阅读说明：本技术 一种应用于家电包装vcm覆膜板用胶水及其制备方法 (Glue applied to VCM (vinyl chloride monomer) laminated board for household appliance packaging and preparation method of glue ) 是由 虞明东 李明阳 吴小娟 刘天人 丁万强 于 2019-09-19 设计创作，主要内容包括：本发明公开了一种应用于家电包装VCM覆膜板用胶水组合物及其制备方法,所述胶水组合物包括主剂和固化剂；所述主剂包括以下重量百分比含量的各组分：聚酯树脂15～40％,二聚酸改性环氧树脂2～5％,聚醚多元醇1～5％,多元醇0.1～0.5％,助剂0.1～0.5％,溶剂49～74％。本发明制备的胶水具有如下的有益效果：1、较高的初始及拉伸后剥离；2、较好的杯突性能；3、较广的基膜适应性；4、优异的水煮剥离力；5、高温覆膜不橘皮。(The invention discloses a glue composition for a VCM (vinyl chloride monomer) film-coated plate applied to household appliance packaging and a preparation method thereof, wherein the glue composition comprises a main agent and a curing agent; the main agent comprises the following components in percentage by weight: 15-40% of polyester resin, 2-5% of dimer acid modified epoxy resin, 1-5% of polyether polyol, 0.1-0.5% of auxiliary agent and 49-74% of solvent. The glue prepared by the invention has the following beneficial effects: 1. higher initial and post-stretch peel; 2. better cupping performance; 3. wider adaptability of the basement membrane; 4. excellent poaching peel force; 5. the high-temperature film covering does not need orange peel.)

1. The glue composition for the VCM film coated plate applied to household appliance packaging is characterized by comprising a main agent and a curing agent; the main agent comprises the following components in percentage by weight:

2. the glue composition applied to the VCM film covering plate for home appliance packaging according to claim 1, wherein the polyester resin comprises one or more of polyester resin and modified polyester resin.

3. The glue composition applied to a VCM film coated plate for home appliance packaging as claimed in claim 1, wherein the dimer acid modified epoxy resin comprises one or more of EPD-172, EPD-171 or self-synthesized dimer acid modified epoxy resin.

4. The glue composition applied to the VCM film coated plate for home appliance packaging according to claim 3, wherein the preparation method of the self-synthesized dimer acid modified epoxy resin comprises the following steps:

adding epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid in proportion to form a reactant, introducing nitrogen and stirring, replacing air in the system completely, and heating; weighing a catalyst and adding the catalyst into a system; and continuously heating for reaction until the acid value is less than 1.5ml/KOH/g, and cooling to obtain the finished product.

5. The glue composition applied to the VCM film covering plate for home appliance packaging as claimed in claim 1, wherein the polyether polyol comprises one or more of EP-330NG, PPG-400, CHE-204, CHE210 and CHE 2208.

6. The glue composition applied to a VCM coating plate for home appliance packaging according to claim 1, wherein said polyhydric alcohol comprises one or more of dipropylene glycol, diethylene glycol, neopentyl glycol, and trimethylolpropane.

7. The glue composition applied to a VCM film laminated plate for home appliance packaging according to claim 1, wherein the auxiliary agent comprises at least one of carbodiimide, silane coupling agent, titanate coupling agent, T890 and self-synthesized organic silicon oligomer; the solvent comprises at least one of ethyl ester and butanone.

8. The glue composition applied to the VCM film laminated plate for home appliance packaging according to claim 7, wherein the preparation method of the self-synthesized organic silicon oligomer comprises the following steps:

adding three kinds of alkoxy silane monomers and xylene to form reactants, stirring and heating, then dropwise adding a mixed solution of deionized water and hydrochloric acid, after dropwise adding, carrying out reflux reaction, then distilling and filtering to obtain the self-synthesized organic silicon oligomer containing ethoxy.

9. The glue composition applied to the VCM film coated plate for home appliance packaging according to claim 1, wherein the curing agent is isocyanate prepolymer; the mass ratio of the main agent to the curing agent is 100/8-100/15.

