MXPA97009145A - Adhesive process - Google Patents

Abstract

The present invention relates to the process for joining two substrates with an anhydrous adhesive or with low water content, partially crystalline, solid at room temperature, the process is characterized in that the adhesive is first activated by internal and / or external friction. Then, the substrates are joined with the intermediate adhesive. When left in a rut, the structure achieves its final resistance after a period of a few seconds to a few days. The friction destroys the crystalline structure and makes the adhesive sticky, and the recrystallization of its final strength and eliminates the sticky consistency. The adhesive is preferably based on polyester or polyurethane and is preferably used in the form of an adhesive strip without impermeable packaging. It is especially suitable for joining paper, since it does not cause corrugation

Description

ADHESIVITY PROCESS This invention relates to a process for bonding substrates using a partially crystalline adhesive, without water or with little water, solid at room temperature, to the adhesive and its production. The processes for joining substrates with solid adhesives at room temperature are known, in this way, the thermal fusion adhesives, solids at room temperature, are first heated until they become sticky and then the substrates are applied in the form of a melt that are going to join. After the substrates have been bonded, the hot-melt adhesives physically harden and solidify upon cooling through crystallization or an increase in viscosity. The raw materials for these thermal fusion adhesives are, for example, polyethylene vinyl acetate, polyamide, polyester and polyurethane. One of these PU thermal fusion adhesives is described in WO 94/137726. This document claims a water-soluble, high molecular weight, partially crystalline, non-ionic polyurethane as the base for a thermal melt adhesive. The polyurethane is characterized by the following structural units: a) -0 (-CH, -CH, -0) n-, where n = 8 to 500 and, more particularly, 20 to 300, b) -CO-NH- X-NH-CO-, wherein X is an aliphatic or cycloaliphatic residue, more particularly, a residue of an m-tetramethylxylene diisocyanate (TMXDI), and c) -0-Y-0-, wherein Y is a hydrophobic residue, more particularly (-CH2-CH (CHj) -0) m -CH1-CH (CH3) -, (-CH1-CH (C1H1J) -0) m -CH1-CH (C2H1, ) - and (-CH / -CH1-CH1-CH2-0) m-CH2-CH / -CH2-CH - wherein m = 8 to 500 and, more particularly, 20 to 300, or an alkylene or cycloalkylene containing 2 to 44 carbon atoms and, more particularly, from 6 to 36 carbon atoms, c) constitutes from 0 to 40% by weight, more particularly from 2 to 30% by weight and preferably 5 to 25% by weight based on a) + c) in the polyurethane. Thermal melt adhesives have the general disadvantage that a heat source is required for melting. Solid adhesives at room temperature which are suitable for bonding without melting, for example, adhesive sticks, are also known. To bond the substrates with an adhesive stick, the stick is simply dragged onto the substrate to be joined and the substrate thus covered with adhesive is joined to the other substrate. The adhesive that is sticky at room temperature is hardened by evaporation of the solvent or water or by diffusion of the solvent or water in the substrate. One of these adhesive sticks is described in EP 405 329. The dimensionally stable soft rub adhesive stick consists of an aqueous formulation of polyurethane as a binder, a soapy gel as the gel-forming component and, if desired, auxiliaries. The polyurethane is a reaction product of a polyol or mixture of polyols, an isocyanate component with a functionality of two or more, a component capable of forming salt in aqueous alkaline solution and / or a non-ionic hydrofolic modifier, and if desired , a chain extender agent. In Example 1d, a polyurethane was prepared from 29.7 parts by weight of isophorone diisocyanate, 100 parts by weight of polyethylene propylene glycol with an EO content of 10% and a molecular weight of 2000, 6.8 parts by weight of dimethylol acid. propionic and 2.2 parts by weight of NaOH. In the acetone process, an aqueous dispersion with a solids content of 36% by weight was prepared. Finally, the adhesive was produced from 82 parts by weight of this PU dispersion and two parts by weight of water, 7 parts by weight of glycerol, 3 parts by weight of PPG 600, 3 parts by weight of sodium palmitate and 3 parts by weight of sodium stearate. The adhesive had a hot viscosity of 2. a. s oü * 'C. An adhesive stick of the type in question has the disadvantage that it requires a hermetic packing, otherwise it would be in danger of drying and its properties would be adversely affected. further, the paper is folded under the effect of the high water content of the adhesive. These disadvantages are avoided in an adhesive stick containing a solid adhesive component and a microencapsulated solvent (see GB 995, 524). Unfortunately, this stick has the disadvantage that, after use, a skin forms on its surface and has to be removed with difficulty before the stick can be used again. The disadvantages of the water-based adhesive stick are also avoided with the adhesive stick based on wax, polypropylene and rosin according to DE 20 22 464. The bar is activated by the heat of friction, the melting of the highest adhesive layer . With the cooling the adhesive hardens almost instantaneously, so that there is no possible correction. In addition, the handling of this known bar is complicated by the formation of filaments. Finally, the presence of rosin has to be indicated on the label.

