DE2215815A1 - Adhesive composition and its use - Google Patents

Description

DR. O. DlTTMANN K. L. SCHIFF DR. A. ν. FIVE BR DIPL. IN O. P. BTRBHL

β MÖNCHEN BO MAHIAHILFPLATZ S ft 9

KURARAY CO., LTD. 31 MM. 1172

DA-5123

The invention relates to an adhesive composition or a Adhesive composition and in particular an adhesive composition suitable for processing wood and its use.

Adhesive compositions for wood have been widely used in sizes water-soluble condensates of formalin with urea, melamine and / or phenol are used. The wood adhesives where these thermoplastic resins are used have good adhesiveness to wood and form a water-resistant layer due to the thermoplastic resin used. These adhesives are then used if water resistance is to be aimed for and the particular compositions are selected depending on the degree of water resistance desired. These However, adhesive compositions with thermoplastic resins have significant disadvantages. First, assign these. compositions have a formalin odor. The thermoplastic Formalin-based resins contain large amounts of unreacted formalin that is freely released into the air and that the work area with its own harmful Smell fills. Wood materials made with these thermoplastic

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See adhesive compositions manufactured like eS plywood, continuously release small amounts of formalin during and after processing into end products such as furniture, which means that the characteristic formalin smell cannot be removed Months to about 90 i · from. Third, the initial adhesive force is so low that uncomfortably long press times must be used before the workpiece has the minimum initial bond force sufficient to allow it to be transferred to the next processing stage, such as the hot press. This is a great disadvantage in practice, which has a direct influence on the usefulness of the compositions. Fourth, the viscosity of these adhesive compositions is so low that they cannot be used when working with equipment for forming coatings, such as flow coating equipment or curtain coaters. Thus, the use of these compositions prevents the use of various improvements which could make the manufacture of plywood more continuous, thereby saving manpower. The fifth disadvantage is that these compositions must be heated during the sticking time. The heating during the bonding time is necessary in order to evaporate the water contained in the adhesive composition and to accelerate the condensation and the setting of the resin. If one does not heat during the bonding time, no binding force can be achieved. The sixth disadvantage is that the binding power of these compositions depends considerably on the water content of the wood, so that the wood must be dried to a water content of about 10% before use.

The object of the present invention is therefore to provide economical adhesive compositions which Advantages of the well-known thermoplastic resin · on the ground «

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position of formalin and the disadvantages of these materials avoid.

Another object of the invention is to provide an adhesive composition provide for wood, which is able to develop a good water-resistant binding force. ,

Another object of the invention is to provide an adhesive composition for wood which, under severe open-air weather conditions, is strongly taler woodwork can be used.

The object of the invention is now achieved by wetting the adhesive together solved that

(A) a copolymer of an olefin and a carboxylic acid or an alkali metal salt of this copolymer and

(B) a polyvalent metal hydroxide or a polyvalent metal oxide

contains. Furthermore, in a preferred embodiment of the invention the cohesiveness of the adhesive composition in terms of water resistance can be improved by

(C) adding a water-soluble compound which contains at least two epoxy groups in the molecule.

The basic composition according to the invention, which are those given above Containing ingredients (A) and (B) is highly satisfactory for those uses in which moderate water resistance is required, such as B.B. in the manufacture of ordinary plywood or ordinary water-resistant plywood (Japanese Agricultural Standard, Type III and Type II). However, if highly water-resistant Plywood (Japanese Agricultural Standard, Type I) is to be produced, e.g. for the production of outdoor

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Ornaments is needed, it is essential that the composition also contains component (C).

Examples of the copolymer uus an olefin and a unsaturated carboxylic acid or the alkali metal salt of this Copolymers include the following materials:

(1) A copolymer of one or more olefins and one or more unsaturated carboxylic acids, the one or may contain several carboxyl groups, such as acrylic acid, methacrylic acid, crotonic acid, or itaconic acid their monoesters, fumaric acid or their monoenter, citraconic acid or their monoester and mecaconic acid or their Monoester.

(2) A hydrolyzed or alkali-saponified copolymer from an olefin and a monomer containing a functional group that becomes a carboxyl group hydrolyzed or saponified with alkali, such as maleic anhydride, citraconic anhydride, itaconic anhydride, Acrylamide, acrylonitrile, methacrylonitrile, acrylic acid ester, methacrylic acid ester, crotonic acid ester, Maleic acid diester or Puinaric acid diester.

Among these copolymers which contain carboxyl groups, the following polymers are preferred: Copolymers of one or more olefins with one or more monomers, such as maleic anhydride, acrylamide, Acrylonitrile, acrylic acid ester or methacrylic acid ester. Styrene / maleic anhydride copolymers are particularly preferred and olefin / maleic anhydride copolymers. Most preferred are olefin / maleic anhydride mixed polymers. The water-soluble copolymers of this type can be used in aqueous solution, while the copolymers, which are insoluble or only sparingly soluble in water, before use in an aqueous solution of ba3i-

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see substances can be dissolved.

With regard to the relative amount of those contained in the polymer There is a lower limit to carboxyl groups, which is necessary so that the polymer is in water or a aqueous solution of a base can be dissolved and thus the desired properties of the end product obtained Adhesive composition intended for a particular use are required, v / which in particular the water-resistant binding force is achieved. This lower limit depends on the chemical and physical structure of the polymer and the intended use, so that no general Definition for it can be given. It should be noted, however, that at least about 10% by weight, preferably about 10 to about 100% by weight, and most preferably about 30 to 85 wt .- $ of monomer units, the carboxyl groups contained in the side chain, must be present in the polymer.

A degree of polymerisation of at least about 100 is required for sufficient binding force (adhesive force) is achieved.

To dissolve the polymer in water, a basic Substance such as an alkali metal hydroxide (e.g. sodium hydroxide or potassium hydroxide), an alkali metal carbonate, ammonium carbonate, ammonia, an organic amine, an alkali metal acetate or ammonium acetate may be required. One or more of these basic substances can be used.

As stated above, according to the invention, olefin / maleic anhydride copolymers, the most preferred copolymers. According to the invention, olefin / maleic anhydride copolymers are used as; Olefin / maleic anhydride copolymers, olefin / maleic acid monoeter copolymers, Olefin / Mleic acid anhydride / maleic acid monoester or -diester-

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Terpolymers, olefin / maleic acid monoester / maleic acid diester terpolymers or defined as the reaction product of one of these copolymers with an alcohol. The olefin can be straight-chain or branched and a mono- or diolefin having 2 to 8 carbon atoms, preferably 2 to carbon atoms, such as ethylene, propylene, n-butene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-i-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, 1,3-pentadiene, 1,3-hexadiene, 2, 3-dimethylbutadiene, 2-methyl-1,3-pentadiene, 2,5-heptadiene, 1,3-heptadiene _r 2 -methyl-1,3-hexadiene, 1,3-octadiene, styrene and cyclohexene. Of these compounds, the α-olefins are preferred, while isobutene is particularly preferred. Isobutene can be a recycled butene / butane precursor that contains isobutene. The maleic acid monoesters or diesters include maleic acid alkyl esters, maleic acid dialkyl esters, maleic acid aryl ethers, maleic acid diaryl esters, maleic acid aralkyl esters, maleic acid diaralkyl esters, maleic acid monocycloesters or dicycloesters, maleic acid cycloalkyl esters and maleic acid cycloalkyl esters and dicycloalkyl maleic acid, 1 to 3 and alkyl maleic acid dicycloalkyl groups, bis alkyl and dicycloalkyl groups . The reaction product of the copolymer with an alcohol is an ester of the copolymer with an »alcohol, such as an aliphatic alcohol» an aromatic alcohol or an alicyclic alcohol, the aliphatic aromatic or alicyclic radical containing 1 to 8 carbon atoms.

