FI64632B - FOER REFRIGERATION FOR LAMINATION OF LAMINATORS UNDER ANALYZING AV CONDITIONING - Google Patents

Description

U ^ ;! r T ANNOUNCEMENT

| kB- UTLÄGGN ί NGSSKRIFT 6 4 632 C (45) Γ, -ί-er.tbi inyöni '.- ·: · .tv 12 12 1933, tv l Patent ceddelat v (51) Kv.ik. ^ int.ci. 3 0 09 J 5/04 // B 52 B 31/12, 7/12 FINLAND - FINLAND (21) P »wnttlh« k «mi * - P» t «nt» ns # knlnj 762 94 4 (22) Hakamlipllvt - Ansöknlngtdig l4.10.76 (23) Atkupllv * - Glltlghettd »! l4.10.76 (41) Tullut Julklieksl— Bllvlt offerrtllg g e- γγ

National Board of Patents and Registration of Finland NlhtivUOp * ™ And the date of publication

Patent- och registerstyrelsen 'Ansök »n utlajd oeh utl.skrlft * n publfeerad il.uo.oj (32) (33) (31) Pyydetty etuoikeus — Begird prlorltet 04.11.75

Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 2549371.4 (7l) Henkel Kommanditgesellschaft auf Aktien, Heftkelstrasse 67, 4000 Dusseldorf, Federal Republic of Germany Förbundsrepubliken lyskland (DE) (7?) Hans Baurieder, Dusseldorf, Dusseldorf

The present invention relates to a method for the production of laminate sheets using a isocyanate adhesive. a compound containing groups and a second adhesive component is applied to the second plate surface.

Sheets formed by joining are usually made by means of solvent-containing cashering adhesives by applying the adhesive to the path formed by the sheets by means of rollers. In this case, after the solvent has evaporated, the paths coalesce under the influence of short-term pressure. This process, known as dry shercation, uses almost exclusively solvent-containing polyurethane adhesives, which can be moisture-curable prepolymers with end-of-chain isocyanate groups or mixtures of polyol and polyisocyanate. Recently regulated regulations on the release of solvents into the air? Due to the limitations of 64632, it has become necessary to absorb or incinerate the mixture of solvent and air, which are expensive operations.

It is an object of the present invention to provide a method of manufacturing interlocking sheets in which the adhesive is solvent-free and can therefore be made refractory or non-explosive.

It is also an object of the invention to provide a method of manufacturing interlocking sheets by means of which sheets formed by clear, firmly adhered layers can be manufactured at an technologically lower cost.

U.S. Pat. No. 3,598,671 discloses a method of making a laminate in which the laminate is formed of two flexible plastic webs with polyurethane foam interposed therebetween. In this method, water, an emulsifier and an activator are applied to the surface of the web, and a prepolymer containing isocyanate groups is applied to the other surface. When the layers come into contact with each other, water diffuses into the isocyanate layer and initiates a flotation process in which the isocyanate groups and water react to form amino groups and carbon dioxide. The amino groups further react with the isocyanate groups to form urea groups and thus provide a network structure in the polyurethane foam. In contrast to this known flotation-based method, the object of the present invention is that the gluing takes place by means of thin layers of adhesive components applied to the board surfaces to be glued. Such layers have, by means of immediate gluing or iKing, and by means of them the plate surfaces are made to adhere to each other in a short time.

U.S. Pat. No. 3,668,173 further discloses a process for preparing soluble linear polyurethane ureas. According to the publication, these linear polycondensates, which are highly soluble in organic solvents, are used as solutions, i.e. they are unreacted, practically stable storable solvents for coatings which act as film-forming agents. Ko. the known method is thus not useful in pursuing the objectives of the present invention, which require the reactivity of the adhesive components used.

The process according to the invention for achieving the above-mentioned objects is characterized in that a polyether having at least two end-chain isocyanate groups is used as the compound containing isocyanate groups, and that said second adhesive component is used molecular weight is 300-2000, and that said compounds are applied to the plate surfaces in such a way that the molar ratio of isocyanate groups to amino groups is between 1: 1 and 2.0: 1 and the components together form a layer having a thickness of 1.0-6.0 μπ>: η.

Suitable isocyanates having at least two functional groups useful in the process of the invention can be prepared by reacting anhydrous polyether diols with isocyanates having at least two functional groups in a manner known per se. The polyester diols best suited to the process are obtained from glycols having 2 to 4 carbon atoms. Thus, polyethylene and / or polypropylene glycol and / or polytetramethylene ether glycol (prepared from tetrahydrofuran by ring-opening polymerization) are suitable. Suitable isocyanates which react with polyether diols are, in particular, relatively small-molecule isocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate +, tolylene diisocyanate (mixture of isomers) and many others. Care must be taken that the viscosity of the isocyanate compounds obtained does not exceed about 8000-9000 cP during further processing. This reaction component can optionally be set even at a slightly elevated temperature of at most about 50-60 ° C. However, a temperature of 20-30 ° C is generally considered the most suitable.