Contrary to the background of this prior art, the problem taken by the present invention was to provide a process of adhesiveness and a suitable adhesive for it, which does not have any of these disadvantages and can be used with ease. The adhesive must in particular include little or no packing, application with low pressure, a composition that does not have to be shown on the label and simple removal of the adhesive when required. The adhesive should be particularly suitable for papers and cardboards. The solution offered by the invention is defined in the claims and consists, in particular, in a process for joining substrates with a solid adhesive at room temperature, characterized in that the adhesive is activated by internal and / or external friction, the substrates Adhere with the now sticky adhesive between these and the adhesive is allowed to harden leaving it from a few seconds to a few days. To generate internal friction, the volume elements of the adhesive move relative to one another, for example, by working it between the fingers. The adhesive becomes sticky and can be used as an adhesive putty. However, the adhesive is preferably activated by external friction, for which purpose the adhesive and the substrate are rubbed together. The friction generated must be so great that a film of 2 to 200 μ thickness is obtained, more particularly, a film of 10 to 100 μ thickness after the adhesive has been passed over the substrate once at a speed of 1 to 50 cm / sec and preferably from 2 to 100 cm / sec with a pressure of 1 kPa to 10 MPa, preferably 5 kPa to 5MPa, and more preferably 10 kPa to 1.0 MPa. These values apply for normal conditions (20 ° C / 50% relative humidity in the air) and for a paper of the following quality: 5015 Spezial Copier manufactured by Soennecken. The adhesive according to the invention is solid and partially crystalline at room temperature (20 ° C). It is characterized by a) a degree of crystallization, when determined by DSC at a temperature of -40 ° C to + 120 ° C, which corresponds to a melting enthalpy of 10 to 150 J / mg, preferably 15 to 80 J / g and more preferably from 20 to 70 mJ / mg, b) at least one crystallization temperature from 20 to 110 ° C and, more particularly, from 30 to 80 ° C and, c) by a crystallization rate from a few seconds to several days, more particularly, from 30 seconds to 30 minutes. The enthalpy of fusion is determined by DSC. The crystallization temperature is determined by DSC as the temperature at which the melting peak passes its end. The crystallization rate is determined by observing a sticky layer under a polarization microscope. In view of the importance of these parameters for the adhesiveness process, the adhesive is supposed to work as follows: crystalline regions are converted to an amorphous form by mechanical action or rubbing. This amorphous form produces stickiness. As long as the adhesive does not recrystallize, it remains sticky. After recrystallization the adhesive loses its stickiness and develops its final strength. 25 to 100% by weight, more particular 30 to 99% by weight and preferably 60 to 98% by weight of the adhesive according to the invention consists of at least one binder and from 0 to 75% by weight, more particularly 0.1 to 70% by weight and preferably 0.5 to 40% by weight of additives. The binder also acts as a forming substance. The main function of these additives is to influence the behavior of crystallization, adhesion and rubbing. In addition, however, they can perform common functions, that is, stabilization, conservation, coloring, and so on. In a preferred embodiment, the binder generally consists of A) at least one partially crystalline polyester component, and B) at least one amorphous and / or liquid polyester component. Both binder components A) and B) are insoluble in water, ie, less than 10 g and, more particularly, less than 1 g is dissolved in 100 ml of water at 20 ° C. These have an average MWW molecular weight of from 1,000 to 25,000 and, more particularly, from 2,000 to 15,000. According to its crystallinity, component A can consist of 100%. The ratio of the amount of the crystalline component to the amorphous component is important. In general, the partially crystalline polyester should be from 5 to 95% by weight, preferably from 15 to 60% by weight and more preferably from 20 to 40% by weight. Components A and B must have only limited compatibility with each other, so that a mixture of the crystalline and amorphous regions is differentiable (by observation under a polymerization microscope, DSC, X-ray examination). However, a seemingly homogeneous distribution is present macroscopically and should not change over time. There should be no signs of separation, even at high storage temperatures. To achieve compatibility, it is possible to use a compatibilizer, for example a special polyester plasticizer or a special block polymer. However, the preference compatibility is stabilized by the chemical combination of the components A and B with each other, for example by the subsequent chemical bonding of the active groups to the polyisocyanates. In the context of the present invention it is understood that polyesters are polymers containing predominantly ester groups in the main chain. However, it is also suggested that they comprise polymers containing predominantly ester groups in their comb-like side chains, for example polyacrylates in which the alcohol component contains from 1 to 18 carbon atoms, and preferably from 1 to 8. carbon atoms. The other groups can be amide groups (polyester amides) or urethane groups (polyester urethanes). Pure polyesters with ester groups in the main chain are preferred. Basically, any monomer which, after polymerization, forms ester bonds in the main chain (including polycarbonates) are suitable for the production of PES. In addition to the carbon atoms, they may also contain heteroatoms (S, N, halogens, P). In addition to the acid and alcohol functions, other functional groups may also be present. In particular, any monomer of the type already used for the PES component or the PES component of the PUR thermal fusion adhesives can be used. The end groups of the polyesters can be modified by subsequent reaction, for example, by esterification and transesterification. The terminal groups are preferably OH, -COOH or urethane groups. The structural units for the polyesters are dicarboxylic acids, hydrocarboxylic acids and diols. The structural units of the dicarboxylic acids can be used in any reactive form, for example as free acid, acid chloride, ester (especially methyl ester), etc. Suitable acids are polycarboxylic aliphatic acids, especially dicarboxylic acids containing from 1 to 36 carbon atoms, unsaturated and aromatic dicarboxylic acids and dicarboxylic acids containing the S, N and halogen heteroatoms (bromo terephthalic acid, fluoroterephthalic acid) . Specific examples of these acids are oxalic acid, malonic acid, sebasic acid, azelaic acid, decandicarboxylic acid, dodecanedicarboxylic acid, dimethyl-1,4-cyclohexanedicarboxylic acid ester, p-phenylenediacetic acid, 2,5-dimethylterephthalic acid, methylterephthalic acid, 2,6-naphthyldicarboxylic acid, 4,4'-isopropyldibenzoic acid, 1,2-ethylenedioxy-4,4'-dibenzoic acid, 4,4'-dibenzoic acid (diphenic acid), sulfonyl-4,4 'acid -dibenzoic Particularly suitable are succinic acid, glutaric acid, adipic acid, isophthalic acid, terephthalic acid, phthalic acid and macromonomers (prepolymers) containing more than 36 carbon atoms.