Accordingly, the reaction product of the copolymer with an alcohol by the following general formulas

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(D (ID

CH - CH -} -

C = O C = O.

1 t

0 0

(D (in)

(I) (ID

(IV)

(D (IH)

(IV)

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-β- 22158T5

where R ₁ and R _{2 represent} hydrogen atoms, alkyl groups or aliphatic, aromatic or alicyclic radicals, R, an alkyl group or an aliphatic, aromatic or alicyclic radical and R and R 2 represent hydrogen atoms, alkyl groups or aliphatic, aromatic or alicyclic radicals.

These copolymers can be prepared by carrying out the polymerization in the presence of a customary free radical initiator in a suitable solvent. The analysis of the composition shows that the binary copolymer (i) - (II) has a molar ratio of 1: 1, while the mixed polymer (I): (ΪΙΙ) has a molar ratio of 1: = 1. The terpolymer, which contains maleic anhydride and an alkyl maleic acid ester, (I): [(II) + (IV)] and (I): [(III) + (IV)] has a molar ratio of about 1: 1, in which (i) which makes up one half and the rest is provided by [(H) + (IV)] or [(HI) + (IV)]. As a measure of the chain length of the copolymer, a suitable intrinsic viscosity as determined in dimethylformamide at 30 ⁰ C and 0.10, preferably 0.30 to about 5 to about 2 is used. V / enn [η] is smaller than 0.10, the adhesive force is markedly reduced, while in cases where the value of [q] is larger than 5, difficulties in manufacture may arise.

The copolymer, which is soluble in an aqueous alkaline solution, can before use in an aqueous Solution containing a suitable amount of an alkali metal hydroxide, contains an alkali metal carbonate, ammonia or an organic amine.

According to the invention, in the olefin / unsaturated carboxylic acid MiBchpolymerisate copolymerizable monomers incorporated into the polymer will. Examples of other comonomers that

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that can be used for this are vinyl esters (e.g. vinyl acetate), Vinyl chloride and alkyl vinyl ethers (e.g. methyl vinyl ether).

Examples of oxides or hydroxides of the polyvalent metals which can be used according to the invention are Oxides and hydroxides of metals of groups II to VIII of the periodic system, e.g. calcium, magnesium, zinc, barium, * Cadiuium, lead, copper, aluminum and iron. Further examples for these compounds are bentonite, clay, talc and "satin white" (a complex of aluminum sulfate and calcium hydroxide, used in the paper industry). As an aqueous solution of oxides or hydroxides of metals of Group II is alkaline, the pH of the solution can be adjusted freely by adjusting the amount of materials added to be changed. At the same time, the bond between the carboxyl group and the carboxyl group-containing polymer can be freely changed, so that an extremely advantageous adhesive composition is obtained which has a controllable viscosity having.

If oxides or hydroxides of metals of a group other than group II of the periodic table are added, changes the viscosity hardly increases or rather increases.

As metal oxides and hydroxides, the oxides and hydroxides of zinc, calcium, magnesium, copper and aluminum are preferred. These oxides and hydroxides can be used alone or in the form of mixtures.

A suitable for the olefin / carboxylic acid interpolymer amount of metal oxide or hydroxide is below 800 wt .- # _t preferably below 300 wt .- $ and at bevorzugtesten is to 50 to 200 wt .- #. If more than $ 800> is added, the adhesive force is insufficient and in most of them

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In some cases, the adhesive composition cannot be used. A composition of this type results in a suspension and the water rather than a uniform dispersion diffuses and easily penetrates into the y-piece, whereby an initially high adhesive force is achieved.

Examples of water-soluble compounds that are at least zv / ei have epoxy groups, diglycidyl compounds are polyvalent Alcohols (e.g. glycerine or glycols), such as glycerine diglycidyl ether, Ethylene glycol diglycidyl ether, polyethylene glycol dissocidyl ether, Glycerol iriglycidyl ether, Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and diglycidyl ecters of compounds containing at least have two carboxyl groups in the molecule. Compounds having at least two carboxyl groups include the Olefin / unsaturated carboxylic acid copolymers, the as a component of the adhesive composition according to the invention may be present.

Instead of the water-soluble compound which has at least two epoxy groups, epihalohydrins, and in particular Epichlorohydrin can be used. According to this embodiment of the invention, an aqueous mixture is used made alkaline from the carboxyl-containing polymer and the metal oxide or the metal hydroxide, whereupon one Epichlorohydrin is added to the alkaline solution, so that the adhesive composition is obtained.

The water-soluble compound, which has at least two epoxy groups, does not have to be completely water-soluble, but can also include partially water-soluble compounds or epoxy compounds derived from the invention Adhesive composition cannot be deposited.

The epoxy compounds are used in amounts of 0 to 100 mol-96, preferably 5 to 40 moles based on the number of moles

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from carboxyl groups in the copolymer to the olefin / unsaturated Carboxylic acid copolymer exposed. The adhesive composition becomes over time through 'the .Reaction of a carboxyl-containing polymer with an epoxy compound is more viscous, but the increase in viscosity is considerably due to the influence of the concentration the carboxyl groups, the concentration of the epoxy groups or the pH value is changed so that for practically every time / Viscosity requirement a suitable composition can be selected.

The polymerization gray of the carboxyl-containing polymer and the concentration of the adhesive composition of the invention are closely related to the viscosity of the adhesive composition related. If you look at the composition accordingly for a porous low density workpiece such as a surface fabric, it is desirable to use a To avoid a decrease in the binding force due to excessive penetration into the workpiece by increasing the degree of polymerization, the concentration of the entire adhesive phase the suspension increases and the viscosity of the adhesive composition increases as much as possible.

According to the invention, the adhesive composition can still To make water-resistant or water-resistant, a polyvinyl alcohol can also be used.

Examples of polyvinyl alcohols which can be used according to the invention are: partially saponified polyvinyl esters (especially polyvinyl acetate), fully saponified polyvinyl acetate or denatured water-soluble polyvinyl alcohol (e.g. polyvinyl alcohols that are less than 10 mol-56 Groups such as acrylamide groups, allyl ester groups, allylamine groups and / or contain acrylic acid groups). The polyvinyl alcohols should have a degree of polymerization of 100 to 3,000,

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preferably 200 to 1,700 and a degree of saponification of 70 to 100 mol -? »ι preferably 85 to 98 mol - have. If the degree of poly (vinyl alcohol) is less than 100, the bond strength of the adhesive composition decreases while if the degree of polymerization is greater than about 3,000, the viscosity of the adhesive composition increases excessively, so that the processing properties deteriorate will. If the degree of saponification of the polyvinyl alcohol is less than about 70 Mo 1-5 », the strength decreases the adhesive composition.

The polyvinyl alcohol Avird in an amount of 5 to 100 parts by weight, preferably 5 to 20 parts by weight based on 100 Parts by weight of the olefin / unsaturated carboxylic acid copolymer admitted. If the amount of polyvinyl alcohol is less than about 5 parts by weight, the adhesive will lose the binding force Composition from, while at an amount greater than about 100 parts by weight, the viscosity of the adhesive composition increases excessively.

