DE3122146A1 - ADHESIVE PROCEDURE - Google Patents

Description

DR. ING. E. HOFFMANN (1930-1976) DIPL-ING.W.EITLE. DR.RER. NAT. Κ.ΗΟ FFMAN N. Dl PL.-I NG. W. LEH N

DIPL.-ING. K. FOCHSLE. DR. RER. NAT. B. HANSEN ARABELLASTRASSE 4 D-8000 MD NCH EN 81: '. TELEPHONE (089) 911087. TELEX 05-29619 (PATHE)

35 051 o / wa

TAKIRON CO., LTD., OSAKA / JAPAN

Gluing process

The invention relates to an adhesive method using an oil-cyanoacrylate adhesive, and in particular a method of temporary fastening in the field of construction.

C ^ cyanoacrylate adhesives, which are instant adhesives, include to the blocking adhesives, which undergo ionic polymerisation very quickly due to the presence in the air Water or water absorbed on the surface of the object to be connected enters,

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3122H6

and by means of which almost all materials, with the exception of certain types of plastic, can be connected. That's why they are used when a quick connection is required.

But if the surface of the object to be connected is uneven or has absorption properties, such as a porous surface, then it is impossible to do so To use glue as a binder because it has a low viscosity. That fact makes it impossible to temporarily place objects on concrete surfaces, mortar surfaces, plaster surfaces, wooden surfaces and the like, or surfaces made of plywood, tiles, glass glue (such as mirrors) or other wall materials. As a result, one is such Adhesive has hardly been used in construction so far, because the surfaces to be connected are in many cases perpendicular are.

On the other hand, in construction it is often necessary make temporary adhesion and compression for immediate connection. For example, if you Attach wall materials such as decorative panels, plasterboard, mirrors and the like to wall surfaces would like, where the wall surfaces consist of concrete or mortar, epoxy resin adhesive has been used and then a temporary adhesion is carried out with nails or adhesive tape until a complete bond was achieved. But if you use nails, splinters can appear and nail holes remain back, or nailing is impossible due to

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the materials used. In the latter case, it is not possible to achieve sufficient adhesive strength. Therefore it is desirable to have a simple method of creating a strong, temporary bond.

The known methods using an ev-cyanoacrylate adhesive include a process in which a wood bonding surface is bonded to a quaternary Ammonium salt treated (Japanese Patent Publication 11 685/77) and a method in which a primer consisting of a sealing compound and a hardening accelerator is first applied to the bonding surface (JA-OS 40 027/78). However, these procedures are difficult to practice in construction because they are cumbersome and because the immediate bond is damaged if you use a filler Glue (with an increased viscosity) is used.

Based on research, ck cyanoacrylate adhesive with very good instant adhesive properties in construction and especially for temporary attachment now found that you can get a flexible material on. which a curing accelerator has been applied, must attach between the bonding surface of the parts to be joined.

The invention thus relates to a method for connecting a first adhesive part (typically with an uneven surface or a porous surface such as a decorative panel) with a second binding part (also typically with an uneven surface

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or a porous surface such as a wall surface made of concrete) with an adhesive made of a flexible Carrier part that is easily applied to the binding surfaces of the first and second parts to be prebinded and which absorbs the o ^ -Cyanoacrylate adhesive and holds, e.g., absorbent cotton and the like, and a setting accelerator adhered thereto is applied to one or more parts of the bond surface, with a small amount of the adhesive (typically one or a few drops) on the adhesive auxiliary or is applied to the bond surface and wherein by contact with the adhesive aid the first and the second part to be connected are connected. This flexible carrier part is instant fixed by the adhesive in such a state that conforms to the surfaces of the parts to be joined is, d * h. of the first and the second part to be connected, in such a way that the shape of the bonding surface and the gaps between the bonding surfaces match and whereby the two parts immediately and firmly adhere to one another.

The (iO-cyanoacrylate adhesive to be used according to the invention typically comprises an oC cyanoacrylate monomer general formula

CH ₉ = C C-OR

* ■ ι π CN 0

wherein R is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, a cyclohexyl group, a

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Alkenyl group, a cycloalkenyl group, a phenyl group, an allyl group and the like as an adhesive component. An adhesive can also be used containing a small amount of SCU as a stabilizer, an anionic and radical polymerization inhibitor such as hydroquinone and the like, and one Contains esters as plasticizers. Although a thickener can be used, it will in the case of its use, it is used only in a very small amount and it is not preferred to use a thickener to be used because the immediate adhesion property and the penetration into the flexible carrier part is disturbed will.