It is also possible to use the hydroxycarboxylic acid structural units in any reactive form, for example as free acid, acid chloride, ester (especially methyl ester), etc. Suitable are aliphatic hydroxycarboxylic acids containing some hydroxy and carboxylic acid groups, but preferably a hydroxy group and a carboxylic acid group, and from 2 to 36 carbon atoms. The same is true for unsaturated and aromatic hydroxycarboxylic acids and for hydroxycarboxylic acids containing heteroatoms such as S, N and halogens. Specific examples of suitable hydroxycarboxylic acids are 4-hydroxybenzoic acid, pivalolactones, e-caprolactones, 6-hydroxy-2-naphthoic acid, lactic acid and glycolic acid. The structural polyol units can also be used in any reactive form, for example as free alcohol, ester (especially acetic acid ester), etc. Aliphatic polyols, especially diols containing from 1 to 36 carbon atoms are convenient. The same applies to the unsaturated and aromatic polyols and to the polyols containing the S, N and halogen heteroatoms. Specific examples of the suitable polyols are propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, 1-cyclohexanedimethanol, 2,2-dimethylpropane-1,3-triol, decanediol. , 4, 4 '-dihydroxy-1,1' -biphenyl, di-p-hydroxyphenylpropane, 1, -hydroquinone, bicyclo- [2.2.2] -octane dimethylene glycol, methyl-p-phenylene glycol. «Enter the formula of page 7» where n = 1 to 30 (even in position m). Preferred polyols are pentan-1,4-diol, ethylene glycol, hexan-1,3-diol, butan-2,3-diol, neopentyl glycol, 2-methylbutan-1,4-diol and macromonomers (prepolymers) containing more of 36 carbon atoms, for example, polyethylene glycol or poly (tetrahydrofuran) diol. Other suitable monomers and the ratio between monomers and crystallinity are well known to those skilled in the art (see, for example, Encyclopedia of Polymer Science and Technology, Keyword "Polyesters", pp. 62 to 128). Polyester amides are copolymers containing amide and ester groups in the main chain. A statistical copolymer is produced by co-condensing the monomers. The monomers may be diacids, diamines, diols, amino acids, hydroxy acids corresponding to the list of polyesters other than terminal groups. These can be used in any reactive form. Block copolymers can be obtained from various polyester blocks by linking, for example, polyesters terminated in carboxylic acid with diisocyanates (or NCO-terminated polymers). The (di) carboxylic acids can also be reacted with bis-oxazolines or with oxazo-dm-2-ones. Block copolymers can also be obtained from polyamides and polyesters with the aid of isocyanates or by transesterification or transactivation. Structural units for polyesters and polyamides were mentioned in the above in relation to polyesters. These are corresponding compounds with amino groups instead of hydroxyl groups. The preferred structural units again are diamines and diacids or amino- and acid-functionalized monomers, such as lactam. In another preferred embodiment, the binder is a polyurethane which can be produced from the following components: a) at least one aliphatic or aromatic diisocyanate, more particularly, MDI, TDI, HDI, IPDI and, above all, TMXDI, b ) at least one crystallizing diol, more particularly, from the following group: polyethylene glycol with an average molecular weight (average number) in the range from 200 to 40,000, more particularly, in the range from 1,500 to 15,000 and preferably in the range from 4,000 to 8,000, - polytetrahydrofuran with a molecular weight in the range from 200 to 4,000 and, more particularly, in the former range from 1,000 to 3,000, - a copolymer of ethylene oxide and propylene oxide with a molecular weight in the range since 200 to 40,000 and, preferably, in the range from 400 to 10,000, a block copolymer of the PEG / PPG / PEG type with a PEG content of 10 to 80% and, optionally, - polyester diol, more particularly, being better a polycaprolactone diol with a molecular weight in the range from 200 to 50,000 and, more particularly, in the range from 200 to 5,000, c) optionally, at least one diol capable of forming diols, more particularly, carboxylate, sulfate or ammonium ions , d) optionally at least one polyol with a functionality of 3 or more, such as glycerol and TMP, and e) optionally at least one hydrophobic diol, more particularly, of the following group: polypropylene glycol with a molecular weight in the range from 200 to 4,000, more particularly in the range from 500 to 2,000 and - an alkanediol containing from 1 to 100 carbon atoms, more particularly, from 2 to 50 carbon atoms and preferably from 5 to 30 carbon atoms, the relation of l The isocyanate groups at the hydroxyl groups can be variable from 0.5 to 1.2: 1 and more particularly from 0.7 to 1: 1. Polyurethanes can be produced in a one-step process and in a two-step process. In the two-step process, the prepolymer is initially prepared by making a partial preliminary reaction of the polyols, for example, the hydrophilic polyols with the diisicianate. Then the remaining polyol is added. However, the polyurethane according to the invention is preferably produced in a one-step process. In this process, all the initial materials are first mixed in the presence of an organic solvent at a water content of less than 0.5% by weight. The mixture is heated for about 1 to 30 hours and, more particularly, for 1 to 5 hours at a temperature of 70 to 200 ° C, more particularly, at a temperature of 80 to 170 ° C, and preferably at a temperature from 130 to 170 ° C. The reaction time can be shortened by the presence of catalysts, more particularly tertiary amines, for example triethylamine, dimethylbenzylamine, bis-dimethylamino ethyl ether and bis-methylaminomethylphenol. Particularly suitable catalysts are 1-methylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-phenylimidazole, 1,2, 5-tetramethyl-m? Dazoi, 1- (3-a-inopropyl) -imidazole, pyrimidazole , 4-dimethylaminopyridine, 4-pyrrolidino pyridine, 4-morpholino pyridine, 4-methylpyridine. However, the one-step process of preference is carried out without catalyst. It is also advisable to eliminate the solvent. Suitable solvents are inert organic liquids with a boiling point below 200 ° C at normal pressure, more particularly acetone. The polyester urethanes are prepared in the known manner from the polyester polyols and polyisocyanates, more particularly, from the polyester diols and diisocyantes. The polyester polyols were described at the beginning. These can be reacted with aliphatic isocyanates and aromatic isocyanates. Preferred diisocyanates are NDI, HDI, CHDI, IPDI TMDI, m-TMXDI, p-TMXDI, H? -MDI, PPDI, 2, 4-TDI, 80: 20-TDI, 65: 35-TDI, 4.4 'MDI, polymer-MDI and n-TMI. Other preferred isocyanates are DDI 1410, TDI, MDI, 2,4'-MDI; Desmodur R, Desmodur