阅读说明：本技术 一种pvc膜用复合镭射涂料组合物及其制备方法 (Composite laser coating composition for PVC (polyvinyl chloride) film and preparation method thereof ) 是由 薛萌 吴敏达 吕兴军 颜昌琪 何文豪 张亚飞 于 2020-12-29 设计创作，主要内容包括：本发明公开了一种PVC膜用复合镭射涂料组合物及其制备方法,PVC膜用复合镭射涂料组合物,由以下原料组成：聚烯烃树脂、纤维素树脂、聚丙烯酸树脂、聚酯树脂、助剂和溶剂。本发明制备的镭射涂料组合物配制和使用方便,使用常规反应釜以及涂布机就能够满足要求,涂料状态稳定,保质期能够达到两年以上；涂料涂布适应性强,能够在不同厚度的PVC膜上很好的涂布,涂料与PVC膜以及油墨都具有高附着牢度；涂料易于模压,能够形成绚丽的镭射效果。(The invention discloses a composite laser coating composition for a PVC film and a preparation method thereof, wherein the composite laser coating composition for the PVC film is prepared from the following raw materials: polyolefin resin, cellulose resin, polyacrylic resin, polyester resin, an auxiliary agent and a solvent. The laser coating composition prepared by the invention is convenient to prepare and use, can meet the requirements by using a conventional reaction kettle and a coating machine, is stable in coating state, and can be stored for more than two years; the coating has strong coating adaptability, can be well coated on PVC films with different thicknesses, and has high adhesion fastness with the PVC films and the printing ink; the coating is easy to mold and can form gorgeous laser effect.)

1. The composite laser coating composition for the PVC film is characterized by comprising the following raw materials:

polyolefin resin, cellulose resin, polyacrylic resin, polyester resin, an auxiliary agent and a solvent.

2. The composite laser coating composition for the PVC film according to claim 1, which comprises the following raw materials in parts by weight:

3. the composite laser coating composition for the PVC film according to claim 2, which comprises the following raw materials in parts by weight:

4. the composite laser coating composition for PVC films according to claim 3, wherein the polyolefin resin is a modified polyolefin resin based on a modifier;

the modifier comprises; a monomer group A and a monomer group B, the weight ratio (A/B) of the monomer group A to the monomer group B is 1/2-1/1,

monomer group A: 1 or more monomers having a homopolymer glass transition temperature (Tg) of 60 ℃ or higher and containing an ethylenically unsaturated bond and a functional group;

monomer group B: a homopolymer having a glass transition temperature (Tg) of 30 ℃ or lower and containing 1 or more kinds of ethylenically unsaturated bonds and functional groups.

5. The composite laser coating composition for PVC film according to claim 3, wherein said cellulose resin is a mixture of cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate thiopoate.

6. The composite laser coating composition for the PVC film according to claim 3, wherein the polyester resin is one or a mixture of more of a saturated polyester resin with a linear structure, a saturated polyester resin with a benzene ring structure, and a polyurethane modified saturated polyester;

the hydroxyl value of the polyester resin ranges from 40 to 70 mgKOH/g.

7. The composite laser coating composition for the PVC film according to claim 3, wherein the auxiliary agent is a mixture of two or more of a leveling agent, a coupling agent, a slipping agent, a defoaming agent and an adhesion promoter;

the coupling agent comprises one of silane coupling agent and titanate coupling agent.

8. The composite laser coating composition for the PVC film according to claim 3, wherein the solvent is a mixture of three or more of acetone, butanone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isopropanol, n-propanol, n-butanol, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

9. The preparation method of the composite laser coating composition for the PVC film according to any one of claims 1 to 8, wherein the preparation method comprises the following steps:

s1, putting the solvent into the reaction kettle at normal temperature, and uniformly stirring;

s2, putting the polyolefin resin into a reaction kettle, and stirring at a high speed until the polyolefin resin is fully dissolved;

s3, sequentially adding cellulose resin, polyacrylic resin and polyester resin into a reaction kettle, and stirring at a high speed until the cellulose resin, the polyacrylic resin and the polyester resin are fully and uniformly mixed;

s4, adding the auxiliary agent into the reaction kettle, and uniformly stirring at a high speed to obtain the composite laser coating composition for the PVC film.

10. The preparation method of the composite laser coating composition for the PVC film according to claim 9, wherein the preparation method comprises the following steps:

s2, stirring at high speed for 2.0-3.0 hours;

s3, stirring at high speed for 2.5-4.0 h.