Another reaction component used in the process of the invention is an amine having at least two functional groups. Its preparation can be based on the same basic structure, i.e. polyether diols. In this case, it is suitable to proceed by depositing acrylonitrile on [64632] polyetherdiol. Tam 2. The coupling product is then hydrated in a known manner, whereby the nitrite groups form primary amino groups. It is most convenient to use polyether glycols obtained from polyethylene glycol, polypropylene glycol and poly-tetramethylene ether glycol in the preparation of each of the reaction components included in the solvent. having a molecular weight of about 200-1500, especially 300-1000.

It is still possible to use as starting material relatively small molecule diamines having a chain of 2 to 18 carbon atoms, in which the carbon atoms can even be partially replaced by oxygen atoms, and to allow at least two of these diamines to react with amines-functional compounds (chaining). . Examples of such amines are h2n - σκ2 - ch2 - ch2 - o - (ch2) 2_4 - O - ch2 - ch2 - ch2 - nh2

HgK — CH2-— CH2 — OBJ — OC-CHg-OHg-O)., ^ CHg - CH2 - CH2 ~ NHg ^ · ΓΗ CH, ta, OH, /

Hr, N -1 H) - CH2 --- (H) - KH? ^ 3 ch3 ch3 or H2N - (CH2) 6_g -NH2.

Said functional groups may be, for example, epoxide or inocyanate groups, α-unsaturated oysters or halogen atoms. In the reaction, OH groups, secondary amino groups or carbara are formed. over groups or reaction starting material, the contained ester groups may in certain cases have a beneficial effect on the adhesion of the adhesive bond already in the adhesion.

Visit t d ta depo koi di. a or digl y sidy over one 5 5 64632 CK0 - CH - R - CH - CH0 or CH0 - CH - CH ~ - OR - 0CHo — CH — CK0 Λ / \ / \ / 2 ’0 Ό 0 0

wherein R is an aliphatic or cycloaliphatic group having up to about 25 carbon atoms, such as e.g. ethylene, ethylene, propylene, neopentyl, hexylene, dodecylene, cyclohexylene, dicyclohexyl, methylenedicyclohexyl or also a diethylene or triethylene glycol group, '-FH2 corresponding to a diprevine amine in which R * is, for example, an ethylene, butylene, hexylene, diethylene glycol ether, dipropyl glycol ether or triethylene glycol ether group, compounds containing two primary amino groups at the ends of the chain and corresponding primary amino groups are obtained. OH

I I

HgN - R '- NH - CH2 - CH - R - CH - CH2 - NH - Rf - NH2

When extending the molecular chain, isocyanates, such as toluene diisocyanate, hexamethylene. or isophorone diisocyanate to give compounds containing two amino groups at the ends of the chain and urea groups corresponding to the general formula 2 wherein R 'has the same meaning as above and R represents the backbone of the isocyanate molecule.

When the chain is extended (with methacrylic acid esters (for example tri- or tetraethylene glycolide (meth) acrylic esters)) the general formula 0 0 W // is obtained.

C-O-R-O-C

Compounds according to NH4, - R »- NH - CH0 - CH CH - CHO - NH - R · - NH» 2 \ / 2 2 H ^ CH3 H (CH3) F, where H ': n again has the same meaning as above and R represents a dialcohol alcohol backbone of the (meth) acrylic ester, in this case, for example, a tri- or triethylethylene glycol ether backbone. Of course, other di (meth) acrylic acid esters of glycols can also be used, such as esters of glycols of ethylene glycol, propylene glycol, butylene glycol, decandiol and the like.

Finally, it is also possible to carry out the chain extension by means of a dihalo-genide, which is carried out in a known manner according to the same principle. In this case, compounds of the general formula H2N - R * - NH - R - NH - R * - NH2 are formed, in which R represents a group having up to 12 carbon atoms, optionally also an oxygen-containing group, such as a tetraethylene glycol ether group or a tripropylene glycol ether group, and R * has the same meaning as above.

The ratio of diprevine amines to chain extenders is selected such that about 1 mole of two functional groups of epoxide, isocyanate, (meth) acrylic ester or dihalide is used per two moles of amine. The reaction produces mainly the desired compounds containing at least two primary amino groups at the end of the chain and having a molecular weight of about 300-2000. It is suitable that the amine component 11a has a slightly lower viscosity than the large cyanate component. It has proved practical to aim for a viscosity of about 50-1200 o.P at a temperature of 20-30 ° C.

Both reaction components are introduced into the plates by means of rollers so that the molar ratio of isocyanate groups to amino groups is between n.

1: 1 - 2: 1.0. The amount of material is further selected so as to obtain an adhesive film having a total thickness of 1.0 to 6.0 μm.

the plate surfaces coated with each component are pressed together between two rollers, which rollers may also be partially heated. Sufficient primary adhesion (initial stickiness) is formed in the laminate transferred to the determination step, which can possibly be increased by heating, e.g. with warm air, 7 64632

The method according to the invention enables cashering at relatively high speeds. The use of drying channels is not necessary. The displacement of the tracks relative to each other is not performed after the plates have been pressed together, nor even partial lamination.

