WO2021051841A1

WO2021051841A1 - Solvent-free flexible packaging binder for easy construction in different temperature environments and preparation method therefor

Info

Publication number: WO2021051841A1
Application number: PCT/CN2020/090928
Authority: WO
Inventors: 张卫东; 柳红毅; 江平
Original assignee: 旭川化学（苏州）有限公司
Priority date: 2019-09-17
Filing date: 2020-05-19
Publication date: 2021-03-25
Also published as: CN110591634A; CN110591634B

Abstract

A solvent-free flexible packaging binder for easy construction in different temperature environments. The flexible packaging binder comprises a hydroxyl component and an isocyanate component; the hydroxyl component consists of the following components in weight fractions: 40-70% of castor oil, 5-40% of hydroxyl-terminated polybutadiene, 5-15% of ethylene glycol, 0-1% of a coupling agent, 10-40% of polypropylene oxide, and 0-0.5% of a catalyst; the isocyanate component consists of the following components in weight fractions: 30-70% of polyester polyol, 10-40% of hydroxyl-terminated polybutadiene, 20-30% of isocyanate, 0-0.1% of benzoyl chloride. A hydroxyl value component of the binder is prepared by mixing hydroxyl-terminated polybutadiene with polyether, castor oil, etc, and as the amount of hydroxyl groups increases by introduction of the hydroxyl-terminated polybutadiene, the flow characteristics of fluid change, and the fluid changes gradually to a non-Newtonian fluid, the change in viscosity of the system becomes smaller with the change in temperature.

Description

Solvent-free flexible packaging adhesive for easy construction in different temperature environments and preparation method thereof

Technical field

The invention belongs to the technical field of adhesives, and specifically relates to a solvent-free flexible packaging adhesive that is easy to construct in different temperature environments and a preparation method thereof.

Background technique

In recent years, the composite flexible packaging adhesive industry has developed rapidly. Solvent-based flexible packaging adhesives are difficult to recover from the volatilization of solvents during use, causing a large amount of organic solvents to volatilize into the atmosphere and pollute the environment. Solvent-free flexible packaging adhesives are quickly obtained. Develop applications.

The biggest feature of the solvent-free flexible packaging adhesive is that there is no VOC generated in the process, and the site is environmentally friendly and odorless. However, the viscosity of the solvent-free flexible packaging adhesive changes with the change of temperature. The same model has a difference in viscosity in winter and summer. Large, there are some difficulties in site construction. In winter, the material viscosity is high, the coating process is prone to uneven coating and even lead to scrapping, the summer temperature is low, the material viscosity is low, and composite slippage is easy to occur.

Manufacturers who do lamination require products with a wide operating temperature, and they require that the viscosity of the product changes little with changes in ambient temperature. At present, some manufacturers adjust products with different viscosities according to the changes of the seasons for customers to use, but in the high temperature environment in summer, the viscosity of the products is still very low and the operability is poor.

Summary of the invention

Purpose of the invention: In order to solve the problems existing in the prior art, the present invention provides a solvent-free flexible packaging adhesive that is easy to construct in different temperature environments. The original adhesive component is Newtonian fluid and part of the non-Newtonian fluid is added. With the increase of the number of Newtonian fluids, the viscosity change of the system will become smaller as the temperature changes, and the difference between the viscosity of the final system in winter and summer will be reduced, so as to meet the requirements of construction in different seasons.

The technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned solvent-free flexible packaging adhesive that is easy to construct in different temperature environments.

Technical solution: In order to solve the above technical problems, the present invention adopts the following technical solutions:

A solvent-free flexible packaging adhesive that is easy to construct in different temperature environments. The flexible packaging adhesive includes a hydroxyl component and an isocyanate component,

The hydroxyl component is composed of components including the following weight fractions:

Castor oil 40～70%

Hydroxyl-terminated polybutadiene 5～40%

Ethylene glycol 5～15%

Coupling agent 0～1%

Polypropylene oxide ether 10～40%

Catalyst 0～0.5%;

Said hydroxyl component is preferably: castor oil 44.45%, hydroxyl-terminated polybutadiene 25%, ethylene glycol 10%, coupling agent 0.5%, polypropylene oxide ether 20%, catalyst 0.05%;

The isocyanate component is composed of components including the following weight fractions:

Polyester polyol 30～70%

Hydroxyl-terminated polybutadiene 10～40%

Isocyanate 20～30%

Benzoyl chloride 0～0.1%;

The isocyanate component is preferably: polyester polyol 44.99%, hydroxyl-terminated polybutadiene 30%, isocyanate 25%, and benzoyl chloride 0.01%.

