WO2017080494A1

WO2017080494A1 - High-performance polyamide hot melt adhesive for surface decoration and preparation method therefor

Info

Publication number: WO2017080494A1
Application number: PCT/CN2016/105394
Authority: WO
Inventors: 施才财
Original assignee: 昆山天洋热熔胶有限公司; 上海天洋热熔粘接材料股份有限公司
Priority date: 2015-11-13
Filing date: 2016-11-11
Publication date: 2017-05-18
Also published as: CN105238337A

Abstract

Disclosed are a high-performance polyamide hot melt adhesive for surface decoration and a preparation method therefor. The preparation method is a simple preparation method mainly comprising the steps: selecting specific raw materials comprising aliphatic dicarboxylic acid, cycloaliphatic diamine, other diamines, C6-C12 lactam, polyamide 66 salt, a stearic acid, a glycerin modifier and an antioxidant, limiting proportions of all the raw materials, and performing polycondensation reaction by adopting disposable direct feeding. The surface glossiness of the polyamide hot melt adhesive prepared by the present invention is obviously improved, and the requirements of a specific highlight film product are met.

Description

Polyamide hot melt adhesive for high performance surface decoration and preparation method thereof

Technical field

The invention relates to a polyamide hot melt adhesive for high performance surface decoration and a preparation method thereof, in particular to a polyamide hot melt adhesive with high gloss and high gloss film and a preparation method thereof.

Background technique

High-gloss film is a new type of solvent-free 100% solid decoration material, which is mainly used for surface decoration of clothing bags, home cabinets, etc. There are many kinds of basic materials for making high-gloss films, and polyamide hot-melt adhesives are widely used.

Among them, the surface gloss is an important index for evaluating high gloss film products. The gloss of the polyamide hot melt adhesive as the base material directly affects the gloss of the final high gloss film product. At present, the surface gloss of polyamide hot melt adhesives for high gloss films on the market is generally around 60. For the market demand with high surface gloss requirements, polyamide hot melt adhesives as basic materials cannot meet the requirements.

Summary of the invention

The object of the present invention is to solve the above technical problems, to provide a polyamide hot melt adhesive for high performance surface decoration and a preparation method thereof, in particular to a polyamide hot melt adhesive for high gloss and high gloss film and a preparation method thereof.

The technical scheme adopted by the invention is: a polyamide hot melt adhesive for high performance surface decoration, the raw materials thereof include: aliphatic dicarboxylic acid, alicyclic diamine, other diamine, C6-C12 lactam, Nylon 66 salt, stearic acid, glycerin modifier and antioxidant, among them,

The molar ratio of the aliphatic dicarboxylic acid to the total diamine is from 1:1 to 1:1.1;

The molar ratio of the aliphatic dicarboxylic acid to the C6-C12 lactam is: 0.7:1 to 0.8:1 and the molar ratio of the C6-C12 lactam to the nylon 66 salt is 1:0.9 to 1:1;

The amount of stearic acid added is 0.2 to 0.5% of the total mass of the raw materials;

The amount of the glycerin modifier added is 0.05 to 0.5% of the total mass of the raw material.

The above aliphatic dicarboxylic acid is selected from one of adipic acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid;

The above alicyclic diamine is selected from the group consisting of ethylenediamine, hexamethylenediamine, decanediamine, and dodecanediamine;

The above other diamine is piperazine or polyetheramine, wherein the polyetheramine is D-400;

The above C6-C12 lactam is caprolactam or laurolactam;

The glycerin modifier is selected from the group consisting of glycerin, monoglyceride, diglyceride, and triglyceride;

The type of the above antioxidant is selected from one of 1010, 168, and 1096, and the amount added is 0.1 to 1% of the total mass of the raw material.

A method for preparing a high performance surface decorative polyamide hot melt adhesive, comprising the following steps:

(1) adding the raw material of the high-performance surface decoration polyamide hot melt adhesive and water to the numerical control reaction kettle;

(2) First, replace the nitrogen gas twice, then raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure is released to normal pressure, and then the pressure is discharged after 2 to 3 hours at normal pressure.

