CN114621629A

CN114621629A - Imitation metal etching decorative picture

Info

Publication number: CN114621629A
Application number: CN202111404197.1A
Authority: CN
Inventors: 龚新明
Original assignee: Zhejiang Huazhidu Culture Creativity Co ltd
Current assignee: Zhejiang Huazhidu Culture Creativity Co ltd
Priority date: 2021-11-24
Filing date: 2021-11-24
Publication date: 2022-06-14
Anticipated expiration: 2041-11-24
Also published as: CN114621629B

Abstract

The invention relates to the field of decorative pictures, and discloses a metal-like etched decorative picture, which is prepared by the following steps: and printing the metal-imitation etching coating on the printing surface through a screen with patterns, and irradiating for 3-5 seconds under ultraviolet rays for curing to obtain the metal-imitation etching decorative picture. The metal-like etching coating comprises the following components in parts by weight: 40-70 parts of modified epoxy resin, 15-25 parts of solvent, 1-6 parts of photoinitiator and 1-2 parts of processing aid. The silane coupling agent is utilized to introduce the natural pigment antioxidant and the metal powder pigment into a resin molecular chain, so that the metal powder can be better dispersed in the resin while the resin is subjected to antioxidant modification. The coating is cured on the printing surface by adopting light-initiated curing resin and is quickly dried and cured, and the metal powder pigment in the coating can generate a rough surface, so that the metal-like etching effect is presented after printing.

Description

Metal-like etched decorative picture

Technical Field

The invention relates to the field of decorative pictures, in particular to a metal-like etched decorative picture.

Background

The concept of "light finishing, heavy finishing" has been accepted by most households. People can enjoy the enjoyment of the substances with high economic development and also can trace the spirit of the people, and the household arrangement is fashionable and not in a wonderful way. The metal picture is a relatively common handicraft on the market today, and is mainly used for interior decoration and automobile decoration. Meanwhile, the utility model can also be used in the infant education industry. In the past, the metal decorative painting was mainly gold plating, and there were silver plating, but the cost of gold plating was high, so the sales of the product was limited. In recent years, various metal-like plating processes have been studied and developed, and the effect of metal plating can be simulated on the surfaces of various metals and ornaments of different shapes by using the coating.

The metal-like etching is to print the metal-like etching paint on the printed surface with metal mirror surface gloss by screen printing, and after drying, the image part forms rugged sand-blast like logo relief which forms strong gloss contrast with the unprinted printed material, thereby obtaining a three-dimensional effect. The method is mainly characterized in that a special coating is used, the related research on the coating is limited, and Chinese patent publication No. CN105331183A discloses a quick-drying silk-screen glass metal ink and a preparation process thereof, wherein the quick-drying silk-screen glass metal ink comprises epoxy resin, high-viscosity alkyd resin, nitro resin, organic pigment, organic solvent and auxiliary agent, wherein after the nitro resin dry powder is mixed with the organic solvent, the mixture is ground to slurry fluid with the fineness of 15 mu m by a three-roll grinder, then the epoxy resin, the high-viscosity alkyd resin, the nitro resin, the organic pigment, the organic solvent and the auxiliary agent are added into a container for fully mixing, and the mixture is ground by the three-roll grinder for 30-40min to prepare the slurry fluid mixture, namely the ink; finally, canning the prepared ink to obtain a canned product. The main problems of the imitation metal sheet decorative painting in the preparation process are poor adhesion of the coating to a polished and smooth printing surface in the use process, easy oxidation of metal pigment to lose etching effect and the like.

Disclosure of Invention

The invention aims to solve the problems of poor adhesive force of a smooth printing surface of a coating polished in the preparation process of the existing metal-like etched decorative picture and easy oxidation of a metal pigment, and provides the metal-like etched decorative picture.

In order to achieve the purpose, the invention adopts the following technical scheme:

a metal-like etching decorative picture is prepared by the following steps: and printing the metal-imitation etching coating on the printing surface through a screen with patterns, and irradiating for 3-5 seconds under ultraviolet rays for curing to obtain the metal-imitation etching decorative picture.

The metal powder in the metal-like etching coating can generate a rough surface, so that the metal-like etching effect is presented after printing. The prepared metal-like etched decorative picture has vivid and bright color, strong layering sense, fine picture quality and strong third dimension and depth sense.