Rl, IEM and m-phenylene diisocyanate. These and other polyisocyanates are well known to the experts (see, for example, Encyclopedia of Polymer Science and Technology, Keyword "Polyurethanes", pp. 244 to 248). The polyester urethanes are preferably terminated in OH, COOH, ester and urethane groups. The polyester urethanes (polyether urethanes) modified by terminal groups are produced by preparing initially polyester urethanes (polyether urethanes) containing terminal NCO groups. The free terminal NCO groups are then reacted with preferably monoreactive compounds known in urethane chemistry. For example, terminal alkyl groups containing from 4 to 22 carbon atoms can be introduced through the fatty alcohols. Reactions with aromatic alcohols and polyesters containing an OH or COOH group are also mentioned. In a particularly preferred embodiment of the adhesive according to the invention, the NCO-terminated prepolymer based on an aromatic or cycloaliphatic isocyanate and a polyglycol is prepared initially, after which those NCO groups that have not reacted in this stoichiometric reaction are saturated with aliphatic alcohols containing from 4 to 22 carbon atoms, with aromatic alcohols or with polyesters terminated in OH- or COOH-, so that reaction products are formed without reactive groups. Polyester / polyurethane blends can also be used as the binder. The polyurethane can be a polyester urethane or a polyether urethane or a mixture of a polyester urethane and a polyether urethane. In addition to the binder, the adhesive may contain the following additives: a) from 0 to 50% by weight and, more particularly, from 0 to 20% by weight of at least one crystallinity modifying adhesive, more particularly from the following group: salts of aromatic and aliphatic carboxylic acids (for example, Ca stearate), wax, polyacrylate, polyethylene, polyvinyl acetate, polyamide, polyurethane and polyvinyl chloride, and also polyester or polyurethane, where the binder is a polyurethane or a polyester , b) from 0 to 20% by weight and more particularly from 0 to 10% by weight and preferably from 0.1 to 5% by weight of at least one pigeon or filler material of water-insoluble fine particle, more particularly from following group: alkali metal stearate, graphite, talc, TiO®, highly dispersed silica (Aerosil), bentonite, wollastonite, limestone, magnesium oxide and glass fibers, c) from 0 to 30% by weight and more particularly from 0 to 10% by weight of at least one non-volatile plasticizer, especially from the group of phthalates, cebacates, phosphates, for example: diphenyl phthalate, benzylbutyl phthalate, trioctyl phosphate and n-ethyl-o, p-toluene sulfonamide, d ) from 0 to 5% by weight and more particularly from 0 to 2% by weight of at least one of the following additives: antioxidants, preservatives and dyes, e) water and f) from 0 to 30% by weight and more particularly from 0 to 10% by weight of at least one sticky material, especially the following group: terpene / phenol resin, rosin / glycerol ester, polycyclopentadiene resin, hydrocarbon resin and methyl styrene / styrene copolymer. The type and quality of the adhesives of course varies according to the binder. The above list applies above all to polyesters. For polyurethanes, more particularly for polyether urethanes, the recommended crystallinity modifiers are PEG, PPG, PTHF and / or a polyester added in amounts from 0 to 50% by weight and more particularly from 10 to 40% by weight. Additions from 0 to 50% by weight, more particularly from 0 to 30% by weight and especially from 0 to 10% by weight of at least one water-miscible hydrophilic plasticizer from the group consisting of glycerol, ethylene glycol and Diglima are recommended as the non-volatile plasticizer. The water content of the adhesive is between 0 and 15% by weight, more particularly it is well below 5% by weight, when measured by the Karl Fischer method. The percentages by weight shown are based on the adhesive as a whole. All plasticizers have a boiling point of 150 ° C at normal pressure. Accordingly, the adhesive is substantially free of readily volatile solvents. The binder and the additives are mixed in the melt, preferably until no difference in homogeneity is seen. The adhesive thus obtained should be brought to any required shape, for example, flakes, films or bars. Adhesive bars with a circular, elliptical or angular cross section are preferred. In its easy to use form, the adhesive no longer contains any reactive group. Lastly, it contains less than 10% by weight and preferably less than 5% by weight of volatile organic constituents with a boiling temperature below 150 ° C. The adhesive according to the invention is especially suitable for bonding substrates. For this end, the adhesive is activated by internal and / or external friction, the substrates are bonded with the now sticky adhesive between them and, finally, the adhesive is allowed to dry for a few seconds to a few days. When the adhesive is rubbed onto paper, a film of 2 to 200 μ, and preferably 10 to 100 μ of thickness is formed at a speed of 1 to 500 cm / sec and, preferably, from 2 to 100 cm / sec. , at a pressure of 1.0 kPa to 10 MPa, preferably 5.0 kPa to 5.0 MPa, and more preferably 10 kPa to 1 MPa and a temperature of 20 ° C.

The adhesive according to the invention has the following advantages: - Requires little or no packing for normal environmental conditions (20 ° C / 50% relative humidity). - Your composition does not have to be shown on a label. - It's not flammable. - It is activated mechanically by rubbing with little pressure. - It does not form filaments. - The joint can be broken by heating - The paper does not curve after applying the adhesive. - The hardening speed of the adhesive is very high: the adhesive feels dry (and not sticky) only a few seconds after the application. - The adhesive is easy to produce by virtue of its rapid recrystallization and low viscosity in the melt. The properties mentioned in the above apply above all to the PES binders. Some other binders produce other positive properties. For example, polyether urethanes are easy to wash off fabrics or at least their binding effect can be removed with water. The recrystallization can also be delayed so that the bond can be corrected. The invention is illustrated by the following examples: I. Initial materials 1). Initial materials for the PES - Dynacoll 7360, a partially crystalline copolyester based on adipic acid and hexanediol with a hydroxyl value of 27 to 34 mg KOH / g (DIN 53240), an acid value of < 2 mg KOH / g (DIN 53402), a melting point of 60 ° C (DSC), a softening point of 65 ° C (R + B, ISO 4625), a viscosity of around 2000 mPa.s at 80 ° C C (Brookfield LVT 4) and a molecular weight (from the hydroxyl value) of about 3500.

