Polycarbodiimide compositions, adhesive compositions and methods of making, use

Abstract

The application discloses a polycarbodiimide composition, an adhesive composition and a preparation method and application thereof. The polycarbodiimide composition comprises component A and component B; the component A comprises a compound as shown in a formula I; the component B comprises a compound as shown in a formula II; the mass ratio of the compound of the formula I to the compound of the formula II is 0.25-4:1; R1 is a divalent aliphatic hydrocarbon group with 1-18 carbon atoms or a divalent alicyclic hydrocarbon group with 3-13 carbon atoms; R4 is a divalent aromatic hydrocarbon group with 6-13 carbon atoms; R2, R3, R5 and R6 are independently residues of a hydrophilic compound containing active hydrogen after removing hydrogen atoms; the hydrophilic compound is an alcohol compound, an ether compound or an amine compound, the molecular weight of the hydrophilic compound is less than 1500 g / mol; and n or m is 1-10.

Description

TECHNICAL FIELD

[0001] The present application relates to a polycarbodiimide composition, adhesive composition and preparation method and application. BACKGROUND

[0002] In recent years, with the strengthening of environmental protection in China, the "oil to water" scheme has been introduced, and water-based resins have developed rapidly. In order to obtain a stable dispersion system, hydrophilic groups such as carboxyl, hydroxyl, amino and the like are often introduced into water-based resins. The presence of these hydrophilic groups can improve the water solubility and dispersibility of water-based resins, but the residual groups can reduce the water resistance and strength of the film. Therefore, water-based resins are often used together with water-based crosslinking agents to improve their performance.

[0003] Carbodiimides are a class of compounds that can selectively react with carboxyl groups. Due to their green and low toxicity characteristics, they have been widely used in some fields with high environmental protection requirements. Currently, carbodiimides are widely used in coatings and adhesives for automotive interiors. Among them, the leather finishing agent for automotive seats has special requirements for performance, requiring high wear resistance, high strength and high flexibility. High wear resistance and high strength mean high crosslinking density, which usually cannot satisfy high flexibility at the same time.

[0004] The carbodiimide crosslinking agents on the market can only improve the wear resistance, strength and crosslinking density of the coating, and have no help for improving the flexibility of the coating. How to improve the wear resistance, strength and flexibility of the leather finishing agent through the carbodiimide crosslinking agent is a problem that needs to be solved at present. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the defects of the prior art polycarbodiimide that can only improve the wear resistance, strength and crosslinking density of the coating in the water-based system, and has no help for improving the flexibility of the coating. A polycarbodiimide composition, adhesive composition and preparation method and application are provided. The polycarbodiimide composition of the present application has good application effect in the water-based resin system, which can not only improve the crosslinking density of the coating, improve the effect of high wear resistance and high strength, but also improve the flexibility of the coating, and has wider application range.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] The present application provides a polycarbodiimide composition, which comprises A component and B component; the A component comprises a compound as shown in formula I; the B component comprises a compound as shown in formula II; the mass ratio of the compound of formula I to the compound of formula II is (0.25-4):1;

[0008]

[0009] R1is a divalent aliphatic hydrocarbon group having a carbon number of 1 to 18 or a divalent alicyclic hydrocarbon group having a carbon number of 3 to 13;

[0010] R4is a divalent aromatic hydrocarbon group having a carbon number of 6 to 13;

[0011] R2, R3, R5, R6are independently a residue of a hydrophilic compound containing active hydrogen after removing hydrogen atoms; the hydrophilic compound is an alcohol compound, an ether compound or an amine compound, and the molecular weight of the hydrophilic compound is less than 1500 g / mol;

[0012] n or m is 1 to 10.

[0013] In the present application, the mass ratio of the compound of formula I to the compound of formula II is preferably (0.5 to 3.5) : 1, for example 0.6 : 1, 1 : 1, 1.5 : 1, 2 : 1, 2.5 : 1, 3 : 1 or 3.5 : 1.

