JPS5928597B2 - Adhesion method - Google Patents

Description

Detailed Description of the Invention Japanese Patent Publication No. 53-41699 discloses an adhesive composition containing chlorosulfonated polyethylene dissolved in a vinyl monomer, and an adhesive composition containing chlorinated polyethylene and sulfonyl chloride dissolved in the vinyl monomer. An adhesive composition containing the following is disclosed.

These adhesive compositions provide high strength bonds relatively quickly. The present invention provides a polymer solution in monomer, 2
The present invention relates to an adhesive composition comprising an organic sulfonyl chloride and/or chlorosulfonated polymer having up to 0 carbon atoms, a polymerization catalyst and a promoter.

The polymer (as distinguished from the chlorosulfonated polymer) of the polymer-in-monomer solution is present in an amount of 10 to 75 percent by weight of the solution. This adhesive has a rating of about 2,000 to about 10
It has a viscosity of 00,000 centipoise. The monomers used in this adhesive are acrylic or methacrylic. The organic sulfonyl chloride is present in an amount such that about 3 to 160 mmoles of sulfonyl chloride groups are present per 100 mmol of polymer. The polymerization catalyst is present in an amount up to about 15% by weight of the solution, i.e., polymer, monomer, and organic sulfonyl chloride, and usually in an amount of about 0.2 to 5% by weight of the solution. . Suitable polymerization catalysts are free radical generators such as organic peroxides, organic hydroperoxides and organic peresters. The accelerator should be present in an amount of about 0.01 to 10%, usually about 0.1 to 5%, by weight of the solution. As used herein, the term "polymer(s)" refers to polymer(s) dissolved or to be dissolved in acrylic or methacrylic monomers, including chlorosulfonated polymers ( ) are not included.

Polymers suitable for use in preparing the polymer-in-monomer solutions of this invention should have a molecular weight of about 10,000 to 1,000,000 or more. The polymer must be at least partially soluble in the acrylic monomer. Suitable polymers include, for example:
Fluoroelastomers such as vinylidene fluoride/hexafluoropropene polymers, vinylidene fluoride/hexafluoropropene/tetrafluoroethylene polymers; chlorinated polyethylenes, such as polychloroprene, chloroprene polymers such as methylene methacrylate/chloroprene polymers polyester polymers such as for example bisphenol A/fumaric acid polyesters, polyesters based on terephthalate domaleic acid; vinyl chloride polymers such as vinyl chloride/vinyl acetate copolymers; for example polyethyl acrylate, styrene/ Acrylic acid ester polymers such as ethyl acrylate polymer, ethyl acrylate/methyl methacrylate polymer, ethylene/methyl acrylate polymer, n-butyl methacrylate/isobutyl methacrylate polymer; e.g. polyisoprene, polystyrene, Pale crepe natural rubber, styrene/
hydrocarbon polymers such as butadiene rubber; polyalkylene ethers such as polyepichlorohydrin;
Vinyl acetate polymers such as ethylene/vinyl acetate polymers; e.g. polytetramethylene ether glycol/2,4-toluene diisocyanate polyurethane, polytetramethylene ether glycol/trimethylolpropane diallyl ether/2,4- and 2
6- Polyurethane polymers such as toluene diisocyanate polyurethane; and for example butadiene/
Acrylonitrile polymers such as acrylonitrile. Mixtures of these polymers can also be used.

A preferred polymer is one that is rubbery at the temperature of use. This is because the adhesives produced by the use of such polymers are relatively non-brittle. Acrylic or methacrylic monomers that act as solvents for the polymer and are to be polymerized when the composition is used as an adhesive include: methyl methacrylate;
Ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, cyclohexyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-acrylate Acrylic and diacrylic and methacrylic esters and dimethacrylic esters of ethylhexyl, lauryl acrylate, methacrylic acid, acrylic acid, ethylene glycol and higher glycols.

Suitable monomers are lower alkyl esters of acrylic acid and methacrylic acid and dimethacrylic esters of ethylene glycol and butylene glycol. The sulfonyl chloride contained in the monomer-polymer solution is
It can be any one or a mixture of organic sulfonyl chlorides selected from the class consisting of sulfonyl chlorides having up to 20 carbon atoms and chlorosulfonated polymers soluble in acrylic monomers. .