Dynacoll 7140, an amorphous copolyester based on terephthalic acid, isophthalic acid, ethylene glycol, butan-1,4-diol and hexanediol with an acid value of 18 to 24 mg KOH / g (DIN 53240), an acid value < 2 mg KOH / g (DIN 53402), a glass transition temperature of around + 40 ° C (DSC), a softening point of 90 ° C (R + B, ISO 4625), a viscosity of 100 mPa .sa 130 ° C (Brookfield LVT 4) and a molecular weight (from the hydroxyl value) of about 5,500. - Dynacoll 7110, an amorphous copolyester based largely on terephthalic acid, pentan-1,4-diol and hexanediol with an acid value of 50 to 60 mg KOH / g (DIN 53240), an acid value of 8 to 12 mg KOH / g (DIN 53402), a glass transition temperature of around + 10 ° C (DSC), a softening point of 60 ° C (R + B, ISO 4625), a viscosity of 10 Pa.sa 100 ° C (Brookfield LVT 4) and a molecular weight (from the hydroxyl value) of 2,000. - Dynacoll 7220, a liquid copolyester based on terephthalic acid, adipic acid, 2-methylbutan-1, -diol and butan-1,4-diol with a hydroxyl value of 27 to 34 mg KOH / g (DIN 53240), acid value of < 2 mg KOH / g (DIN 53402), a glass transition temperature of -20 ° C (DSC), a viscosity of 5 Pa.s at 100 ° C (Brookfield LVT 4) a molecular weight (from the hydroxyl value ) of around 3,500. - Dynacoll 7340, a partially crystalline copolyester with a hydroxyl value of 27 to 34 mg KOH / g (DIN 53240), an acid value of < 2 mg KOH / g (DIN 53402), a melting point of 92 ° C (DSC), a glass transition temperature of -40 ° C (DSC), a softening point of 100 ° C (R + B, ISO 4625), a viscosity of 3 Pa.s at 130 ° C (Brookfield LVT 4) and a molecular weight (from the hydroxyl value) of about 3,500. - Dynacoll 8350, a copolyester containing carboxyl, with an acid value of 26 to 30 mg KOH / g (DIN 32402), a glass transition temperature of -50 ° C (DSC), a viscosity of 140 Pa.s at 20 ° C (Brookfield LVT 4) and a molecular weight of about 4,000. Dynacoll 8250, a carboxyl-containing copolyester, with an acid value of 15-19 mg KOH / g (DIN 32402), a glass transition temperature of -50 ° C (DSC), a viscosity of 140 Pa. sa 20 ° C (Brookfield LVT 4) and a molecular weight of 6000. Dynacoll is a registered trademark of Hüls AG. - Layer 240 is a registered trademark of Interox Chemicals Ltd. for a linear poly-e-caprolactone with a hydroxyl value of 28 mg KOH / g, an acid value of <; 0.5 mg KOH / g, a melting range of 55 to 60 ° C and a molecular weight of 4, ü ?? - PES1 is a polyester urethane of Dynacoll 7360 and Desmodur W in a molar ratio of 2: 1. - PES2 is a urethane polyester of Dynacoll 7360, Dynacoll 7140 and Desmodur W in a molar ratio of - PES3 is a urethane polyester of Dynacoll 7360 and TMXDI in a molar ratio of 2: 1. - PES1 is a polyester urethane of Dynacoll 7360 and IPDI in a molar ratio of 2: 1. - PES5 is a polyester urethane of Dynacoll 7360 and 2,4'-MDI in a molar ratio of 2: 1. - PES6 is a urethane pestle modified with terminal octyl dodecanol groups: Dynacoll 7360 and IPDI are reacted in a molar ratio of 2: 3. The product of this reaction is reacted with octyl dodecanol so that the NCO content is below 0.01% and the molar ratio of the polyester to diisocyanate to alcohol is 2: 3: 2. - Foral-85 is a registered trademark of Hercules for a hydrogenated rosin / glycerol ester with an acid value of 9 mg KOH / g, a softening temperature of 80 ° C (R + B) and a viscosity of 100 mPa-s at 160 ° C (Brockfield). - Kristalex F85 is a registered trademark of Hercules for a copolymer of a-methyl styrene / styrene with a softening point around 85 ° C (R + B).

- Bevitak 95 is a registered trademark of Bergvik for a sticky material. - Desmodur W is a registered trademark of Bayer AG for the 12-H-MDI. 2. Initial materials for polyurethanes. a) - Diisocyanate = TMXDI, IPDI, MDI - hexamethylene diisocyanate triisocyanate (Tolonato HDT, Rhone-Poulenc) b) - Diols: - Loxanol = 1, 12-C? b-diol - DMPA = dimethylol propionic acid - Pluronic 6800 = block copolymer PEG-PPG-PEG containing 20% PPG: PM 8,500 - PTHF 2000 = polytetrahydrofuran, MW 2000 - PEG 6000 = polyethylene glycol, MW 6000 - Arbitol E is a registered trademark of Hercules for a technical hydroabietyl alcohol containing 4.75% OH and with a viscosity of 40,000 mPa-s at 40 ° C. - Terathane 1000 is a registered trademark of BASF for a polytetramethylene ether glycol with a molecular weight of 1000. - WS 1 is a reaction product of Terethane 1000 and Desmodur V 44 in an OH: NCO ratio of 1: 1.5, the excess NCO groups are reacted with alcohol CIÜ / CIO in a ratio of 20:80.

