet ASTM D-950-
ASTM Test Methods
Tested by D950-54. The surfaces to be bonded together were first cleaned with solvent, activated after grit blasting, then bonded together and conditioned for two days at room temperature prior to testing. For the adhesive compositions shown below, curing for about 6 hours to about 8 hours results in a final bond strength of about 80%.
% or more was achieved. Suitable Adhesive Compositions The following examples demonstrate the performance of adhesive compositions containing varying proportions of chlorosulfonated polyethylene polymer resin to MABS graft copolymer resin. The adhesive properties of the composition are determined by the procedure outlined above to determine compressive shear strength, lap shear strength,
It was measured by performing peel strength and impact strength tests. The viscosity of adhesive No. 1 and No. 2 is
Measured using a No. 3 spindle at 10 rpm.
The viscosity of adhesive No. 3, No. 4 and No. 5 is at 10 rpm.
Measurements were made using No. 4 TB and TF spindles, respectively.

[Table] Example A shows varying proportions of chlorosulfonated polyethylene polymer resin MABS graft copolymer resin at a substantially constant chlorosulfonated polyethylene polymer and the sum of the graft copolymer solids level. The performance of the adhesive combination comprising the following is further illustrated, and then the adhesion properties of the composition are illustrated again (for examples), as is isolating the effect that variations in the fixation level may have on other aspects. The adhesion properties of the compositions were also determined by testing compressive shear strength, lap shear strength, peel strength, and impact strength according to the procedures outlined above. The viscosity of Adhesive No. 6 was measured using a No. 2 spindle at 20 rpm. The viscosity of Adhesive Nos. 7 and 8 was measured using a TA spindle at 20 rpm. The viscosity of Adhesive Nos. 9-12 was measured using a TC spindle at 10 rpm.

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TABLE The examples given below demonstrate the performance of adhesive compositions compared to methyl methacrylate monomer when other methacrylate group monomers are used in place of the methyl methacrylate monomer. . For various proportions of MABS graft copolymer resin in the methacrylate group monomers shown, chlorosulfonated polyethylene polymer resin, methacrylic acid in approximately the same proportion as that of Example Adhesive No. 3. , cumene hydroperoxide and para-toluene sulfonyl chloride were added. Also, as provided in the example, approximately 40% by weight of a chlorosulfonated polyethylene polymer resin (Hypalon 30) was included in a separate mixture for each specific methacrylate group monomer tested.

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TABLE The examples given below demonstrate the performance of adhesive compositions having various ratios of chlorosulfonated polyethylene polymer resin to ASA graft copolymer resin.

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TABLE Examples A and B given below demonstrate the performance of adhesive compositions having various ratios of chlorosulfonated polyethylene polymer resin to all-acrylic graft copolymer resin.

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TABLE Examples C-G given below demonstrate the performance of adhesive compositions having varying ratios of chlorosulfonated polyethylene polymer resin to MBS graft copolymer resin. Among these MBS graft copolymer resins, KM641 (Example E)
It has a relatively smaller particle size than KM611 (Example D) which has a relatively smaller particle size than KM653 (Example F).

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TABLE The following Examples A-E demonstrate the performance of adhesive compositions containing either a chlorosulfonated polyethylene polymer resin or a graft copolymer resin, but not both. The adhesive composition of Example A includes a chlorosulfonated polyethylene polymer resin. Examples B-D include MBS graft copolymer resins. The adhesive composition of Example E includes an all-acrylic graft copolymer resin.

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In the adhesive composition of the present invention, the polymerization of ester and acid monomers of acrylate groups (preferably methacrylate groups) constitutes and cures the composition. The catalyst initiates the polymerization stage. The activator (or initiator), when included, initiates the catalytic stage. A first preferred method of using the adhesive of the present invention will be described. That is, an adhesive composition that does not contain an activator (or reaction initiator) is applied to at least a first side of at least two surfaces to be joined together. The activator is applied to the other side. The two surfaces are then brought into close proximity such that the activator contacts the adhesive composition, whereby the activator initiates catalysis of the catalyst. This action by the catalyst initiates polymerization of the monomers, thereby forming and curing the composition. In this method, a relatively small amount of activator (relative to the amount of the total adhesive composition) serves to initiate the catalytic action. Next, another method will be described. That is, by combining or mixing the two parts of a so-called two-part adhesive, the two-part adhesive comprises first and second parts of the adhesive composition. The first portion includes some of the adhesive composition components and a catalyst. The second portion includes the remainder of the ingredients of the adhesive composition and an activator. The volume mixing ratio of the two parts may generally range from about 5:95 to about 95:5, with 1:1 often being preferred. however,
Regardless of the selected volumetric mixing ratio, the relative proportions of catalyst and activator (or reaction initiator) components are
It must be selected so that effective polymerization is obtained. The next example given is a soul combination of portions A, B of approximately 1:1 equal volume. Part A, B
When the adhesive compositions are mixed together, the adhesive composition has a working time lasting up to about 2 minutes (i.e., when the composition is substantially workable or fluid) after contact with the catalyst-containing portion and the initiator-containing portion. It is generally accepted that there is a certain amount of time). In particular, the adhesive composition begins to thicken or gel in about 2.5 minutes (after being mixed), exhibits a distinct exotherm upon mixing and curing, and exhibits a distinct exotherm in about 5 minutes (after initial mixing). It was hardened.
Approximately 5 grams of Part A was mixed with approximately 5 grams of Part B. Higher amounts would be expected to cure in a shorter time and exhibit a relatively more significant exotherm. About 80% or more of the final bond strength is achieved in about 6 hours to about 8 hours.

