TWI297017B - Polyesteramide copolymer - Google Patents

Description

1297017 A7 B7 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to a polyurethane polyester copolymer, and particularly for use as an adhesive. BACKGROUND OF THE INVENTION Hot melt adhesives, such as polyamides, polyesters and copolymers thereof, are used in a wide range of applications. Polar guanamine or ester groups provide excellent cohesive strength and adhesion to polar substrates such as paper, wood and metals. At the same time, due in part to the presence of polar groups, the material is a solid that is easy to handle at room temperature and will melt at a defined temperature range, producing an easy to use fluid that will solidify quickly to produce an adhesive bond. An obvious advantage is that there is no solvent, which makes hot melt adhesives an increasingly important technology. Unfortunately, the known polyamine thermal adhesives do not interact well with low energy substrates such as polyglycols, resulting in poor adhesion strength. In addition, low-energy substrates have a soft tendency (such as polyolefin films) and are used under a wide variety of conditions (such as a wide temperature range), which requires good softness (for example, at -60 ° C so low) A suitable adhesive having the ability to absorb differences in the thermal expansion of the substrate. The known polyamine heat-fusible adhesives tend to have insufficient flexibility. This low temperature flexibility and adhesion to low energy substrates, while maintaining a combination of cohesive strength, is difficult to achieve with polyamidamide hot melt adhesives. 0 Previously known polyamide thermal adhesives have been used. It is modified in various ways to improve its properties. US-A-4,409,373 discloses a polyamine adhesive comprising a polyether base in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) on a paper scale of -4-.

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1297017 A7 __87 V. INSTRUCTIONS (2) ~""~"" Obtain low temperature softness. However, its adhesion to low-energy substrates is not good. US-A-4,777,238 describes a polyamidene hot melt adhesive comprising a secondary diamine and said to improve substrate adhesion. In the examples of this patent, Ming, P V C and polyester are each bonded together using the polyamine-based hot-melt adhesive described therein. US-A-4,791,164 discloses a hot melt adhesive which is a mixture of polyamidamine and a polyethylene copolymer or terpolymer. The hot melt adhesive is referred to as being suitable for ligating polyethylene. However, two-component systems are known to be susceptible to problems such as incompatibility, separation, and migration. SUMMARY OF THE INVENTION We have now surprisingly discovered an improved polyamine which can be used as a hot melt adhesive which can reduce or substantially overcome at least one of the foregoing problems. Thus, the present invention provides a polylactide copolymer having a glass transition temperature (T g) of less than or equal to 0 ° C and comprising at least one hard segment comprising at least _ aramid bond, and at least one At least one soft bond segment of vinegar linkage wherein the soft segment is formed from at least one dimer fatty acid and/or dimer fatty acid glycol and/or its equivalent. The present invention also provides an article comprising a substrate layer having a surface energy of less than 50 mN/m and having an adhesive layer on at least one surface thereof; the adhesive layer comprising a polylactide s copolymer having a glass transition temperature (Tg) less than or equal to 〇°e, and comprising at least one hard segment comprising at least one amine-amine bond, and at least one soft segment comprising at least one ester bond, wherein the soft segment is at least A dimer fatty acid and / or dimer diol and / 5 - This paper scale is applicable to China i standard (CNS) A4 specification (210X 297 mm) ' -----