When using the adhesive composition for wood, can it may be advantageous to increase the viscosity and the concentration of pesticides in the adhesive composition by incorporating Fillers such as wood flour, wheat flour, bean flour, glue, zeolite or urea. It can also differ Emulsions and latices (e.g. styrene / butadiene mixed polymer latex, an ethylene / vinyl acetate copolymer emulsion or a polyacrylate emulsion) are incorporated, to increase the adhesive force or to adjust the viscosity depending on the amount incorporated. the Use of a styrene / butadiene mixed polymer latex is particularly preferred. The amounts of styrene / butadiene copolymer latex (as a solid) can range from 0 to 500 wt. preferably 20 to 200 wt .- #, based on the olefin / unsaturated Carboxylic acid Miechpolymerisat extend. With the exception

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of the epoxy compounds, the order in which the individual constituents of the adhesive composition are added can be freely selected without affecting the viscosity and the adhesive force. Desirably, in view of the time available, the epoxy compound is incorporated immediately prior to the use of the adhesive composition. This adhesive composition is dissolved in water. The Feststofxgehalt the adhesive zusaiaraen- ^T reduction in water is in the range of about 15 to 70 preferably 20 to 60 $

The adhesive composition of the present invention has many technical and practical advantages, in particular the following:

(1) The concentration of solids can be greatly increased can be increased over a wide viscosity range without affecting the processability of the adhesive will. Furthermore, since the composition is a suspension system, high initial binding forces can be achieved will. Some of the known heat setting adhesive compositions show at room temperatures only very low initial binding forces. Using such known compositions usually is Requires?.: Lich, first the workpiece 40 minutes to press for up to 10 hours before a sufficient temporary adhesive force develops, which allows Transferring it to a finishing press without damaging the workpiece. As the initial binding force the adhesive composition according to the invention is very high and is not subject to any thermal influence, the The time required for the temporary pressing can be significantly reduced, typically 10 minutes are sufficient. Accordingly, when the adhesive composition of the present invention is used, production can be increased considerably per unit of time.

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-H-

(2) In addition, the adhesive composition of the present invention with the exception of volatile bases or epichlorohydrin used during manufacture, is free from irritating odors. However, Ea do not become harmful or harmful during the heat pressing step releases irritating odors. As a result, the jobs differ in an advantageous manner from those where known thermoplastic adhesive composition settlements be used.

(3>) The binding force of the adhesive composition of the present invention is based on the ionic or chelate reaction between the carboxyl groups and the netal oxide or metal hydroxide and the decomposition reaction between the carboxyl groups and the epoxy groups. Since no by-products are formed, the binding force is relatively stable over longer periods of time and decreases with the expiry of the Time does not go down significantly.

(4) Because the viscosity of the adhesive composition is freely controlled can be and the polymer, which has a high degree of polymerization, is dissolved, the inventive Adhesive composition with pullers such as floor pullers and drip pullers (curtain coaters).

(5) Since the reaction described under 3) takes place at room temperature, sufficiently high bonding forces and moisture strengths can be achieved under milder temperature and time conditions than is the case when a known adhesive composition containing a thermosetting resin is used. Furthermore, the same moisture strength or binding force under humid conditions can be achieved by the cold pressing process as is the case with the hot pressing process .

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(6) Using the adhesive composition of the present invention is used, no prior drying process is required, as the binding force is determined by the water content of the Wood is not affected.

The inventive adhesive composition can according to known Working methods can be applied under normal conditions. Great economic benefits can result Use of the adhesive composition according to the invention can be achieved because many desirable effects can be obtained under ordinary working conditions. It puts is a great advantage "that known covering and gluing processes can be changed to a large extent in an advantageous manner and that the method of manufacture of plywood can be carried out continuously at a very high speed.

The adhesive composition of the invention is special useful as an adhesive composition for wood (e.g. for Plywood, chipboard, fittings for furniture and sporting goods). The composition can also be used for the production of V / ell cardboard, paper, cloth, ceramics, inorganic boards (e.g. mineral fiber boards, such as asbestos boards, rock wool boards etc. and cement boards, such as asbestos / slate boards, Cellulose / cement panels and concrete panels), plastic panels (e.g. polyvinyl chloride panels or asphalt panels), Glass plates and glued wood wool can be used. Furthermore, the adhesive composition can be used to two or more identical or different materials of the type described above as well as materials of other types connect to.

The following examples are intended to explain the invention further, but without restricting them. Unless otherwise indicated, all parts and percentages are by weight.

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example 1

25 g of isobutylene / maleic anhydride copolymer (mol ratio 1: 1, degree of polymerization 1700), 10 g of sodium hydroxide and 65 ° C. water were mixed, whereupon the mixture obtained was ^{heated to 65 °} C. to form a solution. 25 g of slaked lime, 5 g of Shokosan clay and 67 g of water were added to this solution in the order given, and the material was stirred to form a white suspension. Then 25 c of a styrene / butadiene mixed polymer latex (pesticide concentration 48% by weight) were added, whereupon 5 g of a water-soluble epoxy resin (glyceryl cidyl ether) were added and stirred in. The / else obtained in this V present in the form of a solution Klebstoffsusammensetzung showed a Anfangeviskosität 1800 Centipoi.se at 3O ⁰ C and after 10 hours a viscosity of 10,000 centipoise.

For comparison purposes, common thermoplastic resins of the following compositions were prepared:

Urea resin composition: urea resin (48 5 wheat flour ■ water
Ammonium chloride

Me laminated resin composition:

Melamine resin (50 ^) wheat flour
V / ate he
Ammonium chloride

100 parts by weight

20 parts by weight

15 parts by weight

0.3 parts by weight

100 parts by weight

15 parts by weight

15 parts by weight

0.3 parts by weight

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About 30 minutes after the addition of the epoxy resin, these adhesive compositions became different on each side LauenfurrAere (lauan plates) in quantities of 32 g / 900 cn applied, after which the veneers formed plywood samples (0.75 mm χ 1.5 ran χ 0.75 mm) were laminated. To after setting for 10 minutes, the plywood panels were cold-bonded for 10 minutes at a pressure of 10 kg / cm

2 presses, whereupon it during a pressure of 10 kg / cm

* 1 minute at -120 ⁰ C in the heat were pressed.

Table 1 below shows the results of the tests on the adhesive composition according to the invention in comparison with adhesive compositions containing thermoplastic resins. The bonding strengths of the compositions for the plywood, which was obtained only by cold pressing, without pressing at a pressure of 10 kg / cm at 120 ^° C. for 1 minute, are given in brackets in Table 1 below.

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adhesive

invented

manure

moderately

TABEL

' i

Investigated value of binding force (kg / cm)

maximum

minimum

middle

Initial adhesive tack 9.8 (9.8)

8.2 (8.2) 8.9 (8.9)

Bonding power in the dry bonding test

Binding power in the heat-cold impregnation test (Hot and Cold Soaking Test)

Binding power in the test with the boil cycle (Cyclic Boil Test) 14.9 (14.5) 12.1 (12.3) 13.5 (13.0) 12.7 (13.0) 10.5 (10.7) 11.9 (12.0) 11.7 (11.0) 8.5 (9.0) 10.0 (9.6)

_ω urea
Jh harz-O composition

Initial adhesive tack

Bonding power in the dry bonding test

Binding power in the heat-cold impregnation test (Hot and Cold Soaking Test)

Binding power in the test with the boil cycle (Cyclic Boil Test)

0.5 (0.5) 0 (0) 0.1 (0.1) K)
NJ 12.1 (1.2) 9.5 (0) 10.8 (0.5) cn
OO 9.5 (0) 7.8 (0) 8.5 (0) 1.8 (0) 0 (OO 0.3 (0) 0.3 (0.3) 0 (0) ο, ι (0.1) 1 ^, 3 (2.1) 9.8 (0) 12.8 (0.8) 13.9 (0) 8.3 (0) 12.2 (0) 10.5 (0) 8.1 (0) 9.8 (0)

Melamine resin composition

Initial adhesive tack

Bonding power in the dry bonding test

Binding power in the heat-cold impregnation test (Hot and Cold Soaking Test)

Binding power in the test with the boil cycle (Cyclic Boil Test)

In Table 1 above, the initial binding force represents the tensile strength after cold pressing at a pressure of 10 kr / cm ² after 10 minutes. The other binding forces were "beEtir.mt" according to the Japanese Agricultural Standards method (JAS method).