[0014] In R1, the divalent aliphatic hydrocarbon group having a carbon number of 1 to 18 can be a divalent aliphatic hydrocarbon group having a carbon number of 1 to 10; for example, a divalent aliphatic hydrocarbon group having a carbon number of 6; or for example, -(CH2)6-.

[0015] In R1, the divalent alicyclic hydrocarbon group having a carbon number of 3 to 13 can be a divalent alicyclic hydrocarbon group having a carbon number of 5 to 13; for example, a divalent alicyclic hydrocarbon group having a carbon number of 9 to 13; or for example,

[0016] In R4, the divalent aromatic hydrocarbon group having a carbon number of 6 to 13 can be wherein L4and L5are independently substituted or unsubstituted C1-C6alkylene.

[0017] wherein L4and L5may be the same or different.

[0018] wherein the substituent in the substituted C1-C6alkylene in L4and L5may be halogen. The halogen is preferably F, Cl, Br or I; more preferably Cl.

[0019] wherein the C1-C6alkylene in the substituted or unsubstituted C1-C6alkylene in L4and L5may be methylene,

[0020] In certain preferred embodiments of the present application, R4may be

[0021] In the present application, R2and R3may be the same or different.

[0022] In the present application, R5 and R6 can be the same or different.

[0023] In the present application, the hydrophilic compound is preferably an ether compound, more preferably polyethylene glycol monomethyl ether or polypropylene glycol monomethyl ether.

[0024] In the present application, the molecular weight of the hydrophilic compound is preferably less than 1200 g / mol, for example 400 g / mol, 500 g / mol, 750 g / mol or 1000 g / mol.

[0025] In certain preferred embodiments of the present application, the hydrophilic compound can be MPEG-400, MPEG-750 or MPEG-1000, i.e. polyethylene glycol monomethyl ether having a molecular weight of 400, 750 or 1000.

[0026] In the present application, n is generally an integer, for example 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 3-7.

[0027] In the present application, m is generally an integer, for example 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 3-7.

[0028] In preferred embodiments of the present application, the compound of formula I can be any one of the following structural formulae A1-A4:

[0029] A1:

[0030]

[0031] A2:

[0032]

[0033] A3:

[0034]

[0035] A4:

[0036]

[0037] In preferred embodiments of the present application, the compound of formula II can be any one of the following structural formulae B1-B3:

[0038] B1:

[0039]

[0040] B2:

[0041]

[0042] B3:

[0043]

[0044] The repeating units 8.3, 16.3 or 21.9 in the end groups of both ends formed by the end-capping agent in the structural formula of A1-A4 and B1-B3 are average values calculated from the end-capping agent according to common knowledge in the art.

[0045] In the present application, the A component or the B component generally further contains water or a water-soluble organic solvent. The water-soluble organic solvent generally refers to an organic solvent that is miscible with water.

[0046] The solubility parameter of the water-soluble organic solvent is preferably 8.0-14.0, more preferably 8.0-12.0, for example 8.8 or 9.4. The solubility parameter generally refers to a physical constant that measures the solubility of a liquid phase, and its physical meaning is the square root of the cohesive energy density of the liquid substance.

[0047] The water-soluble organic solvent is preferably one or more of an alcohol solvent, a ketone solvent, an ether solvent and an ester solvent.

[0048] The alcohol solvent can be one or more of an alcohol solvent with a carbon atom number of 1-5, for example ethanol, ethylene glycol and propylene glycol.

[0049] The ketone solvent can be one or more of acetone, butanone and methyl isobutyl ketone.

[0050] The ether solvent can be one or more of ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether and dipropylene glycol methyl ether.

[0051] The ester solvent can be one or more of ethyl acetate, n-butyl acetate, ethylene glycol carbonate, ethylene glycol ethyl ether acetate and propylene glycol methyl ether acetate, for example propylene glycol methyl ether acetate and / or ethyl acetate.