However, when chlorinated polyethylene is used as the polymer, a chlorosulfonated polymer is used as the organic sulfonyl chloride. A preferred chlorosulfonated polymer is chlorosulfonated polyethylene. Satisfactory sulfonyl chlorides having up to 20 carbon atoms have the formula R(SO2
Cl)x, where x in the formula is 1 to 5 and R is C1 to C2O alkyl or C6 to C2O
is an aryl; R may contain an oxygen or nitrogen atom.

Particular sulfonyl chloride compounds that are useful include the following: Chlorosulfonated polyethylenes suitable for the present invention can be prepared by the reaction of linear or branched polyethylene with sulfuryl chloride, or sulfur dioxide and chlorine. can.

A suitable polyethylene is ASTM-D-1238-52
It has a melt index of 0.1 to 5007/10 minutes as measured by T. Chlorosulfonated polyethylene is commercially available. The chlorosulfonated polyethylene can also be a chlorosulfonated copolymer of ethylene and a low proportion of propylene or other olefins. Various chlorosulfonated polyethylenes and methods for producing them are disclosed in U.S. Pat. No. 29,827.
It is described in No. 59. A suitable chlorosulfonated polyethylene should contain about 25 to 70 weight percent chlorine and about 0.1 to 8 weight percent sulfur. Any chlorosulfonated polymer that is generally soluble in acrylic or methacrylic monomers can be used as the sulfonyl chloride source.

Copolymers of alpha-olefins with monomers such as styrene, butadiene, vinyl acetate, acrylic acid, methacrylic acid, methyl methacrylate and acrylonitrile are illustrative. Such soluble chlorosulfonated polymers generally contain about 0.1 to 8 weight percent sulfur and about 25 to 70 weight percent chlorine.
The molecular weight of these chlorosulfonated polymers is not critical. Chlorosulfonated polymers with a molecular weight similar to that of the hydrocarbon wax are advantageous, and chlorosulfonated polymers with a significantly higher molecular weight are also satisfactory. An example of a polymer of the above type is an ethylene/methacrylic acid copolymer containing 10 weight percent methacrylic acid. Before chlorosulfonation, the copolymer was
It had a melt index of 57/10 minutes. This polymer was chlorosulfonated to an extent containing 1.05% sulfur and 40.5% chlorine by weight. 5007/1
Another ethylene/methacrylic acid copolymer having a melt index of 0 minutes was mixed with 1.1% sulfur and 41% by weight.
It was chlorosulfonated to the extent that it contained chlorine.

The Bruckfield viscosity of polymer-in-monomer solutions and solutions containing organic sulfonyl chlorides is ASTMV49O.
According to O5OO, it should be within the range of 2,000 to 1,000,000 centiboads, measured with a No. 4 spindle at 12 and 6 revolutions/min. The amount of polymer dissolved in the acrylic or methacrylic monomer is 1% of the solution.
It is within the range of 0 to 75% by weight, and preferably the amount of polymer used is about 15 to 50% by weight of the solution. The amount of organic sulfonyl chloride used in the monomer solution is such that the concentration of sulfonyl chloride groups, i.e., SO2Cl, is in the range of 3 to 160 mmol per 1007 of the polymer; 20 to 100 mmol/1007 is preferred.