25 β isobutylene / maleic anhydride copolymer (molar ratio 1: 1, degree of polymerization 1200), 6.5 g of sodium hydroxide and 68.5 g of water were mixed, whereupon the mixture obtained was heated to 90 to 100 ° C. to form a solution. 25 U of talc, 70 g of an 18% aqueous solution of polyvinyl alcohol (degree of polymerization 480) and 7.5 g of a water-soluble epoxy resin (polyethylene glycol diglycidyl ether) were added to this solution in the order given, and the mixture was stirred to form an adhesive composition. This solution had an initial viscosity at 3O ⁰ C 1 200 centipoise and exhibited after about 4 hours a viscosity of 10,000 centipoise, the adhesive composition were ßperrholzproben made about 1 hour after the addition of the epoxy resin according to the above in example 1 using. These samples The results obtained are summarized in Table 2 below:

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TABLE 2 value Cohesiveness (kg / cm ² ) ,8th 8.3 Investigated maximum Minimum means , 4 15.5 Initial binding force Dry food 8.9 7th , 5 11.2 Cohesiveness with the
adhesion test Heat cold 17.2 13th , 2 9.0 Binding force in the
Impregnation test Test with 11.8 10 Cohesion with the
Cooking cycle 10.3 9

Example 3

25 6 styrene / maleic anhydride copolymer (molar ratio 1: 1, degree of polymerization 1200), 8 g of sodium hydroxide and 67 g of water were mixed, whereupon the mixture obtained was heated to 65 ° C. to form a solution. To this solution, 30 g of slaked lime and 66 g of water were added in that order and the mixture was stirred to form a white suspension. To this suspension were added 25 g of a styrene / butadiene copolymer latex (solids concentration 48%) and 10 g of a water-soluble epoxy resin (glycerol diglycidyl ether) in this order, and the mixture was stirred to form an adhesive composition. This solution showed an initial viscosity at 3O ⁰ C 1500 Centipoiae and showed about 5 hours a viscosity of 10,000 Centipoisc on. The bonding strengths of this adhesive composition 30 minutes after the addition of the epoxy resin were examined as described in Example 1 and the results obtained are shown in Table 3 below.

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Investigated value

Binding force (kg / cm '

Dry food maximum minimum , 3 middle Initial binding force Heat cold 9.1 7th ,1 8.2 Cohesiveness with d-en
adhesion test Test with 13.3 12th , 9 12.8 Cohesiveness with the
Impregnation test 12.0 10 , 6 '11.5 Cohesiveness with the
Cooking cycle 10.1 9 9.7

ρ i e 1

25 g of ethylene / acrylic acid copolymer (molar ratio 80:20, Polyraerisationsgi'ad 1600), 3 g of sodium hydroxide and 72 g of water were mixed, whereupon the mixture obtained was ^{heated to 65 °} C. to form a solution. 30 g of slaked lime, 2.5 g of aluminum hydroxide and 5.9 g of a 4.24 # strength / aqueous solution of polyacrylamide (degree of polymerization 5300) were added to this solution, and the mixture was stirred. Then 7.5 g of a water-soluble epoxy resin (polyethylene glycol diglycidyl ether) was added, and the resulting mixture was stirred to form an adhesive composition. The adhesive solution showed an initial viscosity at 3O ⁰ C of 5100 centipoise, and after 9 hours a viscosity of 10,000 centipoise. The bonding strength of this adhesive composition 30 Muniten after the addition of the epoxy resin was investigated as described in Example 1, and the results obtained are summarized in the following Table 4:

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TABLE 4 Binding force ( Mini space kß / cH ² Investigated value maximum 8.3 middle 10.0 10.5
9.5 9.5 Initial binding force 13.9
10.8 8.0 12.5
9.9 Cohesion at dexi
exercise test
Cohesiveness with the
Impregnation test Dry bonding
Heat cold 9.5 9.0 Cohesiveness with the
cycle Test with cooking

Example 5

30 g of isobutylene / maleic anhydride copolymer (molar ratio 1: 1, degree of polymerization 730), 75 g of sodium hydroxide and 112.5 g of water were mixed. The mixture obtained was ^{heated at 95 °} C. so that a solution was obtained. 15 g of epichlorohydrin were added to this solution and the mixture was reacted at 40 ^° C. for 1/2 hour, so that an aqueous solution of a glycidyl ester compound was obtained. This aqueous solution (100 g) was added to a suspension obtained from 25 g of slaked lime, 55 g of water and 10 g of a styrene / butadiene copolymer latex (solids concentration 48% by weight). The obtained mixture was stirred to form an adhesive composition. The adhesives Btofflösung showed an initial viscosity of 890 centipoise at 30 ⁰ C and about 7 hours later, a viscosity of 10,000 centipoise. The bonding strength of this adhesive composition was investigated as described in Example 1 and the values obtained are summarized in Table 5 below:

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TABLE 5

Examined Fourth

Initial binding force

t bonding power in the dry bonding test

Binding power with the heat-cold impregnation cot

Binding force in the test with cooking cycle

Bind ek raft (kg / cm)

Maximum minimum means

10.2

13.1

12.3

10.8

9.3

9.2

9.7

10.5 11.2

10.3 10.9

9.8

Example 6

Ere mixed, preceded the mixture obtained at 65 ⁰ C heated to obtain a solution; v, 13 g Natrrumhydroxyd and 62 g water: 25 g isobutylene / maleic anhydride copolymer (1, [η] = 0.692 molar ratio 1). To this solution, 50 g of slaked lime and 37.5 g of water was in order, and the mixture was stirred to a ν? Obtain (^ Qe suspension. The solution showed a viscosity of 3,050 cps at 30 ⁰ C. For comparative purposes, common thermoplastic resin adhesives made of the following compositions:

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Urea resin composition Urnθtoffbarζ (48 ^ wheat flour
water
AjDQonium Chloride

Me lamin resin composition: melamine resin
wheat flour
V / ater
Ammonium chloride

100 parts by weight

20 parts by weight

15 parts by weight

0.3 parts by weight

100 parts by weight

15 parts by weight

15 parts by weight

0.3 parts by weight

These adhesive compositions were used in amounts of 20 g / 900 cn on each side of different veneers (lauanplates) applied to plywood samples (0.7mm 1.3mm χ 0.7 mm). After setting for 10 minutes

the plywood was cold-pressed at a pressure of 10 kg / cm for 10 minutes and then at a pressure of 10 kg / cm for 1 minute at 120 ⁰ C in the heat pressed.

The binding forces of the adhesive composition according to the invention are in Table 6 in comparison to the bonding strengths of the adhesive compositions described above, containing thermoplastic resins.

The initial binding force given in Table 6 below is the tensile strength determined with the aid of the plywood became. The adhesive compositions were applied to two ΗοΙζ veneers applied of the same thickness, whereupon a plywood was made, which for 10 minutes at a pressure of

10 kg / cm pressed in the cold and at atmospheric pressure Was allowed to stand 90 minutes before determining the tensile strength. The other binding forces are those according to the JAS method certain tensile strengths.