[0052] When the A component contains a solvent, the solid content of the A component can be 10%-100%, preferably 30%-50%, for example 40%.

[0053] When the B component contains a solvent, the solid content of the B component can be 10%-100%, preferably 30%-50%, for example 40%.

[0054] The present application also provides an adhesive composition comprising the polycarbodiimide composition as described above and a carboxyl-containing water-based resin, and the amount of the polycarbodiimide composition is 2-10%, and the above percentage refers to the mass percentage of the polycarbodiimide composition in the adhesive composition.

[0055] In the present application, the polymeric carbodiimide composition preferably accounts for 3-9.5% of the adhesive composition, such as 3%, 3.5%, 4%, 5%, 6%, 7%, 8% or 9%.

[0056] In the present application, the water-based resin is preferably an acrylic resin or a water-based polyurethane, such as PU-477.

[0057] In the present application, the water-based resin preferably has a solid content of 30%.

[0058] The present application also provides a preparation method of the adhesive composition, which comprises the following steps: mixing the raw materials of the adhesive composition uniformly.

[0059] The present application also provides an application of the polymeric carbodiimide composition or the adhesive composition in the fields of automobiles, furniture, shoe materials and the like.

[0060] On the basis of common knowledge in the art, the above-mentioned preferred conditions can be combined arbitrarily, thereby obtaining various preferred examples of the present application.

[0061] The reagents and raw materials used in the present application are commercially available.

[0062] The positive progress effect of the present application is that:

[0063] The polymeric carbodiimide composition of the present application has good application effect in the water-based resin system, not only has high gel rate (72-80%), but also improves the crosslinking density of the coating, has high wear resistance (17-25 times), high tensile strength (17-22 MPa), and high elongation at break (280-430%), thereby improving the flexibility of the coating and having wider application range. DETAILED DESCRIPTION

[0064] The present application will be further illustrated by the following examples, but the present application is not limited in the scope of the examples. The experimental methods in the following examples without specific conditions are selected according to conventional methods and conditions or according to the instructions of the products.

[0065] The main raw materials used in the following examples and comparative examples are as follows:

[0066] IPDI, purchased from Wanhua Chemical Group Co., Ltd., WANNATE IPDI≥99.5%;

[0067] HMDI, purchased from Wanhua Chemical Group Co., Ltd., WANNATE HMDI≥99.5%;

[0068] TMDXI, purchased from Zhenxin Resin (China) Co., Ltd., CYTEC TMXDI≥99.5%;

[0069] MPPO, purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd., TCI≥95.0% (RG);

[0070] MPEG-400, purchased from Clariant Polyglykol M 400 PU≥99.5%.

[0071] Use PU-477 was used to detect the application performance of each crosslinking agent. PU-477 is a water-based polyurethane emulsion applied to leather finishing agent, solid content 30%, purchased from Star.

[0072] Preparation of the aqueous dispersion of A1 component in the polycarbodiimide-containing composition:

[0073] In a 5L three-necked flask, 1000g of dicyclohexylmethane diisocyanate (HMDI, 3.81 mol) was added, protected by nitrogen, 4g of 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (MPPO) was added, and the system was reacted at 160°C for 15 hours. The NCO% of the system was 6.2%, and a carbodiimide prepolymer with a polymerization degree of about 5 (860g, 0.64 mol) was obtained. The temperature of the system was reduced to 80°C, 512g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 1.28 mol) was added, and the reaction was carried out for 2 hours. The NCO% of the system was reduced to 0, and 1372g of polycarbodiimide A1 component (dicyclohexylmethane diisocyanate, polymerization degree 5, both ends capped with polyethylene glycol monomethyl ether) was obtained, and its structure is shown as follows:

[0074]

[0075] Take 2058g of deionized water, and add it to the above polycarbodiimide A1 component while stirring, and dissolve thoroughly to obtain an aqueous dispersion of polycarbodiimide A1 component with a solid content of 40%.