Preferably, the molecular weight of the hydroxyl-terminated polybutadiene is 1000-3000; the molecular weight of the polypropylene oxide ether is 1000-4000.

Preferably, the coupling agent is KH560.

Preferably, the catalyst is stannous octoate.

Preferably, the polyester polyol is polyester polyol XCP-822NH produced by Asahikawa Chemical.

Preferably, the isocyanate is TDI-80/20.

The method for preparing the solvent-free flexible packaging adhesive for easy construction in different temperature environments, wherein the method for preparing the hydroxyl component is as follows:

First mix castor oil and polypropylene oxide ether uniformly in proportion, heat up to 100～120℃, remove the water in the system, cool to 80℃, and then add hydroxyl-terminated polybutadiene, coupling agent, catalyst and ethylene Diol, stir at 70-75 degrees for 2 hours to obtain the hydroxyl component.

Wherein, the preparation method of the isocyanate component is as follows:

Mix the polyester polyol and hydroxy-terminated polybutadiene uniformly in proportion, heat up to 100-120°C, dehydrate to less than 0.05% of the water content, add benzoyl chloride, stir evenly and cool down to 50-55°C, add isocyanate at one time , React at 60～65℃ for 2 hours, and package after the test isocyanate content is qualified.

Mix the normal temperature hydroxyl component and normal temperature isocyanate component in a mass ratio of 100:90 to 100:60, and stir evenly.

The flexible packaging adhesive prepared by the above-mentioned preparation method of the solvent-free flexible packaging adhesive for easy construction in different temperature environments falls within the protection scope of the present invention.

Beneficial effects:

In the present invention, hydroxyl-terminated polybutadiene is introduced into the hydroxyl component and isocyanate component of the adhesive. The hydroxyl component without the hydroxyl-terminated polybutadiene is a Newtonian fluid, and the viscosity of the component fluctuates relatively greatly with temperature. With the introduction of hydroxy-terminated polybutadiene, the fluid flow characteristics change gradually to a non-Newtonian fluid. The viscosity change of the system becomes smaller with temperature changes. The final viscosity of the system decreases in winter and summer to achieve different The requirements of seasonal construction are convenient for construction in different seasons, and it can also meet the bonding strength requirements of the adhesive.

detailed description

The present invention will be further described below in conjunction with specific implementation examples.

Examples 1 to 4:

The hydroxyl components of Examples 1 to 4 were obtained by the following method:

According to the formula in Table 1, add castor oil and polypropylene oxide ether into the reactor, heat up to 110°C for constant dehydration for 2 hours, then lower the temperature to 90°C, add coupling agent (KH560), hydroxyl-terminated polybutadiene, Stir for 1 hour, then lower the temperature to 70°C, add catalyst (stannous octoate) and ethylene glycol, stir well and pack.

Table 1 The raw material formula of the hydroxyl component of Examples 1-4

Table 2 Implementation Cases 1-4 Formula Viscosity Test Results at Different Temperatures

The formulations of Examples 1-4 were made into the adhesive hydroxyl component and the preferred isocyanate component of Example 5 to 8 were mixed with Example 7 to test the adhesion properties of PET and OPP. The test results are shown in Table 3. The mass ratio of the hydroxyl component to the isocyanate component is 100:90 in the binding process.

Table 3 Test results of Examples 1-4

Example 5-8:

As shown in Table 4, the isocyanate components according to Examples 5-8 are obtained by the following method: Mix the polyester polyol and hydroxyl-terminated polybutadiene in the formula quantity, heat up to 110 degrees, and dehydrate to less than 0.05% of the moisture content. , Add the specified amount of benzoyl chloride and stir uniformly to cool down to 60 degrees, add quantitative isocyanate at one time, react for 2 hours, test the content of isocyanate and then package.

The formulations of Examples 5 to 8 were made into adhesive isocyanate component and mixed with the preferred hydroxyl component of Example 1 to 4 in Example 3 to test the bonding properties of PET and OPP. The test results are shown in Table 6. The mass ratio of the hydroxyl component to the isocyanate component is 100:90 in the binding process.