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A7 B7 1297017 V. Invention description (3) or its equivalent. The present invention still provides a method of forming a polyamidoester copolymer having a glass transition temperature (T g ) of less than or equal to 0 ° C and comprising at least one hard comprising at least one guanamine bond. a segment, and at least one soft segment comprising at least one ester bond, wherein the soft segment is formed from at least one dimer fatty acid and/or dimer fatty acid glycol and/or its equivalent. The method comprises (i) preforming a hard segment, and (ii) forming a soft segment in situ in the presence of a hard segment. The present invention further provides the use of a polyamidoester copolymer having an glass transition temperature (T g ) of less than or equal to 〇 ° C and comprising at least one amine-containing bond. A hard segment, and at least one soft segment comprising at least one ester bond, wherein the soft segment is formed from at least one dimer fatty acid and/or dimer lipodiol and/or its equivalent. The hard segment of the copolymer according to the invention comprises at least one, preferably from 2 to 35, more preferably from 3 to 20, especially from 4 to 15, and especially from 5 to 1 Torr. Amine bond. Therefore, the hard segment is preferably an oligomeric amine or a polyamine (hereinafter referred to as polyamine). The composition of the hard segments can vary over a wide range. The polyamine is usually produced in the condensation reaction of a dicarboxylic acid with a diamine. There are two main types of dicarboxylic acids that can be used to form polyamines, which are dimerized aliphatic di-skin acids and non-dimerized aliphatic dicarboxylic acids. Monomeric fatty acids are well known in the art and are dimeric products of mono- or polyunsaturated fatty acids and/or their esters. Preferred dimers 疋Ciq to C3G, more preferably Ci2 to C24, especially C14 to C22, -6- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm)

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1297017 A7 — — — — ___B7__ V. DESCRIPTION OF THE INVENTION (4) and in particular a dimer of a Cu alkyl chain. Suitable dimeric fatty acids include dimerization products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid and elaidic acid. Dimerization products of unsaturated fatty acid mixtures obtained in the hydrolysis of natural fats and oils such as sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and tall oil may also be used. For example, a dimer fatty acid which is hydrogenated by using a nickel catalyst can also be used. In addition to dimer fatty acids, dimerization usually results in the presence of varying amounts of oligomeric fatty acids (so-called "trimers") and monomeric fatty acids (so-called "monomeric") residues or their cool species. The amount of monomer can be reduced, for example, by evaporation. Particularly preferred dimer fatty acids have a dicarboxy (or dimer) content of greater than 70%, more preferably greater than 85%, and especially greater than 94 weight percent. Suitable non-dimer aliphatic dicarboxylic acids (hereinafter referred to as non-dimerized fatty acids) may be aliphatic or aromatic, and include ditoxaic acid and its esters (preferably a base) a preferred one is a carbon chain having 2 to 20, more preferably 6 to 12 carbon atoms, and a linear diterpic acid containing a terminal group such as adipic acid, pimelic acid, suberic acid , azelaic acid, sebacic acid, heptane dicarboxylic acid, octane diacid, decane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid and higher a homologue. The polyamine hard bond segment is preferably formed from a dimer fatty acid and a non-dimer fatty acid, wherein the dimerization is based on the weight of the total dicarboxylic acid. The fatty acid to non-dimer fatty acid system is from 〇 to 100%: 0 to 100%, more preferably 50 to 1 〇〇〇 / 0: 〇 to 50%, and especially 80 to 10% by weight: A ratio of 〇 to 20% exists. Suitable diamines include the amine equivalents of the aforementioned dicarboxylic acids (but the shorter chain of paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 1297017

Quality is usually preferred, especially those containing from 2 to 7 carbon atoms. Diamines such as ethylenediamine, 1,2-propylenediamine, 1,4-butanediamine, pentanediamine, 1,6-hexanediamine and dimer fatty diamines (derived from dimer fatty acids) It is better. Suitable aromatic diamines include materials derived from benzene, toluene and other substituted aromatic materials such as 2,6-toluenediamine, 4,4-dimethanediamine and xylylenediamine. Other suitable diamines include those containing one or two secondary amine groups and heterocyclic monoamines such as ruthenium. Branched diamines such as 3-methylpentanediamine can also be used. The ratio of the dicarboxylic acid to diamine starting material used to form the polyamine segment is preferably from 1.0 to 5.0:1, more preferably from 1 〇5 to 3.0:1, especially from 丨丨 to 2.0·1. 'And in particular in the range of 1.2 to 1. 