[0076] Preparation of the aqueous dispersion of A2 component in the polycarbodiimide-containing composition:

[0077] Into a 5L three-necked flask, 1000g of isophorone diisocyanate (IPDI, 4.5 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1-oxide (MPPO) was added under nitrogen protection. The reaction was carried out at 130°C for 12 hours, and the NCO% of the system was 7.6%. A carbodiimide prepolymer (835g, 0.75 mol) with a polymerization degree of about 5 was obtained. The temperature of the system was lowered to 80°C, and 600g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 1.5 mol) was added. The reaction was carried out for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A2 component (based on isophorone diisocyanate, a polycarbodiimide capped with MPEG-400 with a polymerization degree of 5) with a solid content of 40% was obtained, and its structure is shown below:

[0078]

[0079] Into a 5L three-necked flask, 1000g of isophorone diisocyanate (IPDI, 4.5 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1-oxide (MPPO) was added under nitrogen protection. The reaction was carried out at 130°C for 12 hours, and the NCO% of the system was 7.6%. A carbodiimide prepolymer (835g, 0.75 mol) with a polymerization degree of about 5 was obtained. The temperature of the system was lowered to 80°C, and 600g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 1.5 mol) was added. The reaction was carried out for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A2 component (based on isophorone diisocyanate, a polycarbodiimide capped with MPEG-400 with a polymerization degree of 5) with a solid content of 40% was obtained, and its structure is shown below:

[0080] Preparation of a water dispersion of the A3 component in the polycarbodiimide composition:

[0081] Into a 5L three-necked flask, 1000g of isophorone diisocyanate (IPDI, 4.5 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1-oxide (MPPO) was added under nitrogen protection. The reaction was carried out at 130°C for 12 hours, and the NCO% of the system was 7.6%. A carbodiimide prepolymer (835g, 0.75 mol) with a polymerization degree of about 5 was obtained. The temperature of the system was lowered to 80°C, and 600g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 1.5 mol) was added. The reaction was carried out for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A2 component (based on isophorone diisocyanate, a polycarbodiimide capped with MPEG-400 with a polymerization degree of 5) with a solid content of 40% was obtained, and its structure is shown below:

[0082]

[0083] Into a 5L three-necked flask, 1000g of isophorone diisocyanate (IPDI, 4.5 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1-oxide (MPPO) was added under nitrogen protection. The reaction was carried out at 130°C for 12 hours, and the NCO% of the system was 7.6%. A carbodiimide prepolymer (835g, 0.75 mol) with a polymerization degree of about 5 was obtained. The temperature of the system was lowered to 80°C, and 600g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 1.5 mol) was added. The reaction was carried out for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A2 component (based on isophorone diisocyanate, a polycarbodiimide capped with MPEG-400 with a polymerization degree of 5) with a solid content of 40% was obtained, and its structure is shown below:

[0084] Preparation of a water dispersion of the A3 component in the polycarbodiimide composition:

[0085] In a 5L three-necked flask, 1000g of dicyclohexylmethane diisocyanate (HMDI, 3.81 mol) was added, and 4g of 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (MPPO) was added under nitrogen protection. The system was reacted at 160°C for 18 hours, and the NCO% of the system was 4.7%. A carbodiimide prepolymer (853g, 0.48 mol) with a polymerization degree of about 7 was obtained. The temperature of the system was reduced to 80°C, and 384g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 0.96 mol) was added. The system was reacted for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A4 component (dicyclohexylmethane diisocyanate, polycarbodiimide with a polymerization degree of 7 and terminated by polyethylene glycol monomethyl ether at both ends) was obtained, and the structure thereof is shown as follows:

[0086]

[0087] Deionized water (1856g) was taken, and added to the polycarbodiimide A4 component under stirring. After sufficient dissolution, a water dispersion containing the polycarbodiimide A4 component with a solid content of 40% was obtained.