Although the function of sulfonyl chloride is not completely understood,
It is believed that the sulfonyl chloride reacts with the polymerization catalyst at the point where the adhesive bond is to be formed, promoting and strengthening the final bond. Adhesive compositions require the presence of free radical type catalysts. Suitable catalysts include organic peroxides, organic hydroperoxides and organic peresters. Specific catalysts that can be used include benzoyl peroxide, cumene hydroperoxide, acetyl peroxide, tert-butyl hydroperoxide, lauroyl peroxide,
Methyl ethyl ketone peroxide. The amount of catalyst needed to rapidly polymerize the adhesive will vary depending on the material selected, but is typically about 1/2 of the adhesive mixture.
It is present in amounts up to 5% by weight. It is usually preferred to have the catalyst present in an amount of about 0.2 to 5% by weight of the mixture; however, in some cases the amount of polymerization catalyst can be lower than 0.2% by weight. In fact, if there are little or no inhibitors, antioxidants or other inhibiting additives in the mixture,
The peroxide that naturally forms upon exposure of the acrylic monomer to air is sufficient to cause polymerization of the mixture in the presence of a promoter to form a satisfactory adhesive bond.
Example 22, which will be described later, shows such an aspect. The adhesive composition must also contain an effective amount of a promoter. The exact amount required to effectively polymerize the adhesive mixture will depend on the concentrations of the other ingredients, but generally the amount will be within the range of about 0.1 to 5% by weight of the adhesive composition. be. Accelerators that have been found to be effective in the adhesive compositions of the present invention include aldehyde-amine condensates, such as condensates of butyraldehyde and primary amines such as aniline or 6-butylamine. . Accelerators of this type are commercially available from many companies. Other materials can also be added to the adhesive composition to control the rate of reaction. For example, it is known that inhibitors such as hydroquinone can reduce the rate of polymerization if desired. Organic salts of transition metals such as cobalt, nickel, manganese or iron naphthenate, copper octoate, iron hexanoate and iron propionate can also be added to further increase the reaction rate. The adhesive composition can be formulated by mixing a polymer-in-monomer solution containing sulfonyl chloride with a polymerization catalyst and promoter, and then applying the mixture to the substrate to be bonded; Alternatively, the accelerator can be applied to the substrate followed by a polymer-in-monomer solution containing the sulfonyl chloride and peroxide.

Because polymerization usually proceeds rapidly when all components are mixed, it is often necessary to apply the accelerator to one substrate and the remaining components to the other substrate, so that both substrates to be joined are coated in the gap between them. when the material is brought close enough to be filled with
It is desirable to produce an adhesive composition. Adhesive compositions made from polymer-in-monomer solutions cure at room temperature in the presence or absence of air.

The adhesive composition can be used to bond porous or smooth surfaces. The composition bonds oily metals as well as corroded aluminum, copper, brass, polymeric materials with polar groups such as polyester, polyamide, polyvinyl chloride, glass, wood, paper and printed surfaces. It can be used to In the following examples illustrating the invention, all parts and percentages are by weight unless otherwise indicated.

Examples Example 1 Methyl methacrylate (69% by weight) of 6907 (50-
90 ppm hydroquinone inhibitor), 100
t of glacial methacrylic acid (10% by weight) (250 ppm of 4
- methoxyphenol), and 107 ethylene glycol dimethacrylic acid ester (1% by weight)
A polymer solution was prepared by adding 200y of commercially available polyethyl acrylate elastomer (20% by weight) to a mixture of acrylic monomers consisting of:

The mixture was rotated in a shear at room temperature until the polymer was completely dissolved (48-64 hours). This solution had a Bruckfield viscosity of 31,250 centiboads as measured using a #4 spindle at 12 revolutions per minute. The polymer used contained more than 95% by weight of polymerized units of ethyl acrylate and small amounts of polymerized units of other vinyl monomers.

Other vinyl monomers contained some chlorine atoms. This polymer had a pre-mask cement viscosity of 25,000 centiboads when dissolved in methyl ethyl ketone at a concentration of 20% by weight. The polymer viscosity ML-4 (under 212) is 45-65.
In a portion of this solution, 0.5 parts per 100 parts (based on the total solution) of cumene hydroperoxide and 10 parts of polymer
82 mmol of methanesulfonyl chloride was added per 0.7 mmol.

A grid-blasted and perchlorethylene-degreased steel piece measuring 1" x 3" x 0.062I was coated with a commercially available accelerator (DuPont Accelerator 833), which is a mixture of a condensate of butyraldehyde and n-butylamine. Lap shear specimens were prepared by applying a 300 ml of lap shear specimens (commercially available as ゜゛).