The adhesive aid which is used according to the invention consists of a hardening accelerator for accelerated hardening of the ^ cyanoacrylate adhesive and a carrier part to which the hardening accelerator adheres by fixing, absorption or chemical bonding (hereinafter collectively referred to as adhesion).

The support part is a flexible part that can be adjusted to fit between the crevices, uneven surfaces and the different shapes if it is between a first binding part and a second binding part inserted to fit and which effectively holds the curing accelerator. It also lasts effective the adhesive in that the adhesive quickly penetrates the flexible carrier part when the adhesive is applied to it causing the adhesive and the curing accelerator to come into contact takes place effectively and the carrier part solidifies and the first binding part to the

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second binding part binds and fills the space between them. For example, cotton goods such as absorbent cotton or a cotton cloth and the like which easily changes shape by pressure can be effectively used. In addition, flax, wool, rayon, acetate, polyester, nylon, vinylon (ie, a synthetic polyvinyl alcohol fiber), glass fiber, and other organic or inorganic natural or synthetic fibers can be used in place of cotton. These may include any form have as cotton wool, adhesive tapes, felts, sheets, nonwovens, strands and the like, as far as they are flexible and easy to adapt to uneven surfaces, hold the cure accelerator effective and also hold the <i -Cyanoacrylatkleber effectively by rapid penetration. As a result, it is possible to use materials with continuous, open-cell foams that easily change shape, such as sponges or urethane foams. Filter paper, pulp and the like can also be used.

As a curing accelerator, it is possible to use all compounds which are capable of being anionic Initiate polymerization of d ^ cyanoacrylate or speed up. Well-known hardening accelerators are e.g. hydroxides of alkali metals such as lithium, Sodium or potassium; Compounds that these alkali metals with mono-, di- or tribasic acids, such as Hydrochloric acid, sulfuric acid or phosphoric acid, or organic acids such as acrylic acid or acetic acid; Oxides and hydroxides of alkaline earth metals such as magnesium or calcium; Metal soaps made from organic acids,

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such as naphthenic acid and the like, and cobalt, vanadium, manganese, lead or iron; Amines, such as monoethanolamine, Diethanolamine, triethanolamine, amylamine, ethylhydrazine or hexamethylenediamine, or basic compounds, which contain at least one primary, secondary, tertiary or quaternary nitrogen atom in the molecule. Since all of these compounds have different abilities to cure o ^ cyanoacrylate glue, they can be used use by changing the type and amount depending on the type of support part, or by combining them with the subsequent Fixing agents or penetrants and the like, depending on the purpose used, combined.

The adhesive auxiliary agent according to the invention is preferred produced by one or more of the aforementioned curing accelerators in water or an organic solvent and the carrier part, such as absorbent cotton, in the appropriate Solution dips, dries (or removes the solvent), leaving the molecules of the curing accelerator are on the surface of the fibers and then air dry. The dehydration is preferably carried out by centrifugal separation and the like so that the attached curing accelerator is firmly adhered thereto. If an organic solvent is used, it can be removed in the usual way. Still exists not only the possibility of attachment by fixation or absorption, but also by chemical Binding, e.g. in the case of alkali cellulose. The above-mentioned solution can, if desired, also use auxiliaries such as fixing agents for better adhesion of the curing accelerator to the carrier fibers or penetrants

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to improve the penetration of the hardening accelerator into the fibers, as well as chemical ones Means to bring about improved penetration and retention of the C 1-4 cyanoacrylate adhesive. Carboxymethyl cellulose (CMC) or its Derivatives such as dimethylcarboxymethyl cellulose sodium salt, acrylic acid esters, polyacrylic acid and their salts, linseed oil, Polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate and copolymers thereof are used depending on the type of the support member and the curing accelerator. As a penetrant you can use surfactants, e.g. Noigen 130T (trade name) may be used, but substances that have both functions (i.e., the fixatives and penetrants are), such as sodium polyacrylate or dimethylcarboxymethyl cellulose sodium salt, can also be used will. Furthermore, it is possible to reduce the curing time by combining these additives with the curing accelerators monitor because some of these additives accelerate the hardening of the c ^ cyanoacrylate adhesive or delay.