[0088] Preparation of a water dispersion of the B1 component in the polycarbodiimide-containing composition:

[0089] In a 5L three-necked flask, 1000g of dicyclohexylmethane diisocyanate (HMDI, 3.81 mol) was added, and 4g of 3-methyl-1-phenyl-2-cyclophosphene-1-oxide (MPPO) was added under nitrogen protection. The system was reacted at 160°C for 18 hours, and the NCO% of the system was 4.7%. A carbodiimide prepolymer (853g, 0.48 mol) with a polymerization degree of about 7 was obtained. The temperature of the system was reduced to 80°C, and 384g of polyethylene glycol monomethyl ether (MPEG-400, molecular weight 400g / mol, 0.96 mol) was added. The system was reacted for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide A4 component (dicyclohexylmethane diisocyanate, polycarbodiimide with a polymerization degree of 7 and terminated by polyethylene glycol monomethyl ether at both ends) was obtained, and the structure thereof is shown as follows:

[0090]

[0091] Deionized water (1856g) was taken, and added to the polycarbodiimide A4 component under stirring. After sufficient dissolution, a water dispersion containing the polycarbodiimide A4 component with a solid content of 40% was obtained.

[0092] Preparation of a water dispersion of the B1 component in the polycarbodiimide-containing composition:

[0093] Into a 5L three-necked flask, 1000g of tetramethylxylylene diisocyanate (TMXDI, 4.10 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1- oxide (MPPO) was added under nitrogen protection. The system was reacted at 180°C for 20 hours, and the NCO% of the system was 6.8%. A carbodiimide prepolymer with a polymerization degree of about 5 (850g, 0.76 mol) was obtained. The temperature of the system was lowered to 80°C, and 1140g of polyethylene glycol monomethyl ether (MPEG-750, molecular weight 750g / mol, 1.52 mol) was added. The system was reacted for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide B2 component (based on tetramethylxylylene diisocyanate, a polycarbodiimide capped with MPEG-750 with a polymerization degree of 5) was obtained, and the structure thereof is shown below:

[0094]

[0095] Into the polycarbodiimide B2 component, 2985g of deionized water was added while stirring, and was sufficiently dissolved to obtain a water dispersion of the polycarbodiimide B2 component with a solid content of 40%.

[0096] Preparation of a water dispersion of a polycarbodiimide B3 component in a polycarbodiimide composition:

[0097] Into a 5L three-necked flask, 1000g of tetramethylxylylene diisocyanate (TMXDI, 4.10 mol) was added, and 4g of 3-methyl-l-phenyl-2-cyclophosphor-1- oxide (MPPO) was added under nitrogen protection. The system was reacted at 180°C for 20 hours, and the NCO% of the system was 6.8%. A carbodiimide prepolymer with a polymerization degree of about 5 (850g, 0.76 mol) was obtained. The temperature of the system was lowered to 80°C, and 1140g of polyethylene glycol monomethyl ether (MPEG-750, molecular weight 750g / mol, 1.52 mol) was added. The system was reacted for 2 hours, and the NCO% of the system was reduced to 0. A polycarbodiimide B2 component (based on tetramethylxylylene diisocyanate, a polycarbodiimide capped with MPEG-750 with a polymerization degree of 5) was obtained, and the structure thereof is shown below:

[0098]

[0099] Into the polycarbodiimide B3 component, 3555g of deionized water was added while stirring, and was sufficiently dissolved to obtain a water dispersion of the polycarbodiimide B3 component with a solid content of 40%.