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TABEL

adhesive

Investigated value

cn fs »

according to the invention

Initial binding force

Bond strength in the dry bond test

Binding power in the heat-cold impregnation test

Binding force in the test with cooking cycle Binding force (kg / cm)

Maximum minimum means

11.5 11.0

11.2

8.8
8.4

9.5 13.1

9.9 9.2

Urea resin composition

Initial binding force 1.3

Bond strength in the dry bond test 11.5

Binding force with the heat-cold-impregnation

kidney test 10.8

Binding power in the test with boiling cycle 1.5

0.3
9.2

8.3

0.5 o, 5

9.5 0.2

Melamine*

composition

Arifang binding force

Bond strength in the dry bond test

Binding force in the heat-cold impregnation test

Binary strength in the test with cooking cycle

O ₉ 3

10.8

0
9.2

8.5

12.5

12.0 9 _S 5

CJl CD

The binding force of the adhesive composition according to the invention, bectinrat on the plywood samples, changes in the course from 8 months only from 13.1 kg / cra to 12.9 kg / cm. These Tatcache shows that the binding force increases when the Don't change time. The binding forces of the urea composition however, ax of time decreased considerably, e.g.

2 2

over the course of 8 months from 10.5 kg / cm to 8.2 kg / cm.

In the course of 1 week, no change in the viscosity of the adhesive composition according to the invention could be observed during the viscosity of the Karnstoffhatz composition increased so much that the material gelled, making the practical use of this material impossible became.

Example 7

25 g propylene / maleic anhydride copolymer (molar ratio 1: 1, [α] = 0.350), 14.3 g sodium hydroxide and 60.7 g water were mixed, whereupon the mixture was heated to 65 ° C. to obtain a solution. 42.5 g of slaked lime, 5 g of clay and 30 g of water were added to the solution in this order, and the mixture obtained was stirred to form a white suspension which had a viscosity of 1500 centipoise ^{at 30 ° C.} Using this suspension, plywood samples were produced as described in Example 1, whereupon the binding forces of the suspension were examined. The results obtained are given in Table 7:

209852/0940

Investigated value Dry food Binding forces (kg / cm minimum middle 0 TABLE 7 Hitae cold maximum 8.0 9, 5 Initial binding force Test with cooking 10.2. 2.2 12, 2 Cohesiveness with the
adhesive test 14.3 8.2 9, 1 Cohesiveness with the
Impregnation test 11.0 2.0 3, Cohesiveness with the
cycle 4.0

example

25 g of isobutylene / maleic acid monoethyl ester copolymer (molar ratio 1: 1, [Q] = 0.882), 5.4 g of sodium hydroxide and 70 g of water were mixed at room temperature to form a solution. TOO g of zinc oxide, 5 g, were added to this solution Shokosän clay, 5 g wood flour (lauan wood powder), the mm through a sieve having a mesh width of 0.149 (100 mesh) was driven and 65 g of water in this order and stirring the mixture to form a suspension at 30 ⁰ C had a viscosity of 2100 centipoise. Using this suspension, a plywood was produced as described in Example 1, and its bonding strength was investigated. The results obtained are given in Table 8:

209852/0940

Investigated value Ils Dry food Cohesiveness ρ
(kg / cm 1 7, 2 Hot-cold LX ir 9 12, 2 - 28 - Initial binding force Tcst with O ₁ 5 9, 0 TABLE 8 Cohesiveness with the
adhesion test H ₁ ό ■ ■ :, Cohesiveness with the
Impregnation test 1O ₁ Minimum means Cohesiveness with the
Cooking cycle 6, cum 11 , 3 8th, VJl ■ '» , 3 0

Example 9

25 g of isobiitylene / l-maleic anhydride copolymer (molar ratio 1: 1, [η] = 0.711), 13 g of sodium hydroxide and 62 g of water were mixed and the resulting mixture was ^{heated to 65 °} C. to form a solution. To this solution were added 42.5 g slaked lime, 1.25 g zinc hydroxide, 20 g styrene / butadiene latex (Dow latex with a pesticide concentration of 48 ^c />) and 30 g water in this order and the mixture was stirred to form a white suspension which had a viscosity of 4500 centipoise ^{at 30 0 O.}

Using this suspension, plywood was produced as described in Example 1, and its binding force was investigated became. The results obtained are summarized in Table 9 below:

209852/0940

to the TABLE 9 ert Bind ekraft (kg / cm ² ) 5 middle to the maximum minimum 9 12.3 Examined W the
1 12.8 11 9 19.9 Dry food 20.5 18 Ci 11.1 Heat-IOilte- 12.5 9, 2.8 Initial binding force Teüt rait 4.0 ¹ 1 Binding force at
adhesion test Binding force at
Impregnation test Binding force at
Kochijykluss

example

10

25 g of isobutylene / maleic anhydride copolymer (molar ratio 1: 1, Polyraerisationegrad 1800 [r \] - 1.5), 10 g of sodium hydroxide and 65 g V. ^r ater were mixed, followed by heating the resulting mixture at 8O ⁰ C, to get a solution. To the solution, 16 g hydrated lime and 141 g of water were, in this order, and the mixture was stirred to form a white suspension ^1. Then 25 g of styrene / butadiene mixed polymer latex (pesticide concentration 50% by weight) were added and the mixture was stirred to form an adhesive composition. The adhesive composition was applied in the various indicated in the following Table 10 sets to one side of a conventional corrugated cardboard boxes with A-shaped ribs, followed by hanging up a conventional topsheet and the whole for 5 seconds pressed with an electric iron with a temperature of 150 ⁰ C. . After pressing, the corrugated cardboard was left to stand for 5 seconds and then the cover sheet was pulled off again by hand. The initial binding

209852/0940

strength is due to the tearing off ($) of the glued-on piece of paper shown. The binding force in the case of dry

bungstect is indicated as kg / (5x8) cm, which determines in a conventional manner with a needle tester v / urde after the corrugated cardboard had fo 24 hours at 2O ⁰ C and a relative humidity of 65 leave.

The bonding forces of the adhesive composition according to the invention are given in Table 10 below. The amount of towel applied is given in grams

(Solids in the adhesive ) / m (combined areas of both pieces):

2098S? / 0940

ι-Τ tJ

W. CQ «Al E-)

Ci

Ό C «Η

cn

(H

-IJ -P • Η

Γ;

• π C.

• Η X cd

C- Ι

Q)

f-.

-ρ E

<υ ο ^.

lii to U)

CM

(Ω

ω E-t

u ω

-ρ

O O CO O O O T-I CM r-l

σ σ ο ο

νο οο

CM τ-Ι

CU

U 0)

ω U) C. CD

«Μ

O O νο he » O O τ-Ι τ-1 τ-) τ-Ι

co O σ \ cm

τΗ CM

VO CO

cn cm

CO
W.
C.

XJ

(U

ϋ O

Pl

(L) Ό

X) -P

CD

CM

co: <ιη

O-P ^ -

C α bO

Ή. (U X

CQ -P ν-

209852 / 09-0

Example 11

25 g Isobutylon / maleic anhydride copolymer (MoI verhältnic 1: 1, Polyraerisationsgrad 2200 [tJ = 1.76), 10 g Iis.trnumhydroxyd and 65 g of water were mixed, and the resulting mixture laan 80 to 90 ⁰ C heated to get a solution. To the solution were added 28 g of slaked lime, 25 β of an iltyrol / butadicn copolymer latex (pesticide concentration 50 Gev. $) And 192 g of water in this order and the mixture was stirred to obtain a white suspension. Then v.'urden 5 g of a water-soluble Epoxyharscs (Clycerindiglycidyläther) was added to mulled preceded the Micchung to an adhesive composition having a Anfangcviskoßität at 30 ⁰ C of 300 centipoise, and after about 8 hours had a viscosity of 450 centipoise.

