DE2106155C3 - Process for the production of bonds - Google Patents

Description

ΐ '

CH, -C

O = C-Ο —CH, -CH —CH,

"I.

OH

joins together and allows the adhesive to harden, characterized in that one component (main component) consists of
(A) 40 to 80 parts by weight of at least one divinyl compound of the general formula (I)

R,

// Vc

) —CH, - CH-CH,

OH

C = CH,

-o — c ο
¹ ID

in which Ri and R2 are a hydrogen atom or the methyl or ethyl group and η is an integer from 1 to 20,

(b) 0.05 to 10 parts by weight of at least one organic peroxide,

(c) 0.5 to 15 parts by weight of an acrylonitrile-butadiene-styrene terpolymer or acrylonitrile-butadiene copolymer and

(d) 2 to 120 parts by weight of at least one vinyl monomer, but not more than 40 parts by weight of any vinyl monomer,

and the second component (accelerator component)

(e) 0.01 to 10 parts by weight of at least one thiourea derivative,

(f) 0.01 to 10 parts by weight nt, <x'-bipyridyl,

(g) 0.001 to 5 parts by weight of at least one metal salt of an organic or inorganic one Acid,

and wherein the component concept and optionally the main component as a whole
(h) 100 to 75 parts by weight of at least one volatile organic solvent and the main component and / or the accelerator component, if appropriate

(i) Contains dyes, plasticizers and / or blowing agents and other common additives and processing aids.

2. The method according to claim 1, characterized in that the quantitative ratios

50 to 60 parts by weight of component (a),
0.5 to 5 parts by weight of component (b),
1 to 10 parts by weight of component (c),
10 to 120 parts by weight of component (d),
0.1 to 7 parts by weight of component (e),
0.05 to 5 parts by weight of component (f),
0.001 to 3 parts by weight of component (g) and
100 to 75 parts by weight of the component (h)
be

3. The method according to claim 1 and 2, characterized in that the accelerator component, consisting of the components (e), (f), (g) and (h) on one of the two surfaces to be glued applies and this surface dries before bonding.

Various two-component adhesives are already known which cure at room temperature can be. Before use, the two components must be carefully weighed out with each other be mixed. If the quantitative ratio is not strictly adhered to or if the two Components are inadequately mixed with one another, the adhesive strength wedge can be adversely affected will. In addition, two-part adhesives have only a limited amount after mixing Pot life. After this time, processing is due to the greatly increased viscosity, which ultimately leads to Gelling of the adhesive is no longer possible. Furthermore, the economics of most so far known adhesives impaired in that the curing takes considerable time. To this To mitigate the disadvantage, work is sometimes carried out with the application of heat, but for this purpose special devices are necessary.

It is known that acrylic or methacrylic acid esters of various alcohols together with organic Peroxides represent anaerobically hardening mixtures that are used as adhesives or sealants can be. According to an unpublished proposal, the tensile shear strength can be as high as that obtained with these Mixtures obtained compounds by mixing reaction products free of epoxy groups from glycidyl ethers of polyhydric phenols and acrylic b / .w. Methacrylic acid can be improved.

The invention is based on the object of Zwcikomponenten-Klcangebotec in which the components are characterized by excellent durability and which harden extremely quickly with the exclusion of oxygen and at room temperature and bond with them result in very high strength values. This object is achieved by the invention.

The invention thus relates to that in the claims featured item.

In the process according to the invention, preference is given to using a two-component adhesive, the proportions of which
up to 60 gcwichlslcile of component (a),

0.5 to 5 parts by weight of component (b), 1 to 10 parts by weight of component (c), 10 to 120 parts by weight of component (d), 0.1 to 7 parts by weight of component (e), 0.05 to 5 parts by weight of component (f) 0.001 to 3 parts by weight of component (g) and 100 to 75 parts by weight of component (h), and optionally a dye, Contains plasticizer and / or a propellant.

The method of the invention can be carried out so that components (a) through (h) are prior to use are mixed together and this mixture is applied to the two surfaces to be bonded. However, the method is preferably carried out so that the main component, consisting of the Components (a) to (d), consisting of a surface to be bonded and the accelerator component from the components (e) to (h), towards the other

I c 'H ₂ - ⁽ • ο C. n. cn cn -o -f ' cn. O ( on I.
; -c i CIl,

adhesive surface is applied. The fact that the main component and the accelerator component do not have to be mixed before use, is a particular advantage of the invention Process and increases the economic efficiency of the gluing without the need for special devices or action would be required.

The solvent component (h) can, depending on the application, be a main component and an accelerator component be distributed. Preferably, however, the total amount of the solvent is in the Accelerator component included. The additives (i) can also be in the main component and / or the accelerator component. Preferably the additives are the main component incorporated.

The divinyl compound of the general formula 1

K ₂

C CIl,

ο cn, cn cn, ο c ο on

in which Ri and R.2 are a hydrogen atom or the methyl or ethyl group and π is an integer from 1 to 20 is described in US Pat. No. 3,373,075 and GB Pat. No. 10 06 587.