[0100] Preparation of an adhesive composition:

[0101] Example 1

[0102] The water dispersion of 2.5 parts by mass of the above polymeric carbodiimide A1 component, the water dispersion of 2.5 parts by mass of the above polymeric carbodiimide B1 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0103] Example 2

[0104] The water dispersion of 2.5 parts by mass of the above polymeric carbodiimide A2 component, the water dispersion of 2.5 parts by mass of the above polymeric carbodiimide B1 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0105] Example 3

[0106] The water dispersion of 1 part by mass of the above polymeric carbodiimide A1 component, the water dispersion of 1 part by mass of the above polymeric carbodiimide B1 component, and 98 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0107] Example 4

[0108] The water dispersion of 3.5 parts by mass of the above polymeric carbodiimide A1 component, the water dispersion of 3.5 parts by mass of the above polymeric carbodiimide B1 component, and 93 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0109] Example 5

[0110] The water dispersion of 5 parts by mass of the above polymeric carbodiimide A1 component, the water dispersion of 5 parts by mass of the above polymeric carbodiimide B1 component, and 90 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0111] Example 6

[0112] The water dispersion of 1 part by mass of the above polymeric carbodiimide A1 component, the water dispersion of 4 parts by mass of the above polymeric carbodiimide B1 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0113] Example 7

[0114] The water dispersion of 4 parts by mass of the above polymeric carbodiimide A1 component, the water dispersion of 1 part by mass of the above polymeric carbodiimide B1 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to homogenize, to produce an adhesive composition.

[0115] Example 8

[0116] A water dispersion of 2.5 parts by mass of the above polymeric carbodiimide Al component, a water dispersion of 2.5 parts by mass of the above polymeric carbodiimide B2 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition. Example 8

[0117] Example 9

[0118] A water dispersion of 2.5 parts by mass of the above polymeric carbodiimide Al component, a water dispersion of 2.5 parts by mass of the above polymeric carbodiimide B3 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition. Example 9

[0119] Example 10

[0120] A water dispersion of 2.5 parts by mass of the above polymeric carbodiimide A3 component, a water dispersion of 2.5 parts by mass of the above polymeric carbodiimide Bl component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition. Example 10

[0121] Example 11

[0122] A water dispersion of 2.5 parts by mass of the above polymeric carbodiimide A4 component, a water dispersion of 2.5 parts by mass of the above polymeric carbodiimide Bl component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition. Example 11

[0123] Comparative Example 1

[0124] Blank: only PU-477. Comparative Example 1

[0125] Comparative Examples 2 to 4

[0126] A water dispersion of 5 parts by mass of the above polymeric carbodiimide Al component, a water dispersion of the A2 component, a water dispersion of the Bl component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition of Comparative Examples 2 to 4. Comparative Examples 2 to 4

[0127] Comparative Example 5

[0128] A water dispersion of 2.5 parts by mass of the above polymeric carbodiimide Al component, a water dispersion of 2.5 parts by mass of the above polymeric carbodiimide A2 component, and 95 parts by mass of PU-477 were mixed, and stirred sufficiently to be uniform, to produce an adhesive composition. The PU-477 is mixed and stirred well to obtain an adhesive composition.

[0129] Example 1

[0130] The adhesive compositions of the use examples and comparative examples are subjected to alcohol rubbing resistance test, gel fraction test and mechanical property test.

[0131] 1. Alcohol rubbing resistance test:

[0132] The adhesive composition is uniformly coated on the PVC leather with a wire bar, and the coating thickness is 20 μm. The wet film is placed in a 120 °C air oven for 30 min for sufficient drying and curing, and is left at room temperature for 1 day. The leather sample after drying is stretched by 10% along the rubbing direction. The wool felt is placed in a test solution (e.g. 95% alcohol) for more than 1 min to be completely wetted (not more than 24 h), the felt is taken out of the solution, and is placed in the middle of four water-absorbing filter papers (two on the top and two on the bottom, and the test surface is horizontally contacted with the filter papers). A weight of 900 ± 10 g is placed on the filter papers for 1 min, and the solution is squeezed out to make the weight of the felt about 1 g, which can be used for the test. The felt is fixed on the test head, and the test head is gently pressed on the surface of the rubbing platform sample to make the felt completely horizontally contacted with the sample, and the load is 9 N. The rubbing test is started. The rubbing number when the coating is whitened is recorded, and the results are shown in Table 1. The higher the number is, the better the alcohol resistance is.