4:1. The polyamine is preferably terminated at both ends by a lean group. In particular, it is a dimer fatty acid as described herein. The hard segment is suitably a block, preferably having a range of from 5 〇〇 to 15,000, more preferably from 1,000 to 10,000, especially from 15 〇〇 to 6 〇〇〇, and especially from 2,000 to 4,000. Number average molecular weight. The hard segment preferably has a softening point in the range of from 60 to 200 ° C, more preferably from 65 to 150 ° C, especially from 70 to 125 °, and especially from 75 to 100 3⁄4. The hard segment has a relatively low acid value in the range from 10 to 200, more preferably from 20 to 100, especially from 25 to 50 and especially from 3 to 40 mg KOH/g (measured as described herein) . Furthermore, the hard segments preferably have less than 1 〇, more preferably less than 5, especially less than 3, and in particular less than! The amine value of mgK〇H/g (measured as described herein). The soft bond segment of the copolymer according to the invention comprises at least one, preferably _ 8 - the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 1297017

5. Description of the invention (6 疋 in the range of 1 to 20, more preferably 2 to 15, especially 2 to 10, and especially 3 to 5, an ester bond. Therefore, the soft segment is preferably an oligoester. Or polyester (hereinafter referred to as polyester). The brewing is usually produced in a condensation reaction between a dicarboxylic acid and a diol. Suitable diacids include those described above for forming a hard segment. Suitable diols include linear aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4·butanediol, 1>6•hexanediol; branched glycols such as neopentyl glycol, A Pentyl glycol, 1,2-propanediol and cyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and (1,4·cyclohexanedimethanol) a linear aliphatic diol of 6 carbon atoms, especially 1,6-hexanediol. The soft sulphate is composed of a dimer fatty acid and/or its ester derivative and/or dimer diol Formed. The dimer fatty acid is as described above for the hard segment, and the dimer lipodiol can be produced by hydrogenation of a comparable dimer acid. The same as the dimer fatty acid component of the hard segment described above. Choose to For use in a dimer fatty acid and/or a dimer fatty diol component of a soft segment. In a preferred embodiment, the soft segment is comprised of a dimer fatty acid and at least one A linear aliphatic diol having 6 carbon atoms, especially 1,6-hexanediol. The soft segment of the copolymer preferably has a temperature of from -60 to 0 ° C, more preferably from -50 to -l玻璃 ° C, especially -40 to -20 ° C, and especially glass transition temperature (Tg) in the range of -35 to -25 ° C. The soft segment preferably has from 5 to 220, more preferably 25 a hydroxyl number (as measured herein) and/or an acid value (as measured herein) up to 200, especially 40 to 190, and especially 55 to 180 mg KOH/g. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). V. Description of the invention (7) In a preferred embodiment, the soft segment has a hydroxyl value or an acid value in the above-mentioned range, and Outside this range, preferably less than the hydroxyl value or acid value of the hydrazine. The soft bond segment preferably has a range of from 5 Å to W, more preferably from 5 Å to 8, and 〇〇〇', especially from 550 to 3 , 〇〇., and especially 6.数目 to 2, the number average molecular weight in the enthalpy. The ratio of the hard segment to the soft segment in the copolymer, preferably from 1 to 25:1, more preferably from 4 to 2:1 by weight Especially in the range of 6 to 15:1, and especially 8 to 10:1. The polyamidoester copolymer is preferably comprised between 1 and 35, more preferably 2 to 20, especially 3 to 10, and In particular, a combination of hard and soft segments of the combination of 4 to 6 (i.e., added together). The copolymer preferably has from 5,000 to 80,000, more preferably from 1 to 5 〇〇〇〇, especially 13〇〇〇 to 30,000, and especially 15, 〇〇〇 to 2〇, the number average molecular weight in the garden. The copolymer preferably comprises less than > 5, more preferably less than 1 Torr, especially less than 5, and especially less than 2% by weight of ether or polyether groups. Thus, in a preferred embodiment, the copolymer is substantially free of ether or polyether groups, and more preferably, as defined herein, consists essentially of a polybenzazole hard segment and a polyester soft segment. . The wei copolymer preferably has a softening at 6 (^2 〇 (rc, more preferably 65 to 15 〇) (:, especially 70 to 