The organic peroxides (b) serve as polymerization initiators. In general, e.g. B. Hydroperoxides, such as cumene hydroperoxide, methyl ethyl ketone hydroperoxide, 2-methylbutylene-1-hydroperoxide, 2,5-dimethylhexane dihydroperoxide or tert-butyl hydroperoxide is used.

The acrylonitrile-buladiene-styrene terpolymer or the acrylonitrile-butadiene rubber (c) serve for the improvement the impact strength and the shear strength of the bond.

Examples of vinyl monomers (d) are acrylic acid, vinyl acetate or β-hydroxyethyl methacrylate. Through the Presence of the vinyl monomer (s) will increase the cure rate and the initial tack elevated.

Examples of thiourea derivatives (e) are trimethylthiourea, Dipropionylthiourea, diacetylthiourea, or tetramethylthiourea.

Examples of metal salts of organic or inorganic acids (g) are hydrochlorides and sulfates. Nitrates, phosphates or the salts of aliphatic and aromatic carboxylic acids with copper, cobalt, manganese, Vanadium or chromium. The salts of lower alkanoic acids, such as acetates, are particularly preferred or the naphlhenates of the aforementioned metals.

Although each of the components (c), (f) and (g) acts as an accelerator on its own, one only achieves with the mentioned combination in the specified proportions the advantageous, almost instantaneous Curing and the excellent initial bond strength of the adhesive according to the invention. Another advantage the aforementioned accelerator component is its good stability. Therefore the accelerator component is can be stored for a long time.

Examples of solvents (h) are alcohols such as methanol, ketones such as acetone or methyl ethyl ketone, Esters or halogenated hydrocarbons such as methylene chloride, trichlorethylene or chlorofluoroethylene.

In the preferred implementation of the method of the invention, the main components are composed from components (a) to (d). on the one and the accelerator component, consisting of the Components (e) to (h), applied to the other of the surfaces to be bonded. After the heartfelt Curing takes place when the two surfaces are joined. This is obtained at room temperature currently good adhesion with adequate tensile and shear strength. When performing the invention Process can also proceed in such a way that the accelerator components are in one a preferred working step on which a contact surface is applied, so that one is involved in the actual gluing process how to work with a one-component adhesive.

The two adhesive components are applied in a conventional manner, e.g. B. by painting or spray. The method is suitable e.g. B. for bonding metals such as iron, copper or Nickel, plastics such as polyvinyl chloride, acrylic polymers or epoxy resins, wood, glass or Ceramics.

The examples illustrate the invention. Parts and percentages are based on weight.

The acrylonitrile-butadiene-styrene terpolymers used in the examples and acrylonitrile-butadiene copolymers are rubber-like customary for this purpose Polymers.

Preparation of the divinyl compound

in a mixture of 190 parts of a liquid bisphenol-A Uiglycidyl ethers with an epoxy equivalent weight of 175 to 210 and an approximate molecular weight of 380 and 80 parts of methacrylic acid is at

5.8 parts of triethylamine are added to 50 ° C. with stirring. The mixture is heated to 50 ° C. for 5 hours, then 20 parts of acrylic acid are added and the mixture is heated to 50 ° C. for a further 10 hours. 290 parts of the liquid divinyl compound having a viscosity of 5000 to 10,000 cP.

example 1

100 parts of the divinyl compound are mixed with the vinyl monomers listed in Table I, 3 parts Cumene hydroperoxide and 6 parts of an acrylonitrile-butadiene copolymer mixed to one main component. Separately, 0.8 TeHe tetramethylthiourea, 0.01 part cobalt acetate, 1.0 part α, α-bipyridyl and 0.05 part of cobalt naphthenate dissolved in 100 parts of acetone to form an accelerator component.

The accelerator component is applied to the surface of a steel cylinder with a 1 cm ² cross section. After 30 seconds, this surface is intimately bonded to the surface of the same steel cylinder to which the main component has been applied. The tensile strength is determined at time intervals. The results are shown in Table I. Table I shows that the incorporation of the vinyl monomer improves tensile strength and initial bond strength.

Table II

Table I. 5 Without Parts Tensile strength (kg / cm ² )
after 15 min 24 h 235 Vinyl monomer Vinyl acetate 0 5 min 120 280 _{| 0} acrylic acid 30th 38 210 269 jff-hydroxyethyl-
methacrylate 10 195 190 327 30th 60 260 189

Example 2

100 parts of the divinyl compound are mixed with 4 parts Cumene hydroperoxide, the amounts of acrylonitrile-butadiene copolymer indicated in Table II, 20 Parts of acrylic acid and 10 parts of vinyl acetate are mixed to form a main component. Using this The main component and the accelerator components listed in Table II are steel cylinders glued according to example 1. The tensile strength is determined at time intervals. The results are in the table Table II shows that following the process of the invention in an extremely short time a considerable adhesive strength is achieved.