Table 1 (a) shows examples obtained by using Carries out adhesive tests for various parts of the binding. From these results it can be seen that the inventive Method an adhesive strength (tear strength) of about 10 kg / cm or more obtainable is in cases where at least one of the parts to be connected has a porous absorbent surface, like an asbestos board or plywood, which is in contrast to the impossibility of gluing if you do not use the bonding aid.

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In all cases, with the exception of iron-iron, the material is destroyed. As a result is the method according to the invention is extremely effective, to bond objects with uneven surfaces or porous surfaces, because of the weight of the Parts to be connected not only for a temporary connection, but also for normal gluing is sufficiently worn.

The results shown in Table 1 (a) were obtained as follows. An adhesive aid in the table The composition shown in Fig. 1 (b) was thinly sprayed on the edge portions of the second joint part (test piece) and two drops of c ^ cyanoacrylate glue (ALTECO EE, trade name, manufactured by Alpha Giken Co.) were dripped on the edges of the first Binding part (test piece) was applied, and the first and second binding parts were lightly connected to each other pressed for 1 to 3 seconds and thereby connected. After 2 hours had elapsed after connecting the strength in the normal state was measured according to JIS K-6850. The expression used in Table 1 (b) "Smoking properties" refers to smoke (from unreacted substances and others) emitted by the Heat of reaction is formed during curing of the adhesive and which is a criterion for the completion of curing. In the tables below, the occurrence of smoke is shown in the column with smoke properties is overwritten, indicated by the ο character.

A joining of wall surfaces such as those made from

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Plasterboard or decorative plywood and the like, on walls made of concrete and the like, the temporary attachment can be effected very easily and safely by adding some parts of an adhesive e.g. in the size of a bean or a soybean, on a part between the parts to be connected, in particular on the peripheral part after applying an epoxy resin adhesive or other adhesive and then put one or a few drops of a C ^ cyanoacrylate adhesive on it and during some Seconds then lightly pressed together.

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Table T (a)

ω ο ο σ>

σι

first bandage
part (thickness
m / ra) second bin
deteil (thickness
m / m) . with adhesive observation without kie-
auxiliary
material Iron plate
(rough upper
area) (1, 5) Asbestos panel
(3.2) Tear-off
sturdiness
(kg / .cm ^.). . . the asbestos sheet breaks no bin
manure Iron plate
(rough upper
area) (1.5) plywood
(5.5) 15.7 the surface of the plywood
zes (intermediate layer) peels
himself off Il Iron plate
(rough upper
area) (1, 5) non-combustible
re decoration
tion plate
(4.2) 29.5 the non-combustible decoration
tion plate breaks Il Iron plates
(rough upper
area) (1, 5) Iron plate
(rough upper
area) (1.5) 16.6 Il non-combustible
re decoration.
tion plate
(4.2) plywood
(5.5) 150.0 the surface of the plywood
zes (intermediate layer) peels
himself off Il non-combustible
re decoration
tion plate
(4.2) Asbestos panel
(3.2) 9.6 the asbestos sheet breaks Il 9.0

CO

K) CO

Continuation of table 1 (a)

first bandage
part (thickness
(m / m) second bin
deteil (thickness
m / m) . , with adhesive agent observation without kie-
auxiliary
material Mortar (20)
Mortar (20) plywood
(5.5)
non-combustible
re decoration
tion plate
(4.2) Tear-off
sturdiness
(kg / cm ^2. ). . the intermediate layer between
breaks the materials
the intermediate layer between
breaks the materials no bin
manure
Il 8.0
12.0

σ «ι

CO & ro

CD

Table 1 (b)

Carrier part: Absorbent wadding 80g G Accelerator: Diethanolamine 50 G Aids: Noigen 130T 2.5 Solvent: Water 450 g Application amount%: 11.3 Smoking properties: O

The appearance is very nice because of the connection no nails are needed. The temporary fixing of materials that are not held in place by nails Like glass, mirrors or tiles, it can be done very easily without any accidental separation is done as can be done in the case of using adhesive tapes, and this improves work efficiency significantly improved without getting your fingers dirty. In addition, the great of the adhesive aid used is not limited and the auxiliary adhesive can be used not only for temporary adhesion but for ordinary adhesion will. In this way one can avoid the disadvantage of a cfj-cyanoacrylate adhesive, namely that it is not suitable for the connection of numerous materials is suitable, and it can not only be overcome on uneven surfaces or apply porous surfaces, but also on smooth bonding surfaces. Especially when pinning of tiles with mortar, it was previously the case that only a few rows were attached per day

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because they fell down again due to their own weight. By means of the method according to the invention the entire wall can be completed in one day. In addition, great progress is made achieved in the field of construction because, for example, cross battens can be applied to concrete surfaces, on which you can then nail decorative plywood panels.