- WS2 is a reaction product of the following starting materials in the proportion shown: Terathane 1000: Tolonate HDT: Abitol E: Cie alcohol = 31.4: 35.6: 9.4: 23.6. - WS3 is a reaction product of the following starting materials in the proportion shown: Terathane 1000: Tolonate HDT: Abitol E: Cí¿ alcohol = 22.5: 31.8: 14.7: 16.1. - WS3 is a reaction product of the following starting materials in the proportion shown: Terathane 1000: Tolonate HDT: Abitol E: Ci alcohol: Clb alcohol = 21.5: 35.6: 14.3: 5.1: 13.5. 3. Additives - PEG 600 = polyethylene glycol, PM 600 - PEG 1550 = polyethylene glycol, PM 1550 - PEG 35000 = polyethylene glycol, MW 35,000 - Bentonite - Ca II stearate. Production 1. In Examples I, la-g and III., PU was produced as in Example 1.2 except that the water was also removed from the diols. 2. In Examples I.2a-k the PU was produced as follows: PEG 6000 (Lipoxol, Hüls) and di-propionic acid (Angus Chemie) were liberated from water for 2 h at 80 ° C in an oil pump to the vacuum Then m-TMXDI (Cyanamid) was added and the mixture was heated to 145 ° C. The theoretical NCO content of 0% residual NCO was reached after 2h. 3. The adhesive was produced as follows from the binder and the additives: The individual components were combined and melted with stirring. The stirring was continued until the formation of a homogeneous mixture. The melt was poured into molds and removed from them after 24 h. The examples are based on the following compositions (parts by weight): 4. Compositions Examples I. la-g: [% by weight] a) l'U (Pluronic 6800: DMPA: Loxanol: TMXDI = 1: 8.4: 0.8: 9.7) 75% t * 'EG € 00 20% Ca stearate 5% b) PU (Pluronic 6800: DMPA: Loxanol: TMXDI: 1: 8.4: 0.8: 9.7) 75% PEG 600 20% Bentonite 5% c)? U (PEG 6000: DMPA: Loxanol: TMXDI: PTHF 2000 = 0.76: 8.4: 0.8: 9.2: 0.24.}. 85% PEG 600 15% d) PU (Pluronic 6800: DMPA: Loxanol: TMXDI = 1: 8.4: 0.8: 9.7) 85% PEG 600 15% e)? U (Pluronic 6800: DMPA: Loxanol: TMXDI = 1: 16.7: 0.8 : 17.6) 70% PEG 600 30% f)? U. { Pluronic 6800: DMPA: Loxanol: TMXDI = 1: 16.7: 0.8: 17.6) 69% PEG 600 30% PEG 35000 1% g) PU (Pluronic 6800: DMPA: oxanol.-TMXDI = 1: 16.7: 0.8: 17.6) 70 % PEG 1550 30% Examples I.2a-k [% by weight] PU (PEG 6000: DMPA: TMXDI = 1: 8.37: 8.9) 100% b PU (PEG 6000: DMPA: TMXDI = 1: 0.86: 1.67) 100% c PU (PEG 6000: DMPA: TMXDI = 1: 15: 15.2 ) 100% d PU (PEG 6000: DMPA: TMXDI = 1: 15: 15.2) 50% PEG 200 50% e PU (PEG 6000: DMPA: MXDI = 1: 8.37: 8.9) 100% f PU (PEG 6000: DMPA : TMXDI = 1: 8.37: 8.9) 100% Neutralized with PU NaOH (PEG 6000: DMPA: TMXDI = 1: 1.37: 8.9) 90% Glycol 10% PU (PEG 6000: DMPA: TMXDI = 1: 8.37: 8.9) 70 % Glycol 30% PU (PEG 6000: DMPA: TMXDI = 1: 8.37: 8.9) 70% Diglyme 30% PU (PEG 6000: DMPA: TMXDI = 1: 8.37: 8.9) 50% Glycerol 50% PU (PEG 6000: DMPA : TMXDI = 1: 8.37: 8.9) 50% PEG 200 50% Examples II. la-v a Dynacoll 7360: Dynacoll 7140 = 30:70 b Dynacoll 7360: Dynacoll 7140 = Stearate of Ca = 30: 70: 5 c Dynacoll 7360: Dynacoll 7110 = 30:70 d Dynacoll 7360: Dynacoll 7110 = 20:80 e Dynacoll 7340: Dynacoll 7140 = 30:70 f Dynacoll 8350; Dynacoll 7220 = 30:70 g Dynacoll 8350: Dynacoll 8250 = 50:50 h Dynacoll 7360: Dynacoll 7140: butylbenzylphthalate = 28.5: 66.5: 5 i Dynacoll 7360: Dynacoll 7140: butylbenzylphthalate = 27:63:10 and Dynacoll 7360: Dynacoll 7140: butylbenzylphthalate = 24:56:20 k Dynacoll 7360: Dynacoll 7110: Foral 85 = 30:60:10 1 Dynacoll 7360: Dynacoll 7110: Bevitack 95 = 30:60:10 m Dynacoll 7360: Dynacoll 7110: KristalexrF85 = 30 60:10 n Dynacoll 7110: PES1 = 70:30 or Dynacoll 7360: PES2 = 10:90 p Layer 240: Dynacoll 7110: 30:70 q Dynacoll 7360: Dynacoll 7110: Bentonite = 30; 70: 10 r Dynacoll 7360: Dynacoll 7110¡butylbenzylphthalate »20: 80: 2.5 S Dynacoll 7110: PES3 = 7Q: 30 t Dynacoll 7360: Dynacoll 7110: polyethylacrylate = 20: 80: 2.5 or Dynacoll 7110: PES4 = 70:30 v Dynacoll 7110: PES5 = 70:30 w Dynacoll 7110: PES6 = 60:40 Mixtures of polyester urethane and polyether urethane x- PES4 33% - (Pluronic 6800: DMPA: Loxanol: TMXDI "= l: 8.4: 0.8 : 9.7) 66.7% and - PES4 7.5% - (Pluronic 6800: DMPA: Loxanol: TMXDI: 1: 8.4: 0.8: 9.7) 36.7% Dynacoll 7110 17.5% PEG 600 11.3% Examples III. la) -m) a) Terathane 1000: Desmodur 44: Abitol E: Dynacoll 7360: Ci 51.3 alcohol: 20.1: 5.7: 19.6: 3.3 b) Terathane 1000: Desmodur 44: Abitol E: Dynacoll 7360: Cu 56.0 alcohol: 22.0: 6.3: 10.69.9: 4.9 c) Terathane 1000: Tolonate HDT: Abitol EIalcohol of Ci4 32.7: 37.1: 17.6: 15.3 d) Terathane 1000: Tolonate HDT: lcohol of C14 34.7: 39.4: 25.9 e) Ter- ". tl .c I0C0: Tolonatc HDT: Ahi + -ol E: alcohol? e C16 31.4: 35.6: 9.9: 23.6 f) Terathane lOOOtolonate HDT: Abitol E: Clß alcohol: C alcohol «32.6: 36.9: 1438: 10.2: 5.5 g) WS1: Dynacoll 7360: Dynacoll 7130 62.5: 33.3: 4.2 h) WS2: Dynacoll 7360: Dynacoll 7140: butylbenzylphthalate: aluminum silicate: Kristallex F 85 60: 26.7: 3.3: 5.3: 1.3: 18.3 i) WS1: Dynacoll 7360 : Dynacoll 7100: Abitol E: Butylbenzylphthalate: Aluminum silicate: Krsitallex