[0133] 2. Gel fraction test:

[0134] The adhesive composition is weighed in a Teflon dish to form a complete liquid film. The Teflon dish is placed in a 120 °C air oven for 3 h for sufficient drying and curing. The completely dried and cured coating is taken out of the Teflon dish, and is cut into small squares with the same shape and size. The weight a of a 200-mesh stainless steel wire mesh is weighed, the coating sample weight b is placed in the mesh, and is wrapped. The mesh is placed in a Soxhlet extractor with toluene as the solvent for reflux extraction for 3 h. The mesh is dried in an air oven, and the total weight c is weighed. The gel fraction is calculated as 100%*(c-a) / b. The higher the gel fraction is, the higher the crosslinking density is, and the better the performance is. The test results are shown in Table 1.

[0135] 3. Mechanical property test:

[0136] The adhesive composition is poured into a horizontally placed polytetrafluoroethylene plate to form a complete liquid film. The Teflon dish is placed in a 120 °C air oven for 3 h for sufficient drying and curing. The completely dried and cured coating (the film thickness is about 1 mm) is taken out, and is naturally cooled for standby. The film is made into a dumbbell shape with a size of 25 mm x 4 mm. The tensile strength and elongation at break of the film are tested at room temperature by using a SANS microcomputer-controlled electronic universal testing machine, and the tensile speed is 200 mm / min. The test is measured for 3 times to take the average value. The higher the elongation at break is, the better the flexibility is. The test results are shown in Table 1.

[0137] Table 1

[0138]

[0139]

[0140] From the comparison between the embodiment of the present application and the comparative example 1, it can be seen that the polycarbodiimide composition of the present application has good application effect in the water-based resin system, not only has high gel rate, improves the crosslinking density of the coating, has high wear resistance and high tensile strength, but also has high elongation at break, improves the flexibility of the coating, and has wider application range.

[0141] From the comparison between the examples 1-10 and the comparative examples 2-5, it can be seen that only the specific polycarbodiimide composition of the present application can have good application effect in the water-based resin system, and only using one of the substances or using the polycarbodiimide composition in a low amount cannot have good application effect in the water-based resin system.

Claims

1. A polycarbodiimide composition, characterized in that, It comprises component A and component B; component A comprises a compound as shown in Formula I; component B comprises a compound as shown in Formula II; the mass ratio of the compound of Formula I to the compound of Formula II is (0.25-3.5):1; ； ； Wherein, R1 is a divalent alicyclic hydrocarbon group with 3-13 carbon atoms; R4 is a divalent aromatic hydrocarbon group with 6-13 carbon atoms; In R4, the divalent aromatic hydrocarbon group with 6-13 carbon atoms is L4 and L5 are independently substituted or unsubstituted C1-C6 alkylene groups; In L4 and L5, the C1-C6 alkylene groups in the substituted or unsubstituted C1-C6 alkylene groups are: , , or ; R2, R3, R5, and R6 are each residues of a hydrophilic compound containing active hydrogen after removing a hydrogen atom; the hydrophilic compound is an alcohol, ether, or amine compound, and the molecular weight of the hydrophilic compound is less than 1500 g / mol. n or m is 1-10.

2. The polycarbodiimide composition according to claim 1, characterized in that, The polycarbodiimide composition satisfies one or more of the following conditions: a) The mass ratio of compound I to compound II is (0.5-3.5):1; b) The n is 1, 2, 3, 4, 5, 6, 7, 8 or 9; c) The m is 1, 2, 3, 4, 5, 6, 7, 8 or 9.

3. The polycarbodiimide composition according to claim 2, characterized in that, The polycarbodiimide composition satisfies one or more of the following conditions: a) The mass ratio of compound I to compound II is 0.6:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or 3.5:1; b) The n is 3-7; c) The value of m is 3-7.