The accelerator was applied with a cotton swab and then wiped off with a piece of tissue paper to form a thin film. By applying a small amount of the adhesive composition and compressing it between the pieces of steel in a mold,
．． 007~0.010" x 0.57X11 adhesive lines were obtained. The specimens were tested 15 minutes (1〃 overlap) and 24 hours (0.5" overlap) after assembly, respectively. 0.5 inch/min (ASTMD-1876-61T
) and a separation rate of 0.05 inches/minute by shear in an Instron apparatus. The lap shear strength was recorded as the average of 4 specimens and the following results were obtained.
2-8 A polymer solution was prepared as in Example 1 by dissolving the amount of polymer shown in the table below in a mixture of acrylic monomers.

In addition to the polymer, the solution contained 10% by weight glacial methacrylic acid, 1% by weight ethylene glycol dimethacrylate, and the balance was methyl methacrylate. To a portion of each polymer solution, add 0.5 parts/100 parts (of total solution) of cumene hydroperoxide and 10 parts of polymer.
0.07 mmol of methanesulfonyl chloride was added. The test piece is 0.52 for a metal piece with a width of 1〃.
Prepared as described in Example 1 using a superposition of .

The strength was recorded as an average of 4 specimens after 24 hours and is shown in the table below.

Examples 9-15 As shown in the table below, polymer solutions were prepared by the method of Example 1, except that ethylene glycol dimethacrylate was not necessarily included and the acrylic monomer concentration was varied.

The adhesive composition is shown in the table below (expressed in % by weight). Adhesive solution is applied to a portion of each polymer solution at a concentration of 1.0 or 0.
Prepared by adding 5 parts/100 parts (based on total solution) of cumene hydroperoxide and the indicated number of mmoles of methanesulfonyl chloride or diphenyl ether-4,4'-disulfonyl chloride/1007 polymer did.

Lap shear specimens were prepared by applying a thin film of butyraldehyde-amine condensate onto a steel specimen. Apply the adhesive solution between the pieces and then separate the pieces into two 3/42 pieces to give a 1” overlap.
I used paper clips to hold it together. 0.001～
A bond thickness of 0.0037 resulted.

Lap shear strength was recorded using an Instron between 2 and 30 minutes after assembly. The 2 minute and 3 minute connections were superimposed and clipped outside the instron.

Bindings of 10, 15 and 30 minutes were clipped outside the instron.

Examples 9-11 used a commercially available condensate of butyraldehyde and aniline (commercially available as Dupont Accelerator 808) as a primer, while
Examples 12-15 used the same accelerator as Example 1. The rapid development of adhesion is illustrated by the lap shear strength shown in the table below. Examples 16-202 0.5 parts/100 parts of cumene hydroperoxide and 80.4 mmol/10 to the polymer solution of Example 1
Adhesive solutions were prepared by adding various monomeric sulfonyl chlorides of the 07 polymer.

Lap shear specimens were prepared as described in Example 1 using a 0.57 overlap for width pi metal strips, except that Dupont Accelerator 808 was used for all samples. . Lap shear strength was recorded as the average of four specimens 24 or 48 hours after assembly. These examples illustrate some of the various sulfonyl chlorides that can be used in the present invention.

Example 21 By the method of Example 1, 2 in toluene was prepared.
19 centiboads at a concentration of 5% by weight at 3°C, 10
75 centiboaz at % concentration, 300 centiboaz at 15% concentration, 1050 centiboaz at 20% concentration, 2
30% by weight of a commercially available styrene-butadiene block copolymer having a viscosity of 4485 centiboars at a concentration of 5%:
A polymer solution containing 62.5% by weight of methyl methacrylate; and 7.5% by weight of methacrylic acid was prepared.

This solution was applied at 6 revolutions/min using a No. 4 spindle.
It has a Bruckfield viscosity of 3500 centiboads. Adhesive solutions were prepared by adding 1.0 parts/100 parts of cumene hydroperoxide and different amounts of p-trienesulfonyl chloride to each portion of the polymer solution.

Lap shear specimens were prepared according to the method of Example 1.

After the metal pieces were primed with Accelerator 808, they were assembled with an overlap of vinyl. After 15 minutes, the lap shear strength was measured.

This example illustrates the existence of an optimal sulfonyl chloride concentration for the development of adhesive properties for each polymeric adhesive.