In the following table 2 test results are shown for adhesive auxiliaries which are used of 80 g of absorbent wadding as a carrier material and with various hardening accelerators and fixing agents were measured, with the smoking properties as well and the time until smoking started. The smoking properties were observed visually by a piece of the processed absorbent wadding (adhesive adjuvant) was applied to an iron plate and then two drops of the same glue as in table 1, dripped on. There was only a slight amount of smoke one or none at all (which is shown in the table with ^ or χ and where the hardening proceeds slowly) so the time to smoking was measured on a round processed absorbent wadding to increase the density and this is shown in brackets. The acrylic emulsion used in the table (Acryset PK-542, solids content: 39.6%, pH 7.1) is manufactured by Nippon Shokubai Co.

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I. Fixative (g) Dimethylcarboxy
cellulose sodium
salt 3 Table 2 Solution with
tel (g) Smoke: i
smoke Properties
Time (sec.) up
brought
Lot(%) I. til 1
I. of course
ches ma
material Acrylic acid ester
20th Water 780 O 8-10 32.5 Oi)
1 ! 122 emulsion Acrylic acid ester
50 Hardening
faster Water 200 X (15-20) emulsion Sodium poly
acrylate 50 Sodium car
bonat (water
free salt)
60 Water 450 X (20) 15.8 to
O
O Polymer-
salt Flaxseed oil 50 Sodium car
bonat (10
Hydration water)
45 Water 314 Δ (30) 8.6 co
■ »J plants
oil Polypropylene
glycol 5 Hexamethylene
tetramine 25.4 Toluene 350
MEK 100
Ethanol 50 O 12th ^r 0872 Polyglycol Sodium car
bonat (10
hydrate water)
136.2 Water 10 O 5-7 Diethanolamine
2.5
Cobalt naph
thenat 0.25 Calcium stea-
council 10

3122T46

In Tables 3 and 4, the results of the same become Smoke test as shown in the case of Table 2 for processed adhesive auxiliaries made from various Types of support materials passed. In Table 3, the support part was immersed in a solution containing was prepared by dissolving GO g of sodium carbonate as a hardening accelerator and 3 g of dimethyl carboxymethyl cellulose sodium salt as a fixative in 780 g of water, whereupon the carrier part is then dried became. In Table 4, the carrier oil in immersed a solution prepared by dissolving 5 g of diethanolamine as a hardening accelerator and 0.25 g of Noigen 130T as a penetrant and 495 g Water, whereupon the carrier part was dried.

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Table 3

co ο

cn -j

O 00 -J

material Carrier
Raw material 1
source broke up
te amount Smoky eggs
smoking properties
Time (sec) Absorp
tion tree
wool cotton
(Cellulose) Miyake Menko,
The Japanese
Pharmacopoeia,
450 c
Lot No. 540330 32.5 O 5-6 Surface
fleece glass fiber Asahi Fiber Glass,
SM-36O3-E
60 g / m ² 29.0 O 5-6 Non-woven fabric
i
! polyester
fiber Toray Acstar
Spanbond
100 g / m ² 3.9 O 5-6 j sponge
ί Urethane
foam
1 Marketing goods
(domestic)
30x100x150 m / m) 102.5 O
I. 5-6

to O

to

CO

K)

K)

CD

Table 4

material Carrier part
Raw material source upset-
te amount
(%) Smoky batter
smoking properties
Time (sec) Cotton
cloth
■ cloth) cotton Marketing goods 10 O less than 3 Flax fa
ser flax Il 8th O less than 3 Non-woven fabric Polyesterfa ™
ser Toray Acstar
100 g / m ² 4th O less than 3 Filterpa
pier Pulp Toyo Roshi,
No. 5B 9c 3.5 O less than 3