10. The preparation method of the glue composition applied to the VCM film laminated plate for home appliance packaging according to claim 1, characterized by comprising the following steps:

A. preparing a main agent: adding a solvent into a reaction kettle, heating and stirring, and adding polyester resin, epoxy resin, polyether glycol and polyol to completely dissolve; then adding an auxiliary agent, stirring, curing, adjusting solid content and discharging;

B. preparing glue: and (3) adding a curing agent into a solvent for dilution, uniformly stirring, adding into the main agent prepared in the step A, and uniformly stirring to obtain the double-component glue.

Technical Field

The invention belongs to the technical field of glue, and particularly relates to glue applied to a VCM (vinyl chloride monomer) laminated board for home appliance packaging and a preparation method thereof.

Background

The VCM film-coated plate is generally a galvanized substrate, is coated with a color or pattern film, has very smooth and flat surface and rich surface color effect, is generally used for a panel of a refrigerator, or a side plate of a high-grade wine cabinet, a shell of a set-top box and the like, and has higher requirements on the film in product application. The VCM color plate belongs to a high-end product, and a composite film is required by adopting the lamination of a film and a plate, wherein the composite film is formed by compounding multiple films by using an adhesive. In the aspect of specific film composition, the conventional method is compounding of PET and PVC or PET// aluminum foil, a small amount of PET and an aluminum-plated film, and a very small amount of PET/PET/PVC and other more composite structures. It is the multiple structures of the composite substrate, which endows the composite substrate with unique properties: fireproof, waterproof, fireproof, weather-proof and the like, and the surface forms rich and various patterns and designs such as wood grain, stone grain, brick and tile grain, velvet grain, leather grain, camouflage grain, ice grain, sheepskin grain, orange peel grain, refrigerator grain and the like, thereby achieving the effect of integrating the beautiful design, the corrosion prevention and the durability.

But also because of its complex structure and diversified adhesion between substrates, it is very demanding to use glue. However, the glue which can be successfully applied in the market has relatively single function, and the glue material is required to be replaced when the product type is replaced, so that the operation is inconvenient. Therefore, it is urgent to develop a glue with strong universality and wide adaptability.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides glue for a VCM film coated plate applied to household appliance packaging and a preparation method thereof.

The purpose of the invention is realized by the following technical scheme:

the invention provides a glue composition for a VCM film-coated plate applied to household appliance packaging, which comprises a main agent and a curing agent; the main agent comprises the following components in percentage by weight:

preferably, the polyester resin comprises one or more of polyester resin and modified polyester resin.

Preferably, the dimer acid-modified epoxy resin comprises one or more of EPD-172, EPD-171 or self-synthesized dimer acid-modified epoxy resin. More preferably a self-synthesized dimer acid-modified epoxy resin.

Preferably, the preparation method of the self-synthesized dimer acid-modified epoxy resin comprises the following steps:

adding epoxy resin, 1, 6-hexanediol diglycidyl ether and dimer acid in proportion to form a reactant, introducing nitrogen and stirring, replacing air in the system completely, and heating; weighing a catalyst and adding the catalyst into a system; and continuously heating for reaction until the acid value is less than 1.5ml/KOH/g, and cooling to obtain the finished product.

Preferably, the mass ratio of the added substances of the epoxy resin, the 1, 6-hexanediol diglycidyl ether and the dimer acid is 2:1: 1.2; the epoxy resin is E51 epoxy resin.

The stirring speed is 150r/min, and the stirring time is 0.5 h;

the catalyst is tetrabutylammonium bromide, and the addition amount of the catalyst is 0.05 percent of the total mass of the reactants; the catalyst is added when the temperature is raised to 105 ℃;

the temperature of the reaction was 125 ℃.

Preferably, the polyether polyol comprises one or more of EP-330NG, PPG-400, CHE-204, CHE210 and CHE 2208.