Table 4 The raw material formula of the isocyanate component of Examples 5-8

Table 5 Example 5-8 Formulation Viscosity at Different Temperatures

The formulations of Examples 5-8 were made into adhesives to test the bonding performance of PET and OPP. The test results are shown in Table 6. The mass ratio of the hydroxyl component and the isocyanate component used in the bonding process is 100:90.

Table 6 Test results of Examples 5-8

The viscosity in Table 2 and Table 5 refers to the GB/T2794-2013 standard test.

The specific preparation methods of the test samples in Table 3 and Table 6 are as follows:

The mixed sample was directly coated on release paper, the two ends of the obtained sample width direction were removed by 50 mm, and 5 vertical and horizontal samples were uniformly cut along the width direction of the sample. The composite direction is longitudinal. Strip the composite layer and the base material 50mm in advance along the length of the sample, and the stripped part shall not have obvious damage. If the sample is not easy to peel off, you can immerse one end of the sample about 20mm in a suitable solvent for treatment. After the solvent is completely volatilized, perform the peeling force test. If the composite layer cannot be separated from the substrate after this treatment, the test cannot be carried out.

The sample should be placed in an environment with a temperature of 23±2°C and a relative humidity of 45%-55% for more than 4 hours, and then perform the test in the above-mentioned environment.

Among them, the initial bond strength refers to the GB/T8808-1988 standard test; the final bond strength refers to the GB/T8808-1988 standard test; the initial heat resistance refers to the GB/T15332-1994 standard test.

This application includes but is not limited to the above embodiments. Any equivalent substitution or partial improvement made under the principle of the spirit of this application will be deemed to be within the protection scope of this application.

Claims

An easy-to-construct solvent-free flexible packaging adhesive for different temperature environments, characterized in that the flexible packaging adhesive includes a hydroxyl component and an isocyanate component, and the hydroxyl component is composed of components including the following weight fractions: castor oil 44.45 ~49.45%, hydroxyl-terminated polybutadiene 10-25%, ethylene glycol 10-15%, coupling agent 0.5-0.8%, polypropylene oxide ether 5-30%, catalyst 0.05-0.1%, the end The molecular weight of hydroxy polybutadiene is 1000-3000, the molecular weight of the polypropylene oxide ether is 1000-4000, the coupling agent is KH560, the catalyst is stannous octoate; the isocyanate component consists of The components are composed of the following weight fractions: polyester polyol 34.99-64.99%, hydroxyl-terminated polybutadiene 10-40%, isocyanate 25%, and benzoyl chloride 0.01%. The polyester polyol is Asahikawa Chemical's polyester polyol Alcohol XCP-822NH, the isocyanate is TDI-80/20; the mass ratio of the hydroxyl component to the isocyanate component is 100:90-100:60.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to claim 1, wherein the flexible packaging adhesive comprises a hydroxyl component and an isocyanate component, and the hydroxyl component is composed of components including the following weight fractions : Castor oil 44.45%, hydroxyl-terminated polybutadiene 25%, ethylene glycol 10%, coupling agent 0.5%, polypropylene oxide ether 20%, catalyst 0.05%; the isocyanate component consists of the following weight fractions The components are composed of polyester polyol 44.99%, hydroxyl-terminated polybutadiene 30%, isocyanate 25%, and benzoyl chloride 0.01%; the mass ratio of the hydroxyl component to the isocyanate component is 100:90.
A solvent-free flexible packaging adhesive that is easy to construct in different temperature environments, characterized in that the flexible packaging adhesive includes a hydroxyl component and an isocyanate component,

The hydroxyl component is composed of components including the following weight fractions:

Castor oil 40～70%

Hydroxyl-terminated polybutadiene 5～40%

Ethylene glycol 5～15%

Coupling agent 0～1%

Polypropylene oxide ether 10～40%

Catalyst 0～0.5%;

The isocyanate component is composed of components including the following weight fractions:

Polyester polyol 30～70%

Hydroxyl-terminated polybutadiene 10～40%

Isocyanate 20～30%

Benzoyl chloride 0～0.1%.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to claim 3, wherein the hydroxyl component is composed of components including the following weight fractions: castor oil 44.45-49.45%, hydroxyl-terminated polybutadiene 10-25%, ethylene glycol 10-15%, coupling agent 0.5-0.8%, polypropylene oxide ether 20-30%, catalyst 0.05-0.1%.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to claim 4, wherein the hydroxyl component is composed of components including the following weight fractions: castor oil 44.45%, hydroxyl-terminated polybutadiene 25% , Ethylene glycol 10%, coupling agent 0.5%, polypropylene oxide ether 20%, catalyst 0.05%.
According to any one of claims 3 to 5, the easy-to-construct solvent-free flexible packaging adhesive in different temperature environments is characterized in that the molecular weight of the hydroxyl-terminated polybutadiene is 1000-3000; the polyepoxy The molecular weight of propane ether is 1,000 to 4,000.
According to any one of claims 3 to 5, the solvent-free flexible packaging adhesive that is easy to construct in different temperature environments is characterized in that the coupling agent is KH560.
According to any one of claims 3 to 5, the easy-to-construct solvent-free flexible packaging adhesive in different temperature environments is characterized in that the catalyst is stannous octoate.
The easy-to-construct solvent-free flexible packaging adhesive for different temperature environments according to claim 3, characterized in that: the isocyanate component is composed of components including the following weight fractions: polyester polyol 34.99 to 64.99%, hydroxyl terminated Polybutadiene 10-40%, isocyanate 25%, benzoyl chloride 0.01%.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to claim 9, wherein the isocyanate component is composed of components including the following weight fractions: polyester polyol 44.99%, hydroxy-terminated polybutylene Diene 30%, isocyanate 25%, benzoyl chloride 0.01%.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to claim 3 or 9 or 10, wherein the polyester polyol is Asahikawa Chemical Polyester Polyol XCP-822NH.
The easy-to-construct solvent-free flexible packaging adhesive for different temperature environments according to claim 3 or 9 or 10, wherein the isocyanate is TDI-80/20.
The easy-to-construct solvent-free flexible packaging adhesive for different temperature environments according to claim 3, wherein the mass ratio of the hydroxyl component to the isocyanate component is 100:90-100:60.
The easy-to-construct solvent-free flexible packaging adhesive for different temperature environments according to claim 13, wherein the mass ratio of the hydroxyl component to the isocyanate component is 100:90.
According to any one of claims 3 to 5, 9 to 10, and 13 to 14, the easy-to-construct solvent-free flexible packaging adhesive in different temperature environments is characterized in that the preparation method of the hydroxyl component is as follows:

First mix castor oil and polypropylene oxide ether uniformly in proportion, heat up to 100～120℃, remove the water in the system, cool to 80℃, and then add hydroxyl-terminated polybutadiene, coupling agent, catalyst and ethylene Diol, stir at 70-75°C for 2 hours to obtain the hydroxyl component.
The easy-to-construct solvent-free flexible packaging adhesive according to any one of claims 3 to 5, 9 to 10, and 13 to 14 in a different temperature environment is characterized in that the preparation method of the isocyanate component is as follows:

Mix the polyester polyol and hydroxy-terminated polybutadiene uniformly in proportion, heat up to 100-120°C, dehydrate to less than 0.05% of the water content, add benzoyl chloride, stir evenly and cool down to 50-55°C, add isocyanate at one time , React at 60-65°C for 2 hours to obtain isocyanate component.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to any one of claims 3 to 5, 9 to 10, and 13 to 14, characterized in that, during preparation, the hydroxyl component and the isocyanate component are combined Mix according to the mass ratio of 100:90～100:60, and stir evenly.
The easy-to-construct solvent-free flexible packaging adhesive in different temperature environments according to any one of claims 3 to 5, 9 to 10, and 13 to 14, characterized in that the preparation method of the solvent-free flexible packaging adhesive comprises The following steps:

(1) Preparation of hydroxyl component

First, mix castor oil and polypropylene oxide ether uniformly in proportion, heat up to 100-120°C, remove the water in the system, cool down to 90°C, add hydroxy-terminated polybutadiene and coupling agent, and stir for 1 hour. Then lower the temperature to 70～75℃, add the catalyst and ethylene glycol, and stir evenly to obtain the hydroxyl component;

(2) Preparation of isocyanate component

Mix the polyester polyol and hydroxy-terminated polybutadiene uniformly in proportion, heat up to 100-120°C, dehydrate to less than 0.05% of the water content, add benzoyl chloride, stir evenly and cool down to 50-55°C, add isocyanate at one time , React at 60～65℃ for 2 hours to obtain isocyanate component;

(3) Preparation of solvent-free flexible packaging adhesive

The hydroxyl component and the isocyanate component are mixed in a mass ratio of 100:90 to 100:60, and stirred uniformly to obtain the solvent-free flexible packaging adhesive.