Examples 22-24 35% by weight n-butyl methacrylate (50%)/isobutyl methacrylate (50%) was prepared by the method of Examples 2-8.
0%) copolymer solution was prepared.

This polymer had an intrinsic viscosity of 0.61 when measured in chloroform at 25°C. The polymer solution had a Bruckfield viscosity of 1180 at 12 revolutions/minute using a No. 3 spindle. The table below lists the above polymer solutions alone or with various concentrations of cumene hydroperoxide (total solution 100%
(parts per part) and/or methanesulfonyl chloride (mmol/100y polymer).

The table below also shows the results obtained when the polymer solution of Example 1 and the polymer solution of Example 5 were tested. In the case of a 35 weight percent n-butynol methacrylate/isobutyl methacrylate copolymer adhesive, Example 12
Lap shear specimens were prepared according to the method for Example 1, except that the metal strips were clipped outside of the Instron to provide a 0.001-0.003 inch bond line as in ~15 and Tested.

The table below shows the lap shear strength when tested 5 to 30 minutes and 24 hours after assembly.

The table below shows the increase in both peak lap shear strength and rate of bond development by the addition of methanesulfonyl chloride to cumene hydroperoxide containing adhesives. Example 25 19.5% by weight of very rapidly crystallizing adhesive grade polychloroprene (75-90 mu m viscosity at 212'F), 2.8% by weight of the bisphenol shown in Example 4 0.5 for a polymer solution consisting of A epoxy resin, 67.3% by weight n-butyl methacrylate, 9.5% by weight methacrylic acid, and 0.9% by weight ethylene glycol dimethacrylate. An adhesive was prepared by adding parts/100 parts of cumene hydroperoxide and 61.5 mmol/1007 polymer of methanesulfonyl chloride.

The polymer solution had a Bruckfield viscosity of 23,800 as measured using a #4 spindle at 12 revolutions/minute. Lap shear specimens were prepared according to the method of Example 1.

Example 26 By the method of Example 1, 5% by weight chlorosulfonated polyethylene, 20% by weight polychloroprene (commercially available as Neoprene w by Dupont), 64% by weight
A solution of 10% by weight of methacrylic acid and 1% by weight of ethylene glycol dimethacrylate was prepared in methacrylic acid methino.

Chlorosulfonated polyethylene prepared from branched polyethylene with a melt index of 100 contains 43% by weight chlorine and 1.1% by weight sulfur and has a melt index of 30% by weight.
It had a certain viscosity. This solution contained 8.5 mmol sulfonyl chloride groups per 1007 polychloroprene. This solution had a Bruckfield viscosity of 14,000 centiboads (No. 4 spindle, 12 revolutions per minute). Example 1 except that the butyraldehyde-aniline condensate shown in Examples 9-11 was used as the promoter, but the adhesive was prepared by adding 0.5 parts/100 parts of cumene hydroperoxide to the solution. Lap shear test specimens were prepared according to the method of .

Example 27 (1) 25% by weight polychloroprene (commercially available as Neoprene w), (2) 21% by weight methyl methacrylate,
(3) 10% by weight of meth. lylic acid, (4) 3% by weight of a commercially available bisphenol A epoxy resin, and (5) 1
% by weight of polychloroprene in solution for a solution containing ethylene glycol dimethacrylate ester.
56 mmol of methanesulfonyl chloride per 100 parts of solution and 0.5 parts of cumene hydroperoxide per 100 parts of solution were added.

Using the above mixture, prepare 2 different sets (2 sets for 1 set).
cold-rolled steel billets (individual steel billets) were joined together.

A set of steel pieces has both surfaces to be joined approximately 0.0001 mm thick.
to have a coating of ~0.0002 inches;
Coated with Dupont Accelerator 808.

The other set of billets was not coated. The solution was then applied to both sets of steel pieces, and the surface of each set was coated so that the bond line was approximately 0.0
They were stacked to a thickness of 0.02 to 0.004 inches.