Wherein, the amount of water added in the step (1) is determined by the size of the numerical control reactor and the amount of the raw materials, and the person skilled in the art can select according to the actual situation, and the water is drained in the step (2), so The present invention has no particular requirement for the amount of water to be added. The numerical values disclosed in the examples are merely illustrative and should not be construed as limiting.

In addition, the pressurized discharge in the step (2) has no special requirement on the applied pressure, as long as the discharge can be realized under the applied pressure, and those skilled in the art can self-contain according to the actual situation. Line selection.

The beneficial effects of the present invention, because the specific raw materials and ratios are selected, and the simple preparation method of the polycondensation reaction by one-time direct feeding is adopted, the surface glossiness of the polyamide hot melt adhesive prepared by the invention is obviously improved, and the specificity is satisfied. Requirements for high gloss film products.

detailed description

Example 1:

A high-performance surface decorative polyamide hot melt adhesive, the raw material composition thereof comprises: 192.97g of dodecanedioic acid, 115.56g of decanediamine, 74.97g of polyetheramine (D-400), 112.5g of caprolactam, nylon 66 salt 237.5 g, 1.47 g of stearic acid, 3.67 g of triglyceride, and 0.73 g of antioxidant (1010).

The above preparation method of the polyamide hot melt adhesive for high performance surface decoration comprises the following steps:

(1) adding the above raw materials and a certain amount of water 250g to a 2000ml numerical control reaction kettle;

(2) First, replace the nitrogen gas twice, then slowly raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure was slowly released to normal pressure, and then the pressure was discharged after 2 to 3 hours at normal pressure, and the obtained product was labeled as A.

Example 2:

A high-performance surface decorative polyamide hot melt adhesive, the raw material composition thereof comprises: 122.5 g of adipic acid, 134.37 g of dodecanediamine, 74.97 g of polyetheramine (D-400), 112.5 g of caprolactam, and nylon 66 salt 237.5 g, 1.38 g of stearic acid, 0.35 g of diglyceride, and 2 g of antioxidant (168).

(2) First, replace the nitrogen gas twice, then slowly raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising, and when the pressure reaches 1.5 MPa, the pressure is maintained. Between 1.5 and 1.6 MPa, after the temperature is between 250 and 260 ° C for 1.5 h, the pressure is slowly released to normal pressure, and then the pressure is discharged after 2 to 3 hours at normal pressure, and the obtained product is labeled as B.

Example 3:

The invention relates to a polyamide hot melt adhesive for high-performance surface decoration, which comprises: 169.47g of azelaic acid, 77.94g of hexamethylenediamine, 74.97g of polyetheramine (D-400), 112.5g of caprolactam, 233.5g of nylon 66 salt. 3.38 g of stearic acid, 3.34 g of monoglyceride, and 6.68 g of antioxidant (1096).

(2) First, replace the nitrogen gas twice, then slowly raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure was slowly released to normal pressure, and then the pressure was discharged after 2 to 3 hours at normal pressure, and the obtained product was labeled as C.

Example 4:

A polyamide hot melt adhesive for high performance surface decoration, the raw material composition thereof comprises: 216.47 g of tetradecanedioic acid, 40.31 g of ethylenediamine, 74.97 g of polyetheramine (D-400), 112.5 g of caprolactam, and nylon 66 salt. 237.5 g, 3 g of stearic acid, 3.41 g of glycerin, and 3.75 g of antioxidant (1010).

(2) First, replace the nitrogen gas twice, then slowly raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure was slowly released to normal pressure, and then the pressure was discharged after 2 to 3 hours at normal pressure, and the obtained product was labeled as D.

Example 5:

A polyamide hot melt adhesive for high performance surface decoration, the raw material composition thereof comprises: dodecanedioic acid 192.97 g, 115.56 g of decanediamine, 14.04 g of piperazine, 166.71 g of laurolactam, 237.5 g of nylon 66 salt, 2 g of stearic acid, 3 g of triglyceride, and 5 g of antioxidant (1010).