ABR-Tcile

Accelerator component

Share tensile strength (kg / cm) after

30 sec I min 5 min

24 hours

ίΧΛ'-bipyridyl 1.2 TetramethylthiohamstoiT 0.9 Cobalt chloride 0.01 Manganese acetate 0.02 acetone 100 ΛΛ'-bipyridyl 1.2 Tetramethylthiourea 0.9 Cobalt chloride 0.01 Manganese acetate 0.02 acetone 100 ΛΛ'-bipyridyl 0.05 N.N'-diacetylthiourea T. 2.9 Ku ':) fcracetate 0.006 acetone 100 ΛΛ'-bipyridyl 0.7 Trimethy (thiourea 2.3 Cobalt acetate 0.002 acetone 100 α, Λ'-bipyridyl 0.07 Ν, Ν'-DipropionylthioureaT 2.83 Chromium naphthenate 0.012 acetone 100 Λ.Λ'-Bipyridy! 0.05 Tetramethylthiourea 0.1 Vanadium chloride 0.01 Copper naphthenate 0.01 Acetone / ethanol (8: 2) 100

25th

74

180

389

12th

40

162

378

10

13th

14th

43

45

40

172

116

158

407

341

385

28

80

185

350

Example 3

100 parts of the divinyl compound are mixed with 2.5 parts of cumene hydroperoxide, 40 parts of acrylic acid, 30 Parts of vinyl acetate and the amounts of acnlnitrile-butadiene-styrene terpolymer listed in Table III (ABS) or acrylonitrile-butadiene copolymer (AB) mixed to form a main component. Separately from it 0.5 part of tetramethylthiourea becomes 1.0 part (XA'-bipyridyl, 0.05 part cobalt naphthenate and 0.01 Part of cobalt acetate dissolved in 100 parts of acetone to form an accelerator component.

The accelerator component is placed on the surface of a steel plate 12.0 cm long, 2.54 cm wide and 5 minutes of thickness applied so that from an edge starting from about 2 cm are covered. The main component is on the surface of a second, similar one Steel plate applied. The two steel plates are joined together with the prepared surfaces, so that there is an overlap of 1.5 cm. The shear strength is determined after 24 hours.

The results are shown in Table III. Table III shows that by the incorporation of the rubber-like polymer in the main component, the shear strength is increased considerably.

Table IV compiled. Table IV shows that tensile strength values were excellent with the adhesive and the shear strength can be achieved in a very short time after assembly.

10

Table IV tensile strenght Shear strength Time after (kg / cm ² ) (kg / cm ² ) Put together 32 30 see 98 - 1 min '119 - 2 min 185 - 3 min 226 115 5 min 322 290 24 hours 360 _ 48 hours

The accelerator component is filled into a glass bottle and stored in a desiccator ^{at 50 ° C. for 1 month.} Bondings are then carried out again using this accelerator component. The results are shown in Table V. Table V shows that the

Table III Parts Shear strength
speed oescnieunigerComp
Has stability. onenie one out ezeicnneie stock Component (c) (kg / cm ² ) 30 Table V 0 90 Time after tensile strenght Shear strength Without addition 8th
15th
30th
8th
15th
30th 380
256
230
290
298
280 Put together (kg / cm ² ) (kg / cm ² ) ABS polymer
AB polymer 35
30 see
5 min
24 hours
48 hours
40 36
214
340
353 108
272
285

Example 4

100 parts of the divinyl compound are mixed with 40 parts Acrylic acid, 30 parts of vinyl acetate, 7 parts of acrylonitrile-butadiene copolymer, and 4 parts of cumene hydroperoxide mixed into a main component Separately, 0.9 parts of tetramethylthiourea, 0.08 Parts of «A'-bipyridyl, 0.01 part cobalt acetate and 0.01 part Cobalt naphthenate dissolved in 100 parts of acetone to form an accelerator component. The time dependence the tensile strength and the shear strength is determined according to Example 1 and 3. The results are in Comparative example

According to Example 4, adhesive bonds are carried out using accelerator components in which one of the components tetramethylthiourea, «A'-bipyridyl and cobalt acetate + cobalt naphthenate is missing. The results are summarized in Table VI. Table VI shows that with these accelerator components the good values for adhesion are not reached as quickly as in the previous examples, and that these accelerator components also have poorer storage stability.

Table VI.

Accelerator component
(in acetone)

Tensile strength (kg / cm ² ) according to

min 24 hours 3 min *)

24 hours *)

Tetramethylthiourea
«A'-bipyridyl

ot ^ t'-bipyridyl

Cobalt acetate

Cobalt naphthenate

332

326

38

13th

319

330

9 10

continuation

Accelerator component tensile strength (kg / cm ² ) according to

(in acetone) 3 min 24 hrs. 3 min *) 24 hours *)

Tetramethylthiourea F.

Cobalt acetate 130 281 85 277

Cobalt naphthenate

*) 1 month storage of the accelerator component at 50 C.

Claims (1)

Patent claims: 1. Process for the production of bonds, in which one of the to be bonded Surface one component and the other surface the second component of a two-component adhesive or applying the mixture of the two components to both surfaces, the surfaces