125 ° C, and especially 75 to 1 〇 (in the range of rc) The copolymer preferably has a glass in the range of from -60 to 〇 ° C, more preferably from -50 to _10 ° C, especially from -40 to -20 eC, and especially from -35 to _25 ° C. Turn 1297017 A7 ____ Β 7 V. Description of the invention (8~) Transfer temperature (Tg) » The copolymer preferably has from 1.5 to 25, more preferably from 3 to 15, especially from 4.5 to 10, and especially from 5 The acid value in the range of 5 to 7.5 mg KOH/g. Furthermore, the copolymer preferably has an amine value of less than 1 Torr, more preferably less than 5, especially less than 3, and especially less than 1 mgK〇H/g. At the same time, the copolymer preferably has a value of less than 30, more preferably less than 15, especially less than 5, and especially less than 2 mg KOH/g. The copolymer according to the invention may pass through hard and soft chains. The pre-formation of the two stages before the reaction is produced. However, it is preferred to pre-form the hard segment and then form a soft segment in situ in the presence of the hard segment, for example via adding a diol to a sufficient residual acid group. Polyamine prepolymerization Another route for making the copolymer involves preforming a soft segment (oligoester (or polyester)) followed by grafting with an amine, preferably a diamine, to link the oligoester Together, a prepolymer having a relatively high acid value is formed. This low degree of conversion is selected to inhibit the amine transfer of the oligomeric vinegar. The residual acid group can be followed by an isothermal & L vinegar (preferably two The isocyanate reacts to produce additional guanamine linkages without damaging the oligoester structure. When using this method, the copolymer preferably comprises up to 15%, more preferably from i to 1% , especially from 2 to 8%, and especially from 3 to 7 weight percent of the amino carboxylic acid vinegar. A particular advantage of the polyamidamide copolymers described herein is improved substrate adhesion, especially for Preferably, the surface has a low energy surface of less than 5 Å, more preferably from 5 Å to 45 Å, especially from 20 to 40 Å and especially from 25 to 35 mN/m. The preferred substrate is a polyhydroxyl For example, polypropylene, preferably ruthenium polyethylene. The laminate structure can also be used, for example, by using the copolymer-11-h scale scale of the present invention. S material (CNS) A4 specification (21GX 297 mm) " --- 1297017 A7 B7 V. The invention describes the formation of two low surface energy substances (preferably poly-hydroxyl). 'Lamination can be formed by adhering low surface energy materials to high surface energy materials. The physical form of the substrate can vary over a wide range from thin film to 3 degree space objects such as automotive bumpers and electronic connector piping. In a particularly preferred embodiment of the invention, when the copolymer is used as an adhesive layer on a polyene hydroxy material (more preferably polyethylene), it has a thickness greater than 0.4, more preferably greater than 〇8, especially Is an adhesion strength greater than i, and in particular greater than 2 N/mm2 (measured as described herein). Furthermore, the polyurethane polyester copolymer suitably exhibits an improved adhesion to aluminum, preferably having an adhesion of greater than 1 Torr, more preferably greater than 25, especially greater than 65, and especially greater than 1000 Joules/m2. Fracture energy (measured as described herein). The polyamidoester copolymers described herein can be used as an adhesive in a wide variety of applications, such as piping, various automotive applications, and inks, such as printing onto educational packaging. A particularly preferred application is in shrink-wrapped tubing, as an adhesive in electronic connectors. Another use of the copolymer is on thermoplastic elastomers for engineering purposes which exhibit improved elastic and high temperature properties. In this case, the polyamine hard segment is, for example, polycaprolactam (nylon-6), adipic acid and hexamethylene diamine (nylon-6,6), polydodecylpropene Amine (polymer of nylon aminoundecanoic acid (nylon 4) The invention is illustrated by the following non-limiting examples. The following test methods are used in this patent specification. -12-