For comparison purposes, there were added 5 parts by weight of resorcinol to a Dtärkeklebntoff consisting of 100 parts by weight of corn starch, 400 parts by weight .Water and 3 parts by weight of sodium hydroxide and 2 parts by weight of borax was _r, so that an adhesive composition was obtained. Using these adhesive compositions, water-resistant corrugated boards (having A-shaped ribs) were produced as described in Example 10. The initial bond strength and the bond strength in the dry bond test were investigated as indicated in Example 10. The water resistance was determined by allowing a sample at 20 ⁰ C was immersed 24 hours in water and examined the properties with a needle tester. The result obtained is given in kg / (5x8) cm. The results obtained are summarized in Table 11 below:

209852/0940

TABEL

ro ο co co cn ro »X» O CO

Adhesive composition

Investigated value

according to the invention

Resorcinol / starch adhesive composition

Initial binding force {%)

Bond strength in the dry bond test (kg / (5x8) cm ² )

Moisture strength (kg / (5x8) cm *) applied amount (g / n ² )

7.2

12.4

/, 2

7.2

12.4

Cohesiveness

Maximum minimum means

Initial binding force (?)

Bond strength in the dry bond test (kg / (5x8) cm2)

Moisture strength (kg / (5x8) cm2) 7.2 16.4

7.2

16.4

7.2 16 ₉ 4

93

92

22.0 24.8

7.0

8.0

93 89

21.5 23.9

2.5 2 _S 8

84 63

20.0 23.5

5.1 6.7

51 75

19.7 22.0

1.5 2.1

67 75

21.3 24.2

6.1 7, * »

75 '82

20.3 23.0

2.5

Example 12

Using the adhesive composition of Example 11 a cover sheet with a corrugated cardboard (Λ-shaped ribs) each containing 50 g / m paraffin wax, with one another glued to form the pores. The samples vmrden examined as described in Example 10 and the obtained The results are summarized in the following table 12:

TABLE 12 9.6 Cohesiveness 100 middle Investigated value aufgetra 16.8 Maximum minimum 100 100 generous amount
(g / m ² ) 100 14.5
17.6 100 Initial binding force (Ϊ) 9 _t 6 100 3.8 16, H.
17.8 16.8 19.3
18.0 5.5 4.5 Binding force in the dry _q ,
adhesion test ^y *
(kg / (5x8) cm ² ) 16.8 6.7 Moisture resistance
(kg / (5x8) cm ² )

209852/0940

Example 13

120 g of isobutylene / maleic anhydride copolymer (molar ratio 1: 1, polymerization degree 550, [q] = 0.6), 50 g ITatriumhydroxyd and 483 g of water were mixed and the obtained mixture was heated to 9O ⁰ G, to obtain a solution . To this solution were added 180 g of quenched

Lime and 107 g V / asscr in the order given and ν

stirred the mixture to form a white suspension. Then 360 g of styrene / butadiene copolymer latex were added (Solids concentration 50 wt .- ^) ziiggend so that an adhesive composition was obtained.

The initial bond strength of this adhesive composition was determined as follows:

Two sheets of the materials to be bonded with areas of 2.5 cm χ-2.5 cm were produced at 20 ^° C. and 60 ° C. relative humidity. A prescribed amount of the adhesive composition was quickly applied to one side of the sheet, and the other material was quickly placed thereon and pressed with it at a pressure of 6.5 kg / cm for a prescribed time. After 10 seconds, a tensile friction force was determined at a constant tensile speed, whereupon the maximum value was found. The bond strength according to the dry adhesion test was determined by pressing the sample at a pressure of 6.5 kg / cm for a certain time and allowing the sample to stand for 48 hours, whereupon the compressive tear strength was measured at a load of 1 ton / minute at 20 ⁰ C and a relative humidity of 65 $> determined in the usual way. The results obtained are shown in Table 13 below.

The j ^ ebsij ^ ff was used in an amount of TO ί 1 g of adhesive /

- ¥ & GT applied. For comparison purposes, the

20S852 / G940

Initial binding forces of a vinyl acetate emuleion and a Urea resin adhesive composition after cold pre-pressing instead of conventional hot pressing the present proceedings. The initial binding force was 0 to 0.2 kg / cm for 20 seconds after cold pressing, which is compared to the initial binding force of the adhesive compositions of the invention # is a very low value.

Pressing time
(Sec.) TABLE 1 3 Cohesiveness with the
Dry bonding
«■ aof material Initial binding force
(kg / cm ² ) (kg / cm) 20th 50 60
180 2.0 58
62 Lauan
wood 20th 9.0
11.0 65 60
180 4.0 80
87 Cherry
wood 11.0
. 25.0

209852/0940

example

112 g of isobutylene / maleic anhydride Mischpolyinerisat (molar ratio 1: 1, Polyinerisationsgrad 500 [ηJ = 0.55) were mixed, 47 g Iiatriumhyöroxyd and 172 g Wasser.wurden ,, preceded the resulting mixture to 90 ⁰ C raan heated to prepare a solution to receive. 169 g of slaked lime, 162 g of water and 338 g of a styrene / butadiene copolymer latex (pesticide concentration 50% by weight) were added to this solution in the order given, and the mixture was stirred to form a white suspension. Then, v / ere 11g of a water soluble epoxy resin (Glycerindiglycidyläther) eye enter, and the mixture was stirred until nan received an adhesive composition having an initial viscosity at 30 ⁰ C 10 000 centipoise, and sat be after 3 hours a viscosity of 13,000 centipoise ~.

Using this adhesive composition were Samples viie described in Example 13 prepared on which the binding forces are determined as described in Example 13 The results obtained are summarized in Table HA below

Pressing time
(Sec.) OiABELLE HA material 20th
60
180 Initial binding force
(kg / cm ² ) Lauan
Wood 20th
60
l80 2.0
6.0
10.0 Cherry
wood 3.0
10.0
22.0

Bond strength in the dry bond test (kg / cm ² )

52.

70

2098S2 / Q940

The binding forces after cold pressing for 20 seconds were investigated on samples made using the same adhesive composition as described above, with the different in the table HB specified materials were used. The samples given in Table HB were prepared by the adhesive composition in an amount of 10-1 g

Q rO Qht g-

Adhesive a ■ applied and the material during Squeezed 20 champagne bottles. The V / ae resistance was after the JAS process, type II intended for plywood (the process consists in that the plywood is cut into warm and cold water immersed).

Pressing time
(Sec.) TABLE HB Damp & DStig-
speed
(kg / cin) material 20th Cohesiveness with the
Dry bonding
test ρ
(kg / cn /) beech 20th 68 12th board
(Shelf) 20th en 23 Lauan 20th 52 21st America
niche
Duty 51

209852/0940

Example- 15

25 g of isobutylene / maleic anhydride mixed polymer (molar ratio 1: 1, degree of polymerization 1700), 13 g of sodium hydroxide and 62 g of water were mixed, whereupon the mixture obtained was ^{heated to 65 °} C. in order to produce a solution g slaked lime, _# 5 g Shokosan clay and 62 g water / water in this order and the mixture was stirred to form a white suspension. 10 g of a 25% aqueous solution of polyvinyl alcohol (degree of polymerization 550, degree of saponification) were added to this suspension 98 Μο1 ~ #), and the mixture was stirred. Then, 5 g of a water-soluble epoxy resin (Glycerindiglycidylather) 10g was added to the mixture, which was mulled to an adhesive composition comprising an initial viscosity at 30 ⁰ C of 5000 centipoise, and after about 5 hours a viscosity of 10,000 centipoise.