After the sheets have been wound on rolls, they must still be stored for about 3 to 7 days at room temperature, depending on the reactivity of the adhesive film and the reactivity of the reactive components. During this time, the boards gain their ultimate strength. The peel strength of the obtained laminates is in most cases so high that it is no longer possible to peel off the joint without breaking the material.

The process according to the invention can be used to prepare sheets formed together by joining, the components of which include polyethylene (pretreated), polypropylene (pretreated), lacquered or non-lacquered cellulose hydrate, polyethylene terephthalate, polycaprolactam, polyvinyl chloride, aluminum and other metals.

The invention is further illustrated by the following examples. Example 1.

Component A: Isocyanate obtained by coupling polypropylene glycol (average molecular weight 410) and tri-methylhexamethylene diisocyanate in a molar ratio of 1: 2 (molecular weight 830).

Concentration of free large cyanate groups: $ 10.1>

Viscosity at 25 ° C: 3500 cP (Brookfield)

Component B: Aminopropylated polypropylene glycol (average molecular weight 410) prepared by depositing acrylonitrile with glycolene followed by catalytic hydrogenation (theoretical molecular weight 524).

Amine number: 170-180.

Viscosity: 60 cP (Brookfield).

2 2.5 g of component A was placed on a 1 m polyethylene sheet with a lower density and pretreated by corona discharge

O

(sheet thickness 50 μm), and 1.56 g of component B was placed on a 1 m polyester sheet (sheet thickness 12 μm) with a molar ratio of A to B of 1.2: 1 and the amounts of film thicknesses applied to the sheets. were about 2.5 μm and 1.56 μm, and the coated o 64632 sides of the plates were joined together by rollers. The mucous membrane immediately turned sticky, and 20 seconds after the imaging, a peel strength of 3-5 p / 15 mm (tensile speed 100 / min) was measured.

After storage for 24 hours, it is no longer possible to break the joint between the plates without breaking the plates.

Example 2.

Component A: Isocyanate obtained by coupling polypropylene glycol (average molecular weight 630) and tri-. methyl hexamethylene diisocyanate in a molar ratio of 1: 2 (molecular weight 1050).

Concentration of free isocyanate groups: 8.0 Viscosity at 25 ° C: 5000 cP (Brookfield).

At 50 ° C: 1000 cP

Component B: Arane-propylated polypropylene glycol (average molecular weight 630) prepared by depositing acrylonitrile with glycolene followed by catalytic hydrogenation (theoretical molecular weight 744).

Amine number: 142

Viscosity: 130 cP (Brookfield).

2 1.0 g of component A was placed on a 1 m pretreated polyethylene sheet (sheet thickness 50 grooves) and 0.74 g of component B was placed on a 1 m * cellophane sheet (sheet weight 31 → 5 g / m), whereby The molar ratio of A to B was 1.02: 1 and the thicknesses of the films placed on the plates were about 1 and 0.74, and the coated sides were joined together by means of rollers. The laminate formed from the sheets was then immediately heated to 50 ° C for ten seconds. The measured peel strength was then 5-C p / 15 mm (tensile speed 100 mm / rain). After four days of storage, it is no longer possible to break the joint between the plates without damaging the plate.

Example 3 »

Component A: Isocyanate obtained by coupling poly-tetramethylene ether glycol (average molecular weight 990) and 9,64632 toluene diisocyanate in a molar ratio of 1: 2 (molecular weight 1328). Content of free isocyanate groups: 6.33 Viscosity at 25 ° C: 7000 cP (Brookfield) 'component B: Amine according to Example 1.

2

1.38 g of component A were placed on a 1 m pretreated polyethylene sheet (sheet thickness 50) and 0.6 g of component B

Λ was placed on a 1 m polyamide sheet (sheet thickness 60 μm) with a molar ratio of A to B of about 1.1: 1 and the thicknesses of the films placed on the sheets were 1.38 and 0.6 μm, and the sheets the coated sides were joined together by rollers. The ligated plates were briefly heated to 50 ° C. Thereafter, the measured peel strength was 8-10 rpm (tensile speed 100 mm / min). After four days of storage, it is no longer possible to break the joint between the plates without damaging the plates.

Claims (3)

A method for producing laminate sheets using an isocyanate adhesive, wherein a compound containing isocyanate groups is applied to one of the surfaces to be bonded together and a second adhesive component is applied to the other surface of the sheet, said at least as the second adhesive component, longer-chain compounds having at least two primary amino groups at the end of the chain and having a molecular weight of 300 to 2000 are used, and said compounds are applied to the plate surfaces in a molar ratio of isocyanate groups to amino groups of 1: 1 to 2.0: 1; the components together form a Layer having a thickness of 1.0-6.0 μm. 1 o 64632 Process according to Claim 1, characterized in that the reaction products of polyethers and acrylonitrile which have been hydrogenated are used as compounds containing at least two primary amino groups. Process according to Claim 1 or 2, characterized in that polyethylene, polypropylene or polyethylene ethylene glycol having a molecular weight of 200 to 1500, in particular 300 to 300%, is used as starting material in the preparation of polyethers containing isocyanate groups or amino groups. 1,000.