1297017 A7 ____B7 V. INSTRUCTIONS (1〇) (1) Softening point and glass transition temperature (Tg) were measured by a differential scanning calorimeter (DSC) using a Mettler DSC30 at a scan rate of 20 c/min. (ii) The number average molecular weight is measured by end group analysis using a ^^" rule. (iii) The gross value is the equivalent of the light base content of the light base of 1 gram of sample. The reaction, followed by hydrolysis of excess acetic anhydride to measure 'the resulting acetic acid is then titrated with a solution of potassium hydroxide in ethanol. (iv) The acid value is the number of milligrams of potassium hydroxide required to neutralize the free fatty acids in the sample. It is measured by direct titration of a standard potassium hydroxide solution. (v) The amine value is the number of grams of potassium hydroxide in 1 gram of sample, which is directly titrated with a standard potassium hydroxide solution followed by bromophenol blue. When the indicator is measured by salt titration (vi) Adhesion of the substrate: (a) For the polycalypt turtle, the Instr〇n tensile tester is used according to A STM D i〇〇2 by using the lap shear adhesion strength test. To measure, two sheets of low-degree polyethylene wafers with a thickness of 4 mm were melted on the first piece of polyethylene by a copolymer of 25 mm X 25 mm, followed by a second piece of poly /European woman sticks it together. Adhesive can be placed under slight pressure At room temperature, the sample was placed at 50% RV and 23 °C for at least 24 hours before the test. The load that destroys the adhesive bond is the adhesion strength of the polyamide copolymer to polyethylene, and (b) for aluminum. It is then measured in a fixed-arm peel tester. The adhesive layer of the copolymer is applied to the aluminum plate under vacuum to remove trapped air and volatiles. However, in order to tightly control the thickness of the final adhesive layer, the hydraulic press is completely cleaned and The grease-removed aluminum foil strip is placed on the molten adhesive. Then before the test - 13 - This paper scale applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1297017

Description of the invention The test samples were cooled and equilibrated at 50% RV and 23 °C for at least 24 hours. The peel test itself is about 45. The corner strips the aluminum foil strip from the adhesive' and measures the applied force (adhesive breaking energy (Ga)). EXAMPLES Example 1 900 g of "Pripol" 1013 ((trade name) dimer acid, C36 dicarboxyl (from Uniqema)) was placed in a mechanically agitated, condensed tube (to remove the released water) , a nitrogen inlet and a dropping funnel in a round bottom flask and evacuated. Heat the dimer acid to about 8 (TC, and add 76 5 grams of ethylenediamine dropwise to the reaction, taking care to reduce any possibility Exothermic reaction. Allow the reaction to stand at 80 ° C for 1 hour after all the amines have been added. Raise the reaction temperature to 160 ° C for 1 hour, then raise the reaction temperature to 2 ° C and keep it The obtained polyamido prepolymer has the following properties, which are measured as described above: (1) The number average molecular weight is 2,300. (ii) The acid value is 37 mgKOH/g - (iii) The amine value is 0.2 mgKOH/g. 14 14.5 g of 1,6-hexanediol was added dropwise to 370 g of the polyamine prepolymer prepared above, and reacted at 225 ° C for 4 hours. At the last 45 minutes of the reaction time Vacuuming to a value of 30 Torr to remove water. The resulting polylactide copolymer has the following properties, as described above Amount: (1) The softening point is 98 ° C, and the glass transition temperature (Tg) is -39 ° C. (ii) The number average molecular weight is 5900. (iii) The hydroxyl value is 6 mg KOH / g ^ -14 - This paper scale applies China National Standard (CNS) A4 Specification (210X 297 mm) 1297017 A7 B7 V. Description of Invention (12) (iv) The acid value is 9 mgKOH/g. (v) The amine value is 4 mgKOH/g. (vi) The substrate adhesion of the polyene hydroxy group was 0.34 N/mm 2. Destruction refers to the adhesion failure of the adhesive/substrate interface. Example 2 400 g of "Pripol" 1013 was placed in a round bottom flask as in Example 1. The dimer acid was heated to about 225 ° C, and 16.4 g of 1,6-hexanediol was added dropwise to the reaction. After the diol was completely added, the reaction was allowed to stand at 225 ° C for 1 hour. The polyester prepolymer has the following properties, which are measured as described above: (1) The number average molecular weight is about 750. (ii) The acid value is 153 mgKOH/g. (iii) The hydroxyl value is 〇mgKOH/g 〇25 5 g of ethylenediamine was