Technical Field

The invention relates to the technical field of laser coating compositions, in particular to a composite laser coating composition for a PVC film and a preparation method thereof.

Background

The laser paint is a paint with metal light variation effect, and can present different colors along with the change of observation angle when being sprayed on a flat and smooth object, namely, the phenomenon of color change at different angles, has obvious dynamic color change effect, and can generate the effect of rainbow ring under light condensation.

In the prior art, a PVC printing film is a PVC heat shrinkable film that can be used for printing, is a packaging material with high transparency, good shrinkability, environmental protection, energy conservation and excellent flexibility, is popular with consumers, and is widely applied to outer packages of foods, toys, infant products, stationery, cosmetics, daily necessities, medical supplies and the like. PVC printing film printing effect is fabulous, its clear interesting pattern, abundant bright-colored color can play fine propaganda effect. And the PVC printing film can not generate toxic gas during heat sealing, can be recycled after being discarded, and is a packaging material with the advantages of environmental protection, energy conservation, excellent printing effect and excellent flexibility. The PVC printing film has the characteristics of good stretching capacity, extremely high elongation, high transparency and the like, so that the PVC printing film has a wide application range and is popular with consumers and packaging manufacturers.

But with the continuous promotion of demand, have had higher requirement to ordinary printing, for example add a laser effect on ordinary printing's basis, further improve the pleasing to the eye degree of product. However, the PVC substrate cannot be directly molded to produce a laser effect, a layer of moldable coating is needed, and meanwhile, the fastness of the moldable coating and a PVC film is good, and the moldable coating can resist plasticizers precipitated from the PVC substrate. At present, the coating formed by coating the composite laser coating on the PVC substrate has poor weather resistance and poor firmness with the substrate, and a pattern formed in use is easy to deform, so that a new composite laser coating is urgently needed in the market.

Disclosure of Invention

In order to solve the problems, the invention aims to provide a composite laser coating composition for a PVC film and a preparation method thereof.

In order to achieve the above object, the present invention adopts the following aspects

A composite laser coating composition for PVC films is composed of the following raw materials:

polyolefin resin, cellulose resin, polyacrylic resin, polyester resin, an auxiliary agent and a solvent.

The polyolefin resin has the characteristics of small relative density, good chemical resistance and water resistance, good mechanical strength, electrical insulation property and the like, and is used as a film forming agent in the laser coating composition; the cellulose resin is added into the coating, and has good functions of thickening, suspending, dispersing, emulsifying, bonding, film forming, moisture protection, protective colloid supply and the like; the polyacrylic resin is a homopolymer generated by acrylic acid or methacrylic acid monomers through free radical polymerization reaction or a copolymer generated by other vinyl monomers, and can improve the weather resistance of the coating when added into the coating; polyester resins are a general term for high molecular compounds obtained by polycondensation of dihydric alcohols, dibasic acids, or polyhydric alcohols and polybasic acids, and are used as adhesives in paints.

Preferably, the composite laser coating composition for the PVC film comprises the following raw materials in parts by weight:

preferably, the composite laser coating composition for the PVC film comprises the following raw materials in parts by weight:

preferably, the polyolefin resin is a modified polyolefin resin based on a modifier comprising; a monomer group A and a monomer group B, the weight ratio (A/B) of the monomer group A to the monomer group B is 1/2-1/1, the weight ratio of the monomer group A to the monomer group B is: 1 or more monomers having a homopolymer glass transition temperature (Tg) of 60 ℃ or higher and containing an ethylenically unsaturated bond and a functional group; monomer group B: a homopolymer having a glass transition temperature (Tg) of 30 ℃ or lower and containing 1 or more kinds of ethylenically unsaturated bonds and functional groups.

Preferably, the cellulose resin is a mixture of cellulose acetate butyrate, cellulose acetate propionate and cellulose acetate thiopoyl.

Preferably, the polyester resin is one or a mixture of more of saturated polyester resin with a straight-chain structure, saturated polyester resin with a benzene ring structure and polyurethane modified saturated polyester; the hydroxyl value of the polyester resin ranges from 40 to 70 mgKOH/g.

Preferably, the auxiliary agent is a mixture of two or more of a leveling agent, a coupling agent, a slipping agent, a defoaming agent and an adhesion promoter; the coupling agent comprises one of silane coupling agent and titanate coupling agent.