F 85 57.3: 21.3: 1.0: 1.3: 8.5: 2.6 5.3 k) WS3: Dynacoll 7360: Dynacoll 7100: Butylbenzylphthalate: Aluminum silicate 57.7: 30.8: 3.9 : 6.2: 1.5 1) WS4: Dynacoll 7140 88.3: 11.8 m) WS4: Dynacoll 7140 65.2: 34.8 III Tests 1. Adhesiveness The adhesiveness was generally carried out as follows: pressure around 500 kPa, speed: about 100 cm / sec, room temperature, film thickness; around 50 μm. 2. The tests were carried out to determine: a) The adhesive force after 10 seconds; the ends of a cardboard strip were joined to form a ring and the adhesion time was subsequently evaluated (the result was e-expressed as time). A cardboard strip with 29.1 cm x 5 cm was used for a thickness of 250 g / m2. Measuring from the edge, a 2 cm wide margin of a narrow side of the strip was covered with adhesive on one side. The ends of the strip were joined to form a ring and pressed for 10 seconds. The time elapsed before the ring reopened was measured. b) Adhesion strength after one day: Soennecken copying paper (5015 Spezial Copier) was attached with the adhesive, Paper tearing test after one day (percentage of paper tearing (P) / separation (ALSO)) . c) Tensile sliding resistance of wood / wood joints: two test pieces of wood pieces were covered with adhesive at their ends and gathered in such a way that the two ends covered with adhesive overlapped by 2 cm (2 cm joined area) x 2.5cm). The test samples were fixed with two clamps and measured after 24 hours. The result is expressed in N / mm2. d) Rubbing: rubbing on copier paper Soennecken (5015 Spezial Copier). The result is expressed as school marks. e) Crystallinity: measurement of the DSC curves (S: enthalpy of fusion, maximum melting temperature.

The peak may be structured or may consist of several peaks. The temperature of the largest peak is shown. Io heating; R: recrystallization, maximum recrystallization temperature-2 ° heating; - 60 ° C to + 100 ° C, 10 ° c / min, cooling in a stream of nitrogen). f) Behavior in the drying-evaluation of the crystallinity under a polarization microscope (tendency to crystallize characterized as fast, slow or "none"). G) Viscosity in the melting (Epprecht): 125 ° C ÍPas] 2. Results of the test table 1: Example 1 a b [%] c IN / mm2] test of e [mJ / mg ° C] g [Pas] the > 24 h 40% 0.1 3 S: 52/40 R: -28 / ~ 31 Ib > 24 h 70% 0.2 3 S: 53/40 R: -42 / -30 lc > 24 h 50% 0.3 4 S: 55/47 R: -47 / -2 slow ld > 24 h 95% 0.5 4 S: 48/2 R: -30 / -23 slow le 24 h 10% 0.4 4 S: 44/40 R: -38 / -16 slow lf > 24 h 50% 0.2 4 S: 40/44 R: -34 / -15 slow ig > 24 h 95% 1.4 5 S: 69/51 R: -39 / -20 slow-fast 2a 2.2 50 2b 2.0 40 2c 1.8 > 256 2d 0.6 2e 4 70 2f 0.2 100 2g 0.4 2h 3.7 2i 0.1 2j 0.3 2k 0.3 Table 2: Example II. la) -l) example No. test method d) a) c) b) e) f) Sticky rubbing Tearing resistance of Tem. max Temp. max, to cut by recreat melt paper. traction II. la) 3-4 > 24 h 0 31 mJ / 66 ° -11 mJ / - 3 °, 46 ° b) 3-4 > 24 h 0 0 O 2 > 24 h 0.2 50 30 mJ / 58 * d) 2-3 > 24 h 0.5 90 e) 3-4 1.5 h 0.77 0 f) 4 > 24 h 0.34 0 g > 1 20 min 0 0 h) 3-4 > 24 h 0 0 27 mJ / 62 ° -17 mJ / 0 °, 34 ° i) 3 > 24 h 0.33 90 29 mJ / 53 ° -18 mJ / 26 ° j) 4 > 10, < 24 h 0.13 100 26 mJ / 56 ° -21 mJ / 26 ° k) 2-3 > 24 h 0.02 0 1) 2-3 > 24 h 0.35 0 29 mJ / 57 ° -10 mJ / 43 ° Table 2 (continued). Result of the tests of Examples II. lm) -y) example No. test method d) a) c) b) e) f) Sticky rubbing tept resistance Teptp. max Temp. max. to the cut by paper melt recrist. traction) 2-3 > 24 h 0.23 0 33 mJ / 59 ° -7 mJ / 46 ° n) 2 > 24 h 1.30 90 29 mJ / 59 ° -8 mJ / 44 ° o) 6 > 24 h 1.76 0 P) 3 > 24 h 0.24 95 31 mJ / 59 ° q) 3 > 24 h 0.23 90 28 mJ / 53 ° -16 mJ / 42 ° r; 3 > 24 h 0.56 95 s; 2-3 > 24 h 0.12 95 t) 2-3 > 24 h 0.11 70 u) 2-3 > 24 h 1.30 95 25 mJ / 52 ° -4 mJ / 38 ° V) 2 > 24 h 0.85 95 27 mJ / 51 ° -12 mJ / 32 ° w) 2 > 24 h 0.26 95 31 mJ / 48 ° -16 mJ / 29 ° X) 3 > 24 h 1.42 90 53 raJ / 42 ° -19 mJ / -5 ° y) 3 > 24 h 0.67 95 38 mJ / 40 ° -30 mJ / -2.6 ° Table 3: Examples III. la) -m) example No. test method d) a > c) b) e) f) Sticky rubbing Tearing resistance of Temp. max Temp. max. to the cut by paper melt recrist. traction [mJ / mg / ° c] [mJ / mg / ° c] III. la) 5 > 1 h 0.35 30 9/45 b) 4 3 h O. € l 60 11/42 -13/44, c > 5 4 h 0.51 40 7/45 d) 4 5 h 0.35 30 19/40 e) 2 > 24 h 0.45 30 32/40 -17/28 f) 1 > 24 h 1.13 100 41/56 g) 2 > 24 h 1.46 100 51/49 -20/33) 3 > 24 h 0.28 30 31/50 i) 2 > 24 h 1.27 80 37/54 j) 5 > 24 h 0.52 30 22/47 -10/30 k) 4 2 h 0.96 80 34/51 1) 4 > 24 1.71 100 39/59 m) 2 > 24 h 0.89 30 28/49

Claims (12)

1. CLAIMS A process for joining substrates with a partially crystalline adhesive, without water or substantially without water, solid at room temperature, the process is characterized in that the adhesive is activated by internal and / or external friction, the substrates are bonded with the adhesive now sticky between these and, finally, the adhesive is allowed to dry allowing it from a few seconds to a few days.