(1) adding the above raw materials and a certain amount of water 250g to the numerical control reactor;

(2) First, replace the nitrogen gas twice, then slowly raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure was slowly released to normal pressure, and then the pressure was discharged after 2 to 3 hours at normal pressure, and the obtained product was labeled as E.

Performance Testing

The products obtained in the above examples and the commercially available conventional products were tested for performance. Among them, the melting point test standard: GB/T19466-2004; the melting index test standard: GB/T 3682-2000; the surface gloss test standard: GB9754- 88; The relevant performance test results are shown in Table 1 below.

Table 1 Comparison of performance test results of products obtained in each example and commercially available conventional products

指标index	市场普通PAMarket ordinary PA	AA	BB	CC	DD	EE
熔点Melting point	120～130120～130	125125	126126	125125	124124	125125
熔指Melt	70～9070～90	7575	8888	7474	5757	6565
表面光泽度Surface gloss	56～6056~60	8282	7878	8282	8585	8080

From the above Table 1, it can be clearly seen that the polyamide hot melt adhesive obtained by the present invention has a melting point and a solute which are not much different from the commercially available conventional similar products, and are also convenient for the construction operation, but are produced by the present invention. The surface light measurement of polyamide hot melt adhesives has been significantly improved, meeting the actual needs of high gloss film products.

Claims

A polyamide hot melt adhesive for surface decoration, characterized in that the raw material comprises: aliphatic dicarboxylic acid, alicyclic diamine, other diamine, C6-C12 lactam, nylon 66 salt, stearic acid , glycerin modifiers and antioxidants, among them,

The molar ratio of the aliphatic dicarboxylic acid to the total diamine is from 1:1 to 1:1.1;

The molar ratio of the aliphatic dicarboxylic acid to the C6-C12 lactam is from 0.7:1 to 0.8:1 and the molar ratio of the C6-C12 lactam to the nylon 66 salt is from 1:0.9 to 1:1;

The amount of stearic acid added is 0.2 to 0.5% of the total mass of the raw materials;

The amount of the glycerin modifier added is 0.05 to 0.5% of the total mass of the raw material, and the amount of the antioxidant added is 0.1 to 1% of the total mass of the raw material.
The polyamide hot melt adhesive for surface decoration according to claim 1, wherein the aliphatic dicarboxylic acid is selected from one of adipic acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid. Kind.
The polyamide hot melt adhesive for surface decoration according to claim 1, wherein the alicyclic diamine is selected from the group consisting of ethylenediamine, hexamethylenediamine, decanediamine, and dodecanediamine. .
The polyamide hot melt adhesive for surface decoration according to claim 1, wherein the other diamine is piperazine or polyetheramine.
The polyamide hot melt adhesive for surface finishing according to claim 4, wherein the polyetheramine has a designation of D-400.
The polyamide hot melt adhesive for surface decoration according to claim 1, wherein the C6 to C12 lactam is caprolactam or laurolactam.
The polyamide hot melt adhesive for surface decoration according to claim 1, wherein the glycerin-based modifier is one selected from the group consisting of glycerin, monoglyceride, diglyceride, and triglyceride.
The method for preparing a polyamide hot melt adhesive for surface decoration according to any one of claims 1 to 7, comprising the steps of:

(1) Adding the raw material of the above surface decorative polyamide hot melt adhesive and water to the numerical control reactor in;

(2) First, replace the nitrogen gas twice, then raise the temperature to 120 ° C, start the stirring, and then continue to raise the temperature to 250 ° C, during which the pressure is kept rising. When the pressure reaches 1.5 MPa, the pressure is maintained between 1.5 and 1.6 MPa. After 1.5 h between 250 and 260 ° C, the pressure is released to normal pressure, and then the pressure is discharged after 2 to 3 hours at normal pressure.