Preferably, the polyhydric alcohol comprises one or more of dipropylene glycol, diethylene glycol, neopentyl glycol and trimethylolpropane.

Preferably, the auxiliary agent comprises at least one of carbodiimide, silane coupling agent, titanate coupling agent, T890, self-synthesized silicone oligomer; the solvent comprises at least one of ethyl ester and butanone.

Preferably, the preparation method of the self-synthesized silicone oligomer comprises the following steps:

adding three kinds of alkoxy silane monomers and xylene to form reactants, stirring and heating, then dropwise adding a mixed solution of deionized water and hydrochloric acid, after dropwise adding, carrying out reflux reaction, then distilling and filtering to obtain the self-synthesized organic silicon oligomer containing ethoxy.

Preferably, the three alkoxy silane monomers are monomethyl triethoxysilane, dimethyl diethoxy silane and phenyl triethoxysilane, and by adopting the three alkoxy silane monomers, the maximum strength and heat resistance can be obtained; the addition mass ratio of the monomethyl triethoxysilane, the dimethyl diethoxy silane, the phenyl triethoxysilane and the xylene is 1.02: 1: 1.3: 8;

when the temperature is raised to 80 ℃, the mixed solution of the deionized water and the hydrochloric acid is dripped;

the temperature of the reflux reaction is 80-90 ℃;

the distillation is normal pressure distillation and then reduced pressure distillation, and ethanol and part of xylene generated by the reaction are distilled out.

Preferably, the curing agent is an isocyanate prepolymer; the mass ratio of the main agent to the curing agent is 100/8-100/15.

Preferably, the isocyanate prepolymer is one or more of L75, N3390, N3300, D-110N, BL 1100/1, BL 3175 and MDI black material.

The invention also provides a preparation method of the glue composition for the VCM film coated plate applied to the household appliance packaging, which comprises the following steps:

A. preparing a main agent: adding a solvent into a reaction kettle, heating and stirring, and adding polyester resin, epoxy resin, polyether glycol and polyol to completely dissolve; then adding an auxiliary agent, stirring, curing, adjusting solid content and discharging;

B. preparing glue: and (3) adding a curing agent into a solvent for dilution, uniformly stirring, adding into the main agent prepared in the step A, and uniformly stirring to obtain the double-component glue.

Preferably, in the step B, the stirring rotation speed is 250-350r/min, and the stirring time is 10-15 min.

Compared with the prior art, the invention has the following beneficial effects:

1. higher initial and post-stretch peel;

2. better cupping performance;

3. wider adaptability of the basement membrane;

4. excellent poaching peel force;

5. the high-temperature film covering does not need orange peel.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

Examples 1 to 5

The formula of the glue applied to the VCM film laminated board for home appliance packaging in the embodiments 1 to 5 is shown in Table 1, and the method comprises the following process steps:

(1) adding a solvent and polyhydric alcohol into a reaction kettle, heating until the temperature of the reaction kettle is constant at 55 ℃, and keeping stirring;

(2) slowly adding polyester resin, dimer acid modified epoxy resin and polyether polyol into a reaction kettle under the condition of keeping stirring, and stirring for about 3 hours;

(3) after stirring uniformly, slowly adding the auxiliary agent, and keeping stirring at a high speed for about 30 min;

(4) after all the components are uniformly mixed, stopping the machine and curing for more than 12 hours;

(5) measuring the solid content and adjusting to 50%;

(6) then slowly stirring for about 1 hour, weighing and packaging.

The dimer acid modified epoxy resin is self-synthesized dimer acid modified epoxy resin, and the specific preparation method comprises the following steps: adding E51 epoxy resin, 1, 6-hexanediol and glycidyl ether and dimer acid (the adding amount ratio of the E51 oxygen resin, the 1, 6-hexanediol diglycidyl ether and the dimer acid is 2:1:1.2) according to a fixed ratio into a 500mL four-neck flask, introducing nitrogen and mechanically stirring at the rotating speed of 150r/min for 0.5h, replacing air in the system completely, and heating; weighing a catalyst tetrabutylammonium bromide with the total mass of 0.05 percent of reactants, dissolving the tetrabutylammonium bromide in acetone, and adding the tetrabutylammonium bromide into the system when the temperature rises to 105 ℃; and continuously heating to 125 ℃, carrying out heat preservation reaction, measuring the acid value for 1 time every 1 hour until the acid value is less than 1.5ml/KOH/g, and cooling to obtain the finished product.