Preferably, the solvent is a mixture of three or more of acetone, butanone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isopropanol, n-propanol, n-butanol, propylene glycol methyl ether and propylene glycol methyl ether acetate.

A preparation method of a composite laser coating composition for a PVC film comprises the following steps:

s1, putting the solvent into the reaction kettle at normal temperature, and uniformly stirring;

s2, putting the polyolefin resin into a reaction kettle, and stirring at a high speed until the polyolefin resin is fully dissolved;

s3, sequentially adding cellulose resin, polyacrylic resin and polyester resin into a reaction kettle, and stirring at a high speed until the cellulose resin, the polyacrylic resin and the polyester resin are fully and uniformly mixed;

s4, adding the auxiliary agent into the reaction kettle, and uniformly stirring at a high speed to obtain the composite laser coating composition for the PVC film.

Preferably, S2, the high-speed stirring time is 2.0-3.0 hours; s3, stirring at high speed for 2.5-4.0 h.

The invention has the beneficial effects that:

the invention can remarkably improve the adhesion fastness of the coating and the PVC base material and enhance the weather resistance of the coating by using the polyolefin resin, the cellulose resin, the polyacrylic resin and the polyester resin in a matching way to play a synergistic effect.

The coating composition prepared by the invention is convenient to prepare and use, can meet the requirements by using a conventional reaction kettle and a coating machine, is stable in coating state, and can be stored for more than two years; the coating has strong coating adaptability, can be well coated on PVC films with different thicknesses, and has high adhesion fastness with the PVC films and the printing ink; if an aluminum layer or a dielectric layer is added, the fastness of the coating and the aluminum layer or the dielectric layer is also high; the cutting property of the coating is good, the edge cutting is complete, and the powder does not fall off; the coating is easy to mold and can form gorgeous laser effect.

In addition, the cellulose resin is not selected from nitrocellulose (nitrocotton) which has poor stability, is inflammable and explosive, so that the danger in the storage, transportation and production of raw materials can be greatly reduced.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present application, the following will clearly and completely describe the technical solutions in the present application with reference to the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and all other embodiments obtained by a person of ordinary skill in the art without making creative efforts based on the embodiments in the present application shall fall within the protection scope of the present application.

Example 1

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

5 parts of polyolefin resin, 10 parts of cellulose acetate butyrate, 10 parts of cellulose acetate propionate, 20 parts of cellulose acetate thiopyl, 1 part of polyacrylic resin, 4 parts of saturated polyester resin with a straight chain structure, 2 parts of saturated polyester resin with a benzene ring structure, 2 parts of polyurethane modified saturated polyester, 0.1 part of a flatting agent, 0.1 part of a slipping agent, 20 parts of n-butyl alcohol, 30 parts of propylene glycol methyl ether, 20 parts of n-butyl acetate and 10 parts of propylene glycol methyl ether acetate.

Example 2

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

8 parts of polyolefin resin, 15 parts of cellulose acetate butyrate, 15 parts of cellulose acetate propionate, 10 parts of cellulose acetate thiopyl, 2 parts of polyacrylic resin, 3 parts of saturated polyester resin with a straight-chain structure, 3 parts of polyurethane modified saturated polyester, 0.1 part of a flatting agent, 0.2 part of a defoaming agent, 15 parts of ethyl acetate, 15 parts of n-propanol, 15 parts of propylene glycol methyl ether and 30 parts of n-butyl acetate.

Example 3

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

10 parts of polyolefin resin, 5 parts of cellulose acetate butyrate, 10 parts of cellulose acetate propionate, 5 parts of cellulose acetate thiopyl, 3 parts of polyacrylic resin, 2 parts of saturated polyester resin with a straight chain structure, 3 parts of saturated polyester resin with a benzene ring structure, 0.1 part of a leveling agent, 0.2 part of a coupling agent, 0.1 part of a slipping agent, 20 parts of butanone, 10 parts of isopropanol, 10 parts of n-butanol and 10 parts of propylene glycol methyl ether.

Example 4

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

13 parts of polyolefin resin, 5 parts of cellulose acetate butyrate, 3 parts of cellulose acetate propionate, 2 parts of cellulose acetate thiopyl, 4 parts of polyacrylic resin, 3 parts of saturated polyester resin with a linear structure, 0.3 part of adhesion promoter, 0.2 part of slipping agent, 0.2 part of defoaming agent, 15 parts of cyclohexanone, 10 parts of ethyl acetate, 10 parts of isopropanol and 20 parts of n-propyl acetate.