2. The process according to claim 1 is characterized in that the solid adhesive produces a film of 2 to 200 μ and, preferably, of 10 to 100 μ of thickness when applied to the paper at a speed of 1 to 500 cm / sec. , and preferably from 2 to 100 cm / sec, with a pressure of 1.0 kPa to 10 MPa, preferably 50 kPa to 5.0 MPa, and more preferably 10 kPa to 1 MPa and a temperature of 20 ° C.
3. A partially crystalline adhesive, without water or substantially without water, solid at room temperature, characterized by a) a degree of crystallization, when determined by DSC, in the range from -40 ° C to + 120 ° C to which it corresponds a melting enthalpy of 10 to 150 mJ / mg, more particularly, of 15 to 80 mJ / mg, and preferably 20 to 70 mJ / mg, b) at least one crystallization temperature, when determined by DSC, from 20 to 110 ° C and preferably from 30 to 80 ° C, and c) by a crystallization rate of a few seconds to a few days, when determined by observation under the polarization microscope.
4. 4. The adhesive according to claim 3 is characterized in that it consists of 25 to 100% by weight of the binder and from 0 to 75% by weight of additives, the binder consists of a) at least one partially crystalline polyester, and b) at least one amorphous and / or liquid polyester, polyester amide or polyester urethane with MW * molecular weights of 1,000 to 20,000.
5. 5. The adhesive according to claim 3 or 4 is characterized in that in addition to the binder, it contains the following additives: a) from 0 to 50% by weight of at least one additive modifying the crystallinity, b) 0 to 20% by weight of at least one pigment or water-insoluble filler, of fine particles, more particularly of the following group: alkali metal stearates, graphite, talc, TiO2, bentonite, wallostonite, limestone and pyrogenic silica (Aerosil ), magnesium oxide and glass fibers, c) from 0 to 20% by weight, and preferably from 0 to 10% by weight of at least one non-volatile plasticizer, d) from 0 to 5% by weight of at least one of the following additives: antioxidants, preservatives, dyes and perfumes, e) from 0 to 15% by weight, and more particularly from 0 to 5% by weight of water, and f) from 0 to 30% by weight of at least a sticky material.
6. 6. The adhesive according to claim 3, characterized in that it contains from 25 to 100% by weight of binder and from 0 to 75% by weight of additives, the binder being based on polyurethane or a mixture of polyurethanes that can be producing from the following components: a) at least one aliphatic or aromatic diisocyanate, preferably from the following group: MDI, TDI, HDI, IPDI and especially TMXDI, b) at least one polyester or polyether diol crystallizer , more particularly from the following group: polyethylene glycol with a molecular weight (average number) of 200 to 40,000, polytetrahydrofuran with a molecular weight of 200 to 4,000, copolymer of ethylene oxide and propylene oxide with a molecular weight of 200. at 40,000, preferably a block copolymer with the structure PEG / PPG / PEG and with a PEG content of 10 to 80% by weight, and - a polyester diol, more particularly polycaprolactone with a molecular weight of 20. 0 to 50,000, c) optionally, at least one diol capable of forming ions, more particularly, carboxylate ions, d) optionally at least one polyol with a functionality of 3 or higher, such as glycerol and TMP, and e) optionally , at least one hydrophobic diol, more particularly from the following group: polypropylene glycol with a molecular weight of 200 to 4,000, and alkanediol containing from 1 to 100, preferably from 2 to 50, and more preferably from 5 to 30 carbon atoms, the ratio of the isocyanate groups to hydroxyl groups is variable from 0.5 to 1.2: 1 and more particularly from 0.7 to 1: 1.
7. 7. The adhesive according to claim 3 or 6, characterized in that in addition to the binder, it contains the following additives: a) from 0 to 50% by weight of at least one crystallinity modifying additive, more particularly , from the following group: PEG, PPG, THF and polyester, b) from 0 to 20% by weight of at least one pigment or water-insoluble, fine-particle filler, more particularly from the following group: alkali metal stearates , graphite, talc, Ti? 2, bentonite, wallostonite, limestone and fumed silica (Aerosil), c) from 0 to 50% by weight, preferably from 0 to 30% by weight, and more particularly from 0 to 10% by weight weight of at least one non-volatile plasticizer, preferably from the group of the following hydrophilic water-miscible plasticizers: glycerol, ethylene glycol and Diglyme, d) from 0 to 5% by weight of at least one of the following additives: antioxidants , preservatives, colorants and perfumes, and e) from 0 to 15% by weight, and more particularly, from 0 to 5% by weight of water.
8. 8. The adhesive, according to at least one of claims 3 to 7, is characterized in that it contains non-reactive groups and less than 10% and, more particularly, less than 5% volatile solvents.
9. 9. The adhesive, according to at least one of claims 3 to 8, is characterized by its geometric shape, more particularly in the form of a bar with a circular, elliptical or angular cross section.
10. A process for producing the adhesive according to at least one of claims 3 to 9, characterized in that - the binder is produced without solvent, optionally, in the presence of a catalyst, - the binder is mixed in a visibly uniform manner with the additives, and - the adhesive can be shaped.
11. 11. A process for joining substrates according to at least one of claims 1 to 10, characterized in that preferably at least one substrate is paper, paperboard, wood or fabric.
12. 12. The process according to claim 11 is characterized in that the bond is broken by exposure to heat or water.