The auxiliary agent is a self-synthesized organic silicon oligomer and is prepared by hydrolyzing organoalkoxysilane, and the method comprises the following specific steps: adding three alkoxy silane monomers (monomethyl triethoxysilane, dimethyl diethoxy silane and phenyl triethoxysilane) and xylene in a formula amount into a four-neck flask provided with a stirrer, a thermometer and a condensation reflux device, starting stirring and heating, starting dropwise adding a mixed solution of deionized water and hydrochloric acid when the temperature is raised to 80 ℃, after dropwise adding, carrying out reflux reaction at 80-90 ℃ for a specified time, after the reaction is finished, distilling under normal pressure and then distilling under reduced pressure, distilling ethanol and part of xylene generated by the reaction out, and filtering to obtain the ethoxy-containing organic silicon oligomer. Wherein the addition mass ratio of the monomethyl triethoxysilane, the dimethyl diethoxy silane, the phenyl triethoxysilane and the xylene is 1.02: 1: 1.3: 8.

the polyether polyol adopts EP-330 NG; the polyhydric alcohol adopts dipropylene glycol; the solvent adopts ethyl ester.

Example 6

The components and preparation method of the embodiment are basically the same as those of the embodiment 1, and the difference is only that: the dimer acid-modified epoxy resin used in this example was EPD-172.

Example 7

The components and preparation method of the embodiment are basically the same as those of the embodiment 1, and the difference is only that: the assistant used in this example was organoalkoxysilane.

Comparative examples 1 to 3

The formula of the glue for the VCM film coated plate applied to the household appliance packaging and the preparation method thereof in the embodiments 1 to 3 are shown in Table 1, and the specific preparation steps are the same as those in the embodiments.

TABLE 1 weight ratio of the components (kg)

Comparative example 4

This comparative example is essentially the same as example 1 in terms of components and preparation, except that: the other modified epoxy resin used in this comparative example was a polyurethane modified epoxy resin.

Comparative example 5

This comparative example is essentially the same as example 1 in terms of components and preparation, except that: this comparative example uses unmodified E51 epoxy resin instead of dimer acid-modified epoxy resin.

Effect verification:

the glue prepared in the examples 1-7 and the comparative examples 1-5 and the curing agent (isocyanate prepolymer) are mixed according to the proportion of 100/10, and the two-component glue is obtained after uniform stirring. The properties are shown in Table 2, comparing with 2781, GC261 and 2955 which are commercially available.

TABLE 2 comparative test results for samples

As can be seen from the data in table 2, the application range of the competitive products is narrower than that of the competitive product samples 2781, GC261 and 2955, while the applicability of the examples to the base material is wider; compared with the singleness of a competitive product, the sample of the embodiment is more convenient to operate on the computer, and when the order is changed for a product, the order can be freely switched without changing glue of different types. Meanwhile, the examples have the properties of strength, boiling resistance, cupping and appearance within the ranges described in the examples. The examples and the comparative examples show that when the examples are applied to different substrates on the basis of increasing the content of the diacid modified epoxy, the composite strength between the different substrates is not greatly influenced, but the cupping performance can be obviously improved, but the excessive amount of the diacid modified epoxy causes the reduction of the boiling performance. Increasing the polyether polyol increases the strength to some extent, but the decrease in strength after poaching is caused by a decrease in the degree of crosslinking. If the amount is excessive, the degree of crosslinking becomes too large, resulting in a decrease in cupping properties. Delamination and orange peel can occur with other modified or unmodified epoxies.

The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.