added dropwise to 410 g of the oligoester prepolymer prepared above and reacted at 200 ° C for 1.5 hours. The product was dried under full vacuum while cooling to 180 ° C. 19 g of hexamethylene diisocyanate was added dropwise and reacted at 225 ° C for 3 hours, at which time carbon dioxide was released. The obtained polyamidamide copolymer had the following properties, which were measured as described above. : (i) The number average molecular weight is 9,500. (ii) Hydroxyl value less than 1 mgKOH/g 〇 (iii) Acid value is 10·8 mgKOH/g 〇 (iv) The amine value is 0.9 mgKOH/g. O) The adhesion to the substrate of polyene hydroxy is 〇·7 N/mm2. Destruction refers to the adhesion failure of the adhesive/substrate interface. -15· The paper size applies to the China Time Standard (CNS) A4 specification (210X297 mm) "

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1297017 A7 _ B7___ V. INSTRUCTION DESCRIPTION (13) Example 3 23 g of "Pripol" 1013 was placed in a round bottom flask as in Example 1. The dimer acid was heated to 80 ° C and dropped 21 ° One gram of ethylenediamine was added to the reaction. After complete addition, the reaction was allowed to stand at 80 ° C for 1 hour. The reaction temperature was raised to 160 ° C for 1 hour, and then the reaction temperature was raised to 20 (TC and After 1 hour, 66.4 grams of 1,6-hexanediol was added to the reaction mixture. Finally, the reaction temperature was raised to 225 ° C for 4 hours. At the last 45 minutes of the reaction time, the vacuum was evacuated to 3 0. The value of mbar. The obtained polyamidamide copolymer has the following properties, which are measured as described above: (i) The softening point is 91 ° C, and the glass transition temperature (Tg) is -55 ° C. (ii) The number average molecular weight is 4,500. (iii) The hydroxyl value is 7 mgKOH/g 〇(iv) The acid value is 17 mgKOH/g 〇(v) The amine value is 0.7 mgKOH/g. (vi) Adhesion to the substrate of the polyglycos The force is 〇·84 N/mm2. Destruction refers to the adhesion failure of the adhesive/substrate interface. Example 4 25 8 g of "Pripol" 1013 was placed in a round bottom flask as in Example 1. The dimer acid was heated to 80 ° C and 44.4 g of ethylenediamine was added dropwise to the reaction over a period of 3 Torr. After complete addition, the reaction was held at 80 ° C for 1 hour. The reaction temperature was raised to 160 ° C for 40 minutes. Then the reaction temperature was raised to 200 ° C for 1 hour. After that, 24.6 g of "Pripol" 2033 (dimer diol, C 3 6 dicarboxyl group) (from Uniqema)) added to the reaction mixture. Finally raise the reaction temperature to 225. (: and keep 5 small -16 - This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ^ 1297017 A7 B7 V. At the time of the invention (14), the vacuum was then evacuated to a value of 30 mbar and maintained for 2 hours. The obtained polyamidamide copolymer had the following properties, which were measured as described above: (1) The softening point was 95 ° C, and The glass transition temperature (Tg) is _46 ° C. (ii) The number average molecular weight is 12,750. (iii) The hydroxyl value is 7.5 mg KOH / g. (iv) The acid value is 17.5 mg KOH / g ^ (v) The amine value is 0.1 mgKOH/g (vi) Adhesion to aluminum is 28 J/m2. Example 5 Put 23 8 g of "Pripol" I embodiment of the round bottom flask. The dimer acid was heated to 80 ° C, and at 30 minutes was added dropwise 21.1 g of ethylenediamine was added to the reaction. • After complete addition, let the reaction at 8 (rc for i hours. Raise the reaction temperature to 160 ° C for 60 minutes, then raise the reaction temperature to 200. (: and hold for 1 hour. After that, 66.4 grams of "Priplast" 3198 ((trade name) (from uniqema)) was added to the reaction mixture. Finally, raise the reaction temperature to 225 ° C for 5 hours, then evacuate to a value of 30 mbar and maintain 2 hours. The obtained polyamidoester copolymer had the following properties, which were measured as described above: (i) The softening point was 91 ° C, and the glass transition temperature (Tg) was -55 ° C. (ii) Number average The molecular weight is 12,980. (iii) The hydroxyl value is 7 mgKOH/g 〇(iv) The acid value is 17.1 mgKOH/g. (v) The amine value is 〇·1 mgKOH/g. (vi) The adhesion to aluminum substrate is 7 〇 joules / m2. ___-17- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Binding 1297017 B7 V. INSTRUCTION DESCRIPTION (15) The above examples illustrate the improved properties of the polyamidoester copolymer according to the present invention.