Comparative example 1

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

15 parts of cellulose acetate butyrate, 15 parts of cellulose acetate propionate, 10 parts of cellulose acetate thiopoyl, 2 parts of polyacrylic resin, 3 parts of saturated polyester resin with a straight-chain structure, 3 parts of polyurethane modified saturated polyester, 0.1 part of a flatting agent, 0.2 part of a defoaming agent, 15 parts of ethyl acetate, 15 parts of n-propanol, 15 parts of propylene glycol methyl ether and 30 parts of n-butyl acetate.

Comparative example 2

The embodiment provides a composite laser coating composition for a PVC film, which comprises the following raw materials in parts by weight:

8 parts of polyolefin resin, 15 parts of cellulose acetate butyrate, 15 parts of cellulose acetate propionate, 10 parts of cellulose acetate thiopyl, 3 parts of saturated polyester resin with a straight-chain structure, 3 parts of polyurethane modified saturated polyester, 0.1 part of flatting agent, 0.2 part of defoaming agent, 15 parts of ethyl acetate, 15 parts of n-propanol, 15 parts of propylene glycol methyl ether and 30 parts of n-butyl acetate.

The preparation method of the composite laser coating composition for the PVC film, which is described in any one of examples 1-4 and comparative examples 1-2, comprises the following steps:

s1, putting the solvent into the reaction kettle at normal temperature, and uniformly stirring;

s2, putting the polyolefin resin into a reaction kettle, and stirring at a high speed until the polyolefin resin is fully dissolved;

s3, sequentially adding cellulose resin, polyacrylic resin and polyester resin into a reaction kettle, and stirring at a high speed until the cellulose resin, the polyacrylic resin and the polyester resin are fully and uniformly mixed;

s4, adding the auxiliary agent into the reaction kettle, and uniformly stirring at a high speed to obtain the composite laser coating composition for the PVC film.

S2, stirring at high speed for 2.5 hours; s3, the high-speed stirring time is 3.0 hours.

Application process

The process for using the composite laser coating composition for the PVC film in the embodiment and the comparative example specifically comprises the following steps:

1. batching procedure

The coating composition is diluted with a solvent according to requirements to prepare a coating liquid with certain viscosity.

2. Coating, drying and molding

After the coating liquid is uniformly coated on a PVC base film with a certain thickness by using coating equipment, the PVC base film enters a drying tunnel at a set machine speed to dry a solvent, a layer of uniform and compact coating is formed, and a laser effect is extruded by a mould press.

3. Printing process

Printing ink on the laser coating, and further making into a finished product.

Performance detection

The coating compositions prepared in examples 1 to 4 and comparative examples 1 and 2 were sampled, respectively, and applied by a coater so that the coating dry weight was 3g/m²And then embossing, printing ink on top of the coating. And (3) detecting the performance, and determining the fastness of the primer and PVC and the adhesion to the printing ink.

The specific performance detection items and corresponding methods are as follows:

first, firmness with PVC film

The fastness of the sample sheet coating to the PVC film was tested using 610 tape from 3M company.

The evaluation method comprises the following steps: it is excellent in that no exfoliation occurs at all, good in that a small amount of exfoliation occurs, and poor in that a large amount of exfoliation occurs.

Second, adhesive force

The adhesion of the swatches after printing with ink was tested using 610 tape from 3M company.

The evaluation method comprises the following steps: it is excellent in that no exfoliation occurs at all, good in that a small amount of exfoliation occurs, and poor in that a large amount of exfoliation occurs.

The results of the performance measurements are shown in table 1:

	firmness of coating and PVC film	Adhesion of coating to ink
			Example 1	Superior food	Superior food
Example 2	Superior food	Superior food
			Example 3	Superior food	Superior food
Example 4	Superior food	Superior food
			Comparative example 1	Difference (D)	Difference (D)
Comparative example 2	Difference (D)	Difference (D)

TABLE 1

The difference between the comparative example 1 and the example 2 is that the raw material lacks polyolefin resin, and the difference between the comparative example 2 and the example 2 is that the raw material lacks polyacrylic resin, and the comparison between the examples 1 and 2 and the comparative example 2 shows that the coating composition prepared by the invention, namely the polyolefin resin, the cellulose resin, the polyacrylic resin and the polyester resin, has good flatness, good adhesion firmness and good weather resistance only under a certain proportioning relationship, so that the coating composition has the best comprehensive performance, and various problems in the traditional formula process can be really and thoroughly solved.

Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.