4. The polycarbodiimide composition according to claim 1, characterized in that, The polycarbodiimide composition satisfies one or more of the following conditions: a) In R1, the divalent alicyclic hydrocarbon group with 3-13 carbon atoms is a divalent alicyclic hydrocarbon group with 5-13 carbon atoms; b) R4 is ; c) R2 and R3 may be the same or different; d) R5 and R6 may be the same or different.

5. The polycarbodiimide composition according to claim 1, characterized in that, The polycarbodiimide composition satisfies one or more of the following conditions: a) In R1, the divalent alicyclic hydrocarbon group with 3-13 carbon atoms is a divalent alicyclic hydrocarbon group with 9-13 carbon atoms; b) L4 and L5 may be the same or different; c) In L4 and L5, the substituents in the alkylene groups that replace C1-C6 are halogens.

6. The polycarbodiimide composition according to claim 5, characterized in that, In R1, the divalent alicyclic hydrocarbon group with 3-13 carbon atoms is or ; And / or, the halogen is F, Cl, Br or I.

7. The polycarbodiimide composition according to claim 1, characterized in that, The polycarbodiimide composition satisfies one or two of the following conditions: a) The ether compound is polyethylene glycol monomethyl ether or polypropylene glycol monomethyl ether; b) The molecular weight of the hydrophilic compound is less than 1200 g / mol.

8. The polycarbodiimide composition according to claim 7, characterized in that, The polycarbodiimide composition satisfies one or two of the following conditions: a) The ether compound is MPEG-400, MPEG-750, or MPEG-1000; b) The molecular weight of the hydrophilic compound is 400 g / mol, 500 g / mol, 750 g / mol or 1000 g / mol.

9. The polycarbodiimide composition according to claim 1, characterized in that, The compound shown in Formula I is any one of the following structural formulas A1-A4: A1: ； A2： ； A3： ； A4： ； The compound shown in Formula II is any one of the following structural formulas B1-B3: B1： ； B2： ； B3： 。 10. The polycarbodiimide composition according to claim 1, characterized in that, The A component or the B component also contains water or a water-soluble organic solvent; When component A contains a solvent, the solid content of component A is 10%-100%; When component B contains a solvent, the solid content of component B is 10%-100%.

11. The polycarbodiimide composition according to claim 10, characterized in that, When component A contains a solvent, the solid content of component A is 30%-50%; When component B contains a solvent, the solid content of component B is 30%-50%.

12. The polycarbodiimide composition according to claim 11, characterized in that, When component A contains a solvent, the solid content of component A is 40%. When component B contains a solvent, the solid content of component B is 40%.

13. An adhesive composition, characterized in that, It includes the polycarbodiimide composition as described in any one of claims 1-12 and a carboxyl-containing aqueous resin, wherein the amount of the polycarbodiimide composition is 3-10%, and the above percentage is the mass percentage of the polycarbodiimide composition to the adhesive composition.

14. The adhesive composition of claim 13, characterized in that, The adhesive composition satisfies one or more of the following conditions: a) The amount of the polycarbodiimide composition used is 3-9.5%; b) The waterborne resin is an acrylic resin or a waterborne polyurethane; c) The solid content of the water-based resin is 20-40%.

15. The adhesive composition of claim 14, characterized in that, The adhesive composition satisfies one or more of the following conditions: a) The amount of the polycarbodiimide composition is 3%, 3.5%, 4%, 5%, 6%, 7%, 8%, or 9%; b) The aqueous resin is Relca® PU-477; c) The solid content of the water-based resin is 30%.

16. A method for preparing an adhesive composition according to any one of claims 13-15, characterized in that, It includes the following steps: mixing the raw materials of the adhesive composition evenly.

17. The use of a polycarbodiimide composition as described in any one of claims 1-12 or an adhesive composition as described in any one of claims 13-15 in the automotive, furniture and footwear industries.

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