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Claims (1)

In the patent of I29iQi7G933G, the scope of the Chinese patent application is replaced by the scope of the application of the patent. The patent application scope is ~~~ --- Announcement L-polyacetamide copolymer ‘is less than or equal to 〇.玻 玻 glass. Glass transfer temperature (Tg) and at 70 to 125. a softening point in the range of ruthenium, and comprising at least one hard segment comprising at least one guanamine bond, and at least one soft segment comprising at least one vinegar bond; the soft segment of the yttrium is composed of at least one dimer fatty acid and / or dimer diol and / or its equivalent. 2. A copolymer according to the scope of claim 1st Jg &gt;#e i f α祀固乐i, wherein the copolymer has a Tg of less than or equal to -10 °C. 3. The copolymer of claim 2, wherein the copolymer has a softening point in the range of 75 to 1 °C. 4. The copolymer of claim </ RTI> or claim 2, wherein the copolymer has a number average molecular weight in the range of from 1 Torr to 50 Å. 5. The copolymer of claim 5, wherein the copolymer comprises a dispersed segment of a combined hard segment and a soft segment in the range of from 3 to 1 Å. 6. The number average molecular weight in the range of (50) to (4) Μ in the range of 550 to 3,0 。 as in the copolymer of the scope of the patent application. 7. The copolymer of claim 4, wherein the copolymer has an adhesion strength greater than 〇4 N/mm2 for the low density polyethylene. 8. The copolymer of claim i or 2, wherein the weight ratio of the hard segment to the soft segment is in the range of 4 to 2 〇 : 。. 9. The copolymer of claim i or claim 2, wherein the hard bond segment is formed by a f-moon moon squaraine acid and a non-dimer fatty acid, and the sputum is condensed with a total dicarboxylic acid. The polymer fatty acid is present in a ratio of from 5 Å to 100%: 0 to 50% of the non-dimer fatty acid system. 10. A layer of poly-smoke substrate, #includes a surface energy of less than 5 〇 mN/m • 1297017, A8 B8 C8 D8, in the patent application, and having an adhesive layer on at least one surface thereof; the adhesive layer comprises a polyglycosylamine copolymer having a glass of less than or equal to 〇 ° C = shift At least one of the hard chain containing at least one guanamine bond containing at least one soft bond segment containing one bond; wherein the soft bond segment is composed of at least one dimer fatty acid and/or dimer fat The diol and/or its equivalent are formed. Π· A method of forming a polyamidamide copolymer, wherein the polyamidoester copolymer has a glass transition temperature of less than or equal to 0 ° C and a softening point in the range of 7 〇 to i 2 5 t' and includes at least a hard segment comprising at least one guanamine bond, and at least one soft segment comprising at least one ester chain; the soft segment being composed of at least one dimer fatty acid and/or dimer diol and/or equivalent thereof The method is formed; the method comprises (i) pre-forming of the hard segment, and (ii) forming a soft segment in situ in the presence of the hard segment. 12. A copolymer as claimed in claim 1 or 2 which is used as an adhesive. 13. A method of forming a polyamine amine copolymer, wherein the polyamine has a glass transition temperature of less than or equal to 〇°c and a softening point in the range of 70 to 1 25 t: And comprising at least one hard segment comprising at least one guanamine bond, and at least one soft segment comprising at least one ester bond; the soft segment being composed of at least one dimer fatty acid and/or dimer diol and/or Or a counterpart thereof; the method comprising (i) pre-forming an oligoester, (i) reacting the oligoester with an amine to form a prepolymer, and (iii) reacting the prepolymer with an isocyanate. -2- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 裴