Table 5

O O

CD CO

ro

Hardening accelerator
Niger Excipient Solution
middle carrier
part Dehydration
by centrifu
gene separator Weight (g) Air-
dry
know-
w.
(G) Smokers own
societies Time
(s) Tear-off
sturdiness
(kg / cm ^ Diethanolamine
25 g (DBA 5%) Intrusion
medium Noigen
130T 1.25 g water
475 g Absorp
functional
cotton wool
80 g Time (s) 149 87 smoking 3 16.1 Diethanolamine
50 g (DEA 10%) Intrusion
medium Noigen
130T 2.5 g water
450 g Il 30th 139 89 O 2-
2.5 10.8 Diethanolamine
75 g (DEA 15%) Intrusion
medium Noigen ■
130T 5.0 g water
425 g Il 30th 156 98 O 1 12.2 ' Sodium carbonate
10 hydrate 136.2 g fixer
1% aqueous
Solution before. N / A-
trium polyacrylic
lat 50 g water
314 g Il 30th 380
303
269 87 O (30) 25th Ammonium carbon
nat 37.1 g fixer
1% aqueous
Solution before. N / A-
trium polyacrylic
lat 50 g water
413 g M. 30th
60
90 390
237
201 160 Δ 12th
i 40.2 30th
60
30th O

ro

to

U)

CO ro CD

Table 5 continued

O O

oo -α

ro

Curing accelerator Excipient Solution MEK 100 g carrier 11 Dehydration I. Weight (g) Air- Smokers own Time Tear-off Niger middle Ethanol part by centrifu dry societies (s) sturdiness 50 g gene separator know- 10 (kg / cm ^) w. Il (G) smoking Cobalt naphthenate toluene Absorp Time (s) -; _ 113 50 g 450 g functional the end O 14th 38 cotton wool wring 8O g by means of Lead naphthenate toluene hand 365 91 12.5 g. 487.5 g M. O 12th 32.2 Diethanolamine 2.5 g Cobalt naphthenate fixer toluene - 0.25 g Flaxseed oil 350 g O 22.6 50 g

U) I

CO K)

CD

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The results of the measurements of the adhesive strength (tear strength) of the adhesive, made using 80 g absorbent wadding as a carrier part and various hardening accelerators as auxiliaries, are shown in Table 5. The absorption;. wool was used in an amount of 80 g. The measurement conditions and the others were the same as in Table 1 (a) except that a drop was used as the glue was used and that the temporary pressing (light pressing of the surfaces to be connected with hands) for a period of time indicated by the smoking properties. Farther the content of curing accelerator, apart from diethanolamine (DEA), was geared to DEA 10%, which is equimolar (0.476 moles) to the moles of DEA is 10%. the Results (shown in Table 5 as dry weight in air (g) were obtained 24 hours after dehydration and air drying measured.

The results show that the bond is instantaneous up to a few tens of seconds if one the method according to the invention applies, regardless of the inequality or the absorption of the to be connected Surfaces, but it is also possible that Carry out caging within a few minutes to a few 10 minutes if you use a suitable hardening accelerator selects.

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Claims (7)

PATENT CLAIMS 1. Gluing process, characterized that you can make an adhesive auxiliary from a Hardening accelerator for accelerated hardening of an ok-cyanoacrylate adhesive and a flexible one Carrier part on which the hardening accelerator is applied, between a first binding part and a second binding part introduces that an oil-cyanoacrylate adhesive is applied to the binding surfaces of the adhesive auxiliary is applied, and that the first binding part and the second Binding part connects to one another by the adhesive aid. 130067/0872 2. Gluing method according to claim 1, characterized in that the adhesive auxiliary is placed on part of the binding surface. 3. Gluing method according to claim 2, characterized in that the adhesive auxiliary is placed on the peripheral part of the bandage surface. 4. Gluing process according to claims 1, 2 or 3, characterized in that at least the first or the second part to be connected has a porous surface, an absorbent surface or has an uneven surface. 5. Gluing method according to claim 1, characterized characterized in that the curing accelerator is selected from the group alkali hydroxide, a compound of an alkali metal with a monovalent, divalent or trivalent Acid or organic acid, an alkaline earth oxide, an alkaline earth hydroxide, a metal soap, a Amine and a basic compound containing at least one primary, secondary, tertiary or quaternary nitrogen atom in the molecule. 6. Gluing method according to claim 1, characterized characterized in that the flexible carrier part is selected from the group cotton, Flax, wool, rayon, acetate, polyester, nylon, 130067/0872 "" 3122U6 Vinylon, fiberglass, sponge, urethane foam, Filter paper and pulp. 7. binding method according to claim 1, characterized characterized that the flexible support part in the form of wadding, cloth,
a tape, a felt, a sheet, a nonwoven fabric or a tape is present 130067/0872