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TABLE Table 3 given below provides additional information regarding the physical properties of one of the most preferred graft copolymer resins.

TABLE The following examples illustrate adhesive compositions made by varying the relative amounts of methacrylic acid in the adhesive composition mixture. The relative amounts of the remaining components were held approximately constant in order to determine the effect or change of methacrylic acid. The examples given below also include three different types (or types) of chlorosulfonated polyethylene (given above in connection with Table 1A) combined with MABS graft copolymer resins. Adhesive composition is shown.

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Table: Described herein are novel methacrylate-based compositions. Although the novel methacrylate-based compositions of the present invention have been described in connection with use as adhesives, the invention is not so limited. On the contrary, alternatives, modifications or variations will be apparent to those skilled in the art after reading the foregoing description. Accordingly, all such alternatives, modifications and variations are to be considered as forming part of the invention insofar as they fall within the scope and spirit of the claims. For example, in addition to having utility in the area of adhesives, the present invention is believed to have utility generally in the area of repair products, plastic materials, and coatings.
For example, in the repair products field, a piece of fiberglass cloth may be wetted on both sides to form a fiberglass patch according to the present invention. It is further contemplated that the present invention may include effective amounts of metal particles to produce repair products with a variety of commercially desirable characteristics. Furthermore, in the field of plastic materials, the present invention can be used as a carrier for certain components in much the same manner as epoxies are currently used. For example, in the field of coatings, the present invention may be used to permanently coat metal substrates for a variety of reasons.

Claims (1)

[Claims] 1. An ester monomer having an acrylate group or a methacrylate group, and an amount of chlorination or chlorination that provides the adhesive composition with the required compressive shear strength, lap shear strength, peel strength, and impact strength. An adhesive composition comprising a chlorosulfonated polyethylene polymer resin and a graft copolymer resin, and a catalyst which is a free radical generator selected from organic peroxides, organic hydroperoxides, peracids, peresters. 2 an ester monomer having an acrylate group or a methacrylate group, and an amount of chlorinated or chlorosulfonated polyethylene polymer that gives the adhesive composition the required compressive shear strength, lap shear strength, peel strength, and impact strength. a polymeric resin and a graft copolymer resin; a catalyst which is a free radical generator selected from organic peroxides, organic hydroperoxides, peracids, peresters; aldehyde-amine condensates, propane sulfonyl chloride and paratoluene chloride. An adhesive composition comprising a catalyst activator selected from among sulfonyls. 3 An ester monomer having an acrylate group or a methacrylate group, an acid monomer having an acrylate group or a methacrylate group, and the adhesive composition having the required compressive shear strength, lap shear strength, peel strength, and impact strength. an adhesive comprising an amount of a chlorinated or chlorosulfonated polyethylene polymer resin and a graft copolymer resin and a catalyst which is a free radical generator selected from organic peroxides, organic hydroperoxides, peracids, peresters; agent composition. 4 An ester monomer having an acrylate group or a methacrylate group, an acid monomer having an acrylate group or a methacrylate group, and the adhesive composition having the required compressive shear strength, lap shear strength, peel strength, and impact strength. a chlorinated or chlorosulfonated polyethylene polymer resin and a graft copolymer resin in a given amount; a catalyst which is a free radical generator selected from organic peroxides, organic hydroperoxides, peracids, peresters; and an aldehyde. - An adhesive composition comprising a catalyst activator selected from amine condensates, propane sulfonyl chloride and para-toluene sulfonyl chloride. 5. The chlorosulfonated polyethylene polymer resin contains about 43% by weight chlorine, about 1.1% by weight sulfur,
about 34 mmol of sulfonyl chloride moieties per 100 grams thereof.
The adhesive composition according to any one of the above items. 6 The graft copolymer resin is ABS, MBS,
MABS, ASA, all acrylic copolymer resin,
Adhesive composition according to any one of claims 1 to 4, which is selected from the group consisting of SAEPDM and MAS.