For comparison purposes, conventional thermoplastic resin blends were used of the following compositions prepared and investigated :.

Urea resin composition:

Urea resin (48 # 100 parts by weight

Wheat flour 20 parts by weight

Vasser 15 parts by weight

Ammonium chloride 0.3 parts by weight

Melamine resin composition:

Melamine resin ( $ 50>) 100 parts by weight

Wheat flour 15 parts by weight

Water 15 parts by weight

Ammonium chloride 0.3 part by weight

Phenolic resin composition:

Phenolic resin (50 #) 100 parts by weight

Coconut shell powder 10 parts by weight

Water 5 parts by weight

209852/0940

These adhesive compositions were applied in amounts of 32 g / 900 cm to a veneer (lauan boards) about 30 minutes after the addition of the epoxy resin, after which plywood samples (0.75 mm × 1.5 mm × 0.75 mm) were produced. The plywood samples vmrden 10 Hinuten allowed to stand and then for 10 minutes at a pressure of 10 kg / cm in the cold and for 1 minute at a Hruck of 10 kg / cm pressed at a temperature of 12O ⁰ C in the heat, while the samples , which were produced with phenolic resin composition, were pressed at a pressure of 10 kg / cm 2 for 2 minutes at 130 ⁰ C in the heat.

The binding forces of the adhesive composition according to the invention have been determined and are thermoplastic in comparison to the adhesive compositions described above Resins included in Table 15 below. The binding forces that were only obtained by cold pressing are shown in brackets. The initial binding force is the tensile strength after cold pressing at a pressure of 10 kg / cm for 10 minutes. the Binding force after boiling for 100 hours was determined by boiling the test sample for 100 hours and left them in the water until the temperature of the water Had reached room temperature, whereupon the binding force was determined under humid conditions. The remaining binding forces were determined according to the JAS method.

209852/0940

C0T

TABLE 15

Adhesive composition

Investigated value of binding force (kg / cm)

n> invention

° according to
to

maximum

minimum

Initially indekraft

Bond strength in the dry bond test

Binding power in the heat-cold impregnation test

Binding force in the test with the cooking cycle Binding force after 100 hours of cooking IM (14.9)
13.6 (13.3)
13.5 (13.8)

11.8 (11.8) 11.0 (10.8) 10.3 (10.1)

middle

9.6 (9.5) 8.0 (8.0) 8.6 (8.5) 15.3 (15.0) 12.1 (12.3) 13.7 (13.5)

13.5 (13.7) 12.3 (12.0) 11.2 (11.3)

Urea resin

set

Initial binding force

Bond strength in the dry bond test

Binding power in the heat-cold impregnation test

Binding force in the test with the cooking cycle Binding force after 100 hours of boiling 0.5 (0.5)
15.0 (1.5)

10.2 (0)

3.6 (0)

J *? F (0)

0 (0)

11.6 (0)

8.5 (0)

0.5 '(0)

0 (0)

0.1 (0.1)

13.1 (0.5)

9.3 (0)

1.5 (0)

Continued TABLE 15;

Adhesive composition

Investigated value

Binding force (kg / cm)

maximum

minimum

middle

Melamine resins

Together-

Settlement

approx

Initial binding force

Bond strength in the dry bond test

Binding power in the heat-cold impregnation test

Binding power in the cooking cycle test, binding power after 100 hours of cooking 0.3 (0.3)

13.8 (0)

10.5 (0)

8.3 (0)

(0)

. (1.2) 11.5 (0)

10.7 (0) 8.6 (0) 6.0 (0)

0.1 (0.1)

12.5 (0.3)

12.1 (0)

9.3 (0)

7.2 (0)

Phenolic resin compound settlement

Initial binding force

Bond strength in the dry bond test

Binding power in the heat-cold impregnation test

Binding power in the cooking cycle test, binding power after 100 hours of boiling

0.1 (0.5)

11.8 (2.3)

13.5 (0)

13.3 (0)

12.9 (0)

(.0)

11.3 (0)

10.9 '- (Ο)

10.5 (0)

10.0 (0)

0.1 (0.1)

12.8 (0.8)

12.5 (0) 12.0 (0) k> 11.3 (0) ^ J cn

Example 16

100 g of isobutylene / maleic anhydride copolymer (MoI ratio 1: 1, degree of polymerization 1200), 40 g Eatriumhydroxyd and 260 g Yiasser were mixed and the obtained mixture vrurde to 6O ⁰ C is heated, so that a solution was obtained, which in four parts was divided by 100 g each. 50 g of slaked lime, 80 g of water and an aqueous solution of the polyvinyl alcohol shown in Table 16A below were added to each solution in the order given, and the mixture was stirred. Then 5 g of water-soluble epoxy resin (polyethylene glycol diglycidyl ether) was added and each mixture was stirred to form an adhesive composition. Using these adhesive compositions, plywood samples were prepared as described in Example 15 and the bond strengths reported in Table 16B below were examined. The specified in Table 16A under "amount" of first number relates to the grams of polyvinyl alcohol, and the number in brackets represents the weight _e - $ polyvinyl alcohol, based on the weight of the isobutylene / maleic anhydride copolymer.

TABLE 16A

Aqueous poly- concentration (g) polymer saponification vinyl alcohol ( %) {%) degree of solution degree (MoI-Ji)

I. 25th 30th (30) 200 98 II 25th 10 (10) 300 80 III 25th 10 (10) 1000 98 IV 25th 5 (5) 1700 '88

209152/0940

TABLE · 16Β

.Aqueous
Polyvinyl
alcohol solution

Examined test

Binding force (kg / cm) maximum minimum medium

Initial binding force

Binding force in the dry adhesion test Binding force in the heat-cold impregnation test Binding force in the test with cooking cycle Binding force after 100 hours of boiling 10.7
16.3
15.6
15.5

8.2 12.8 12.1 12.1 11.7

9.2

14.7 14.2 13.8 12.5

II

Initial binding force

Binding force in the dry adhesion test Binding force in the heat-cold impregnation test Binding force in the test with cooking cycle Binding force after 100 hours of boiling 10.2
15.5
15.3
14.0
13.6

7.0

12.1 11.7

11.3 9.8

8.6 13.8 13.6 12.5 11.2

III

Initial binding force

Binding force in the dry adhesion test Binding force in the heat-cold impregnation test Binding force in the test with cooking cycle Binding force after 100 hours of boiling 11.7
17.2
16.5
15.0

8.6 13.8 13.5 12.8 11.7

10.5 15.6 15.1 13.9 12.8

IV

Initial binding force

Binding force in the dry adhesion test Binding force in the heat-cold impregnation test Binding force in the test with cooking cycle Binding force after 100 hours of boiling 11.9
16.7
15.9
14.8

13.9

8.1 12.0

11.7 11.2

10.8

10.3

14.0 13.3 12.1

B β egg pie 1

25 g of styrene / maleic anhydride MiDchpolymerisat (molar ratio 1: 1, Polyraerisationsgrad 1200), 8 g and 67 g Satriumhydroxyd V / ater were mixed, followed by die.erhaltene mixture to 65 ⁰ C heated to obtain a solution ,. 30 g of zinc hydroxide and 60 g of water were added to the solution in this order and the mixture was stirred to form my white suspension. 10 g of a 25% aqueous solution of polyvinyl alcohol (polymerization grade 300, degree of saponification 98 mol%) were added to this suspension, and the mixture was stirred. Then, 5 g of a water-soluble epoxy resin (Glycerindiglycidyläther) eye sets and the mixture stirred to obtain an adhesive composition having an initial viscosity at 30 ⁰ C of 2,000 Gentipoise and after 6 hours a viscosity of 10,000 Oentipoise. The binding forces of this composition were determined as in Example 15 30 minutes after the addition of the epoxy resin, the results obtained being given in Table 17:

TABLE 17 Investigated value Binding force (kg / cm ² ) minimum middle Initial binding force maximum 7.6 8.7 ' Binding force in the dry
adhesion test 9.3 "12.3 13.5 Binding force in the heat-cold
Impregnated e st 14.6 11.7 13.0 Cohesive strength in the test
Cooking cycle 14.2 10.5 '11, 3 Binding power after 100 hours
Cook 13.0 10.2 11.8

example

25 g of ethylene / acrylic acid copolymer (molar ratio 80:20, degree of polymerization 1600), 36 sodium hydroxide and 72 g of water were mixed and the resulting mixture was heated to 65 ° C. so that a solution was obtained. 25 g of Kagnesiujnoxide, 5 g of talc and 60 g of water were added to this solution in this order and the mixture was stirred. 10 g of a 25% aqueous solution of polyvinyl alcohol (degree of polymerization 100, saponification degree 88 Ho 1-5) were added to this mixture ») And stirred the suspension. Then, 7.5 g of a water-soluble epoxy resin (Polyäthylenglykoldiglycidyläther) was added and the mixture stirred to form an adhesive composition, which had an initial viscosity at 30 ⁰ C of 4200 centipoise, and after 7 hours a viscosity of 10,000 centipoise. The bonding forces of the adhesive composition according to the invention were determined as in Example 15 30 minutes after the addition of the epoxy resin, the results obtained being shown in Table 18 below.

TABEL Investigated value 18th Binding force (kg / cm ² ) minimum middle Initial binding force maximum 8.0 9.2 Binding force in the dry
adhesion test 10.5 11.3 12.7 Binding force in the heat-cold
Impregnation test 14.1 10.6 12.1 Bond strength in the test with Koch
cycle 13.7 9.5 10.9 Binding power after 100 hours
Cook 12.2 8.6 9.8 10.7

209852/0940

- 47 - ■ ■.

Example 19

30 g of isobutylene / Kaleincäureanhydrid-Msehpolymerisat (MoI ratio 1: 1, degree of polymerization 730), 75 g of liatric hydroxide and 112 g of Viacser were mixed and the obtained The mixture was heated to 95 ° C. so that a solution was obtained. To this solution one gave 15 g of epichlorohydrin and put the mixture for 30 minutes at 40 C, whereby an aqueous solution of the glycidyl ester compound was obtained.

This solution (100 g) is added to a suspension consisting of 25 g of slaked lime, 5 g of Shokocan clay, 50 g of water and 10 g of a 30% aqueous solution of polyvinyl alcohol (Degree of polymerization 500, degree of verse if 98 mol-J-o) whereupon the obtained mixture was stirred to obtain an adhesive composition having an initial vicosity at 30 ° C of 1200 contipoise and after 6 hours a viscosity of 10,000 centipoise. Me Bonding strengths of this adhesive composition were as in Example 1, the results obtained are shown in Table 19 below.

Investigated value to the Dry food 9 ρ
Binding force (kg / cm) minimum middle Initial binding force
Cohesiveness with the
adhesion test to the Heat cold maximum 7.1
10.3 8.6
11.5 Binding force at
Impregnation test Test with cooking 9.8
13.2 9.6 11.0 Binding force at
cycle Binding power after 100 hours
Cook 12.7 9.0 10.2 TABLE 1 11.5 8.2 9.5 10.6

209857/0940

Claims (29)

PATENT CLAIMS: 1. Klebstoi'f ^ usarjnericetzung, characterized in that that they (A) a copolymer of an olefin and a carboxylic acid or an alkali metal salt of this copolymer and (B) a hydroxide of a rhodium metal or an oxide of a polyvalent metal contains. 2. Adhesive composition according to claim 1, characterized characterized in that it additionally contains an epihalohydrin. 3. Adhesive composition according to claim 1, characterized characterized in that it additionally contains a water-soluble compound which has at least two epoxy groups per molecule having. 4. Adhesive composition according to claim 2, characterized characterized in that it additionally contains a polyvinyl alcohol. 209852/0940 5 # adhesive composition according to claim 3 »thereby characterized in that they also contain a polyvinyl alcohol contains. 6. Adhesive composition according to claim 2, characterized marked; that they also contain a styrene / Contains butadiene mixed polymer latex, 7. Adhesive assemblies according to claim 3, characterized characterized in that they also contain a styrene / butadiene-IIischpolyr /> erinatlatox contains. 8. Adhesive composition, characterized in that daflTs them (A) a copolymer of an olefin having 2 to 8 carbon atoms and maleic anhydride or a Alkali metal salt of this copolymer and (B) a polyvalent metal oxide or a polyvalent metal hydroxide contains. 9. Adhesive composition according to claim 8, - characterized characterized in that it additionally contains a water-soluble compound which has at least two epoxy groups per molecule having. 2098S2 / 0940 10. Adhesive composition according to claim 8, characterized characterized in that they also contain an epihalohydrin contains. 11. Adhesive composition according to claim 9 »thereby characterized in that it additionally contains a polyvinyl alcohol. 12. Adhesive composition according to claim 10, characterized characterized in that it additionally contains a polyvinyl alcohol. 13. Adhesive additives according to claim 9 | through this characterized in that they also contain a styrene / butadiene mixed polyamide latex contains. 14. Adhesive composition according to claim 10, characterized characterized in that they also contain a styrene / butadiene Miechpolyrcerisatlatex contains. 15. Adhesive composition according to claim 1, characterized characterized in that it additionally contains a filler. 16. Adhesive composition suitable for pure wood, thereby marked that they 209852/0940 (A) a copolymer of an olefin and an unsaturated one Carboxylic acid or an alkali metal salt of this MiDchpolynerisats and (E) a polyvalent metal oxide or a hydroxide of a polyvalent metal contains. 17. Adhesive composition according to claim 16, characterized in that characterized in that it additionally contains a water-soluble compound which has at least two epoxy groups per Having molecule. 18. Adhesive composition according to claim 16, characterized characterized in that it additionally contains an epihalohydrin. 19. Adhesive composition according to claim 17j characterized in that it additionally contains a polyvinyl alcohol. 20. Adhesive composition according to claim 18, characterized characterized in that it additionally contains a polyvinyl alcohol. 21. Adhesive composition according to claim 17 »characterized characterized in that they additionally contain a styrene / butylene copolymer latex contains. 2Q98S2 / Q9A0 2215813 22. Adhesive composition according to claim 18, characterized characterized in that it additionally contains a styrene / butadiene copolymer latex. 23. Adhesive composition according to claim 1, characterized in that characterized in that it additionally contains a polyvinyl alcohol. 24. Adhesive composition according to claim 1, characterized characterized in that it additionally contains a styrene / butadiene polymer latex. 25. Adhesive composition according to claim 8, characterized characterized in that it additionally contains a polyvinyl alcohol. 26. Adhesive composition according to claim 8, characterized characterized in that it additionally contains a styrene / butadiene copolymer latex. 27. Adhesive composition according to claim 16, characterized in that it additionally contains a polyvinyl alcohol. 28 «Adhesive composition according to Anopruch 16, characterized in that it additionally contains a styrene / butydiene mixed polymer latex. . 2098S2 / G940 29. Appropriate use of the adhesive compositions Claims 1 to 28 for the manufacture of plywood ₀ 209852/0940