The solution filled the gap between both surfaces. The set of billets that were not treated with an accelerator had a set time of greater than 30 minutes (i.e.
time from assembly to when the specimen can be handled without separating) and 1700 ps in 20 hours
The accelerator-treated billet set had a maximum strength of 2330 psi at a set time of 11.5-12 minutes and 20 hours. Example 28 A monomer mixture consisting of butyl methacrylate, butylene dimethacrylate and methacrylic acid was
r''B-79 (polyvinyl butyral manufactured by Monsanto; butyral content - expressed as polyvinyl butyral: 8
8% by weight, acetate content - 0 to 25% by weight expressed as polyvinyl acetate, hydroxyl content = 9 to 13% by weight expressed as polyvinyl alcohol, weight average molecular weight = 34000 to 38000) until the polymer was completely dissolved. The adhesive solution was prepared by stirring at low speed until the adhesive solution was mixed.

Butanesulfonyl chloride and cumene hydroperoxide were added to the polymer/monomer solution. 1 glue
Apply Accelerator 808-5 or Accelerator 833 to a 1-inch square in the center of a 1-inch by 3-inch glass surface, apply Accelerator 808-5 or Accelerator 833 to a 1-inch square in the center of another 1-inch by 3-inch glass surface, and apply two Overlap the faces to form a cross,
The time required for the adhesive to cure until it no longer works under manual pressure was measured.

Test results for adhesive samples of three different compositions are shown in the table below.

Examples 29-31 Commercially available methacrylic acid alkyl esters of 120-1307 (as shown in the table below), methacrylic acid of 187 and 2y
A 50-607 styrene/butyl acrylate copolymer (commercially available as PliOlite AC by Gudoiya Co., Ltd.) was dissolved in a mixture consisting of ethylene glycol dimethacrylate ester.

39.9 mmol (7.6y) of p
-Toluenesulfonyl chloride and 0.5 parts of cumene hydroperoxide per 100 parts of solution were added. 1
1″ x 3″ x 0.0622 (2.4CTfL x 7.2c
A grid-blasted and acetone-degreased steel billet of size Tn x 0.15 cm) was treated with a commercially available accelerator (A
Lap shear specimens were prepared by applying 30% Nax8O8').

The accelerator was applied with a brush and then wiped with tissue paper to form a thin film. By applying a small amount of the adhesive composition and compressing it between the pieces in a mold, the 0.
008~0.010″XO.5″×17(0.024?
Xl. 2? ×2.4? ) was obtained.

The specimens were tested by shear in an Instron machine at a separation rate of 0.05 inches/minute after 48 hours of assembly. The lap shear strength was as shown in the table below as an average of four test pieces. Examples 32-33 30% styrene/butyl acrylate copolymer (Pl
Polymer 10
10 and 40 mmol of sulfonyl chloride per 0.07 were added, respectively.

The sulfonyl chloride was added in the form of chlorosulfonated polyethylene with a chlorine content of 40% and a sulfur content of 1.1% prepared from branched polyethylene with a melt index of 100. Chlorosulfonated polyethylene was added to the copolymer solution at 0.5 parts as a solution containing 35% polymer, 5% ethylene glycol dimethacrylate, 10% methacrylic acid, and 50% isodecyl methacrylate. An adhesive was prepared by adding 1/100 parts of cumene hydroperoxide to this solution.

A test piece was prepared in the same manner as in each of the above examples,
The lap shear strength was tested. As the average of 4 specimens,
The test results are shown in the table below.

Claims (1)

[Claims] 1. An amine-aldehyde polymerization accelerator (e) is applied to at least one of the two surfaces, and then at least one polymerizable monomer (b) selected from the group consisting of acrylic and methacrylic monomers is applied to at least one of the two surfaces. ) at least one polymer (a) dissolved in at least one organic sulfonyl chloride (c) selected from the group consisting of organic sulfonyl chlorides and chlorosulfonated polymers having up to 20 carbon atoms;
, and a free radical polymerization catalyst (d) - provided that when polymer (a) is chlorinated polyethylene, organosulfonyl chloride (c) is a chlorosulfonated polymer - the composition is applied to at least one surface. for bonding two surfaces, characterized in that the surfaces are brought into close enough proximity with a composition containing an accelerator and a dissolved polymer to fill the gap between the surfaces. Method.