Preferably, the imitation metal etching coating comprises the following components in parts by weight:

under the catalysis of a photoinitiator, epoxy groups in the coating undergo a ring-opening reaction to form crosslinking, and the crosslinking is quickly dried on the printing surface. The metal pigment can stably exist in the resin better through antioxidant modification, and the phenomenon that the paint loses metal luster due to oxidation is avoided. The metal powder obtains better dispersibility through surface modification, and the uniformity and stability of the printing effect are ensured.

Preferably, the preparation method of the modified resin comprises the following steps:

(1) soaking metal powder in a silane coupling agent solution containing double bonds with the mass fraction of 0.5-2% for 1-3 h at 40-80 ℃, and filtering to obtain modified metal powder;

(2) mixing modified metal powder and a natural pigment antioxidant in a nitrogen atmosphere, wherein the mass ratio of the modified metal powder to the natural pigment antioxidant is 2-4: 1, and stirring and reacting for 3-6 h at 40-50 ℃ to obtain modified metal powder coupled with the antioxidant;

(3) adding epoxy resin, wherein the ratio of the epoxy functional group in the epoxy resin to the natural pigment antioxidant is 8-12: 1, mixing, heating to 60-80 ℃, reacting for 3-10 h, and removing the solvent to obtain the modified resin.

In order to simulate the metal etching effect, the particle size of the metal powder needs to be controlled. The metal powder with the excessively small particle size can form insufficient diffuse reflection, and the generated rough effect is poor; metal powder having an excessively large particle diameter is difficult to be uniformly distributed in the resin, and cannot be used in the coating material. In order to further improve the dispersibility and compatibility of the metal powder, it is necessary to modify the surface thereof so that the metal powder can be better dispersed in the resin. In the step (1), the metal powder is subjected to surface modification by using a silane coupling agent, long-chain alkyl at one end of the silane coupling agent can be bent and wound with an organic matter, and hydroxyl at the other end can be combined on the surface of metal or metal oxide, so that the hydrophobicity of the metal surface is enhanced, and the metal surface can be better dispersed in an organic resin system.

In the step (2), the modified metal powder and the natural pigment antioxidant are mixed, and the natural pigment antioxidant is grafted to the silane coupling agent by utilizing double bond addition reaction, so that a better antioxidant effect can be achieved, the coating can keep metallic luster for a longer time, and the artistic effect of the metal-like etched decorative picture is achieved.

In the step (3), the epoxy resin is added, so that the silane coupling agent reacts with an epoxy group in an epoxy resin chain segment and is fully crosslinked, the natural pigment antioxidant and the metal powder are introduced into a resin molecular chain, the metal powder is uniformly dispersed in the resin, the dispersibility and compatibility of the metal powder are improved, and the color of the natural pigment antioxidant is utilized to endow the paint with a better artistic effect.

Preferably, the metal powder is one or a combination of gold, silver, copper, titanium, iron and aluminum, and the fineness of the metal powder is 100-300 meshes.

Preferably, the double-bond-containing silane coupling agent is one or a combination of gamma- (methacryloyloxy) propyl trimethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane; the natural pigment antioxidant is one of lycopene, beta-carotene and astaxanthin.

In the reaction of step (2), the ratio of the amount of the silane coupling agent to the amount of the natural pigment antioxidant needs to be controlled, if the silane coupling agent is insufficient, the reaction efficiency of the natural pigment antioxidant is reduced, the subsequent reaction with the resin monomer is affected, and if the silane coupling agent is excessive, too many silicon-oxygen bond segments exist in the resin monomer, the ductility of the resin is reduced, and too much metal powder is brought in, and the printing is difficult.

Preferably, the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of the cyclohexanone to the butyl acetate is 4-8: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 0.1-2 parts of defoaming agent and 0.1-2 parts of flatting agent; the defoaming agent is an acrylic defoaming agent; the leveling agent is one or the combination of polydimethylsiloxane or acrylic ester leveling agent.

Preferably, the screen plate comprises a screen frame and a screen, and the screen frame is an aluminum alloy screen frame. The aluminum alloy screen frame has the characteristics of stable performance, durability, portability and difficult deformation, and is suitable for printing of the imitation metal etched decorative picture. More preferably, the frame and screen are connected by a diagonal stretching. The occurrence of saw-toothed shapes can be reduced, and the plate making sharpness is improved.

Preferably, the screen mesh is a plain weave mesh, and the mesh number of the plain weave mesh is 150 to 300 meshes. Since the particle diameter of the etching ink is relatively large between 15-30 um, the mesh number of the screen should be between 150-300 mesh, more preferably between 180-240 mesh, so as to avoid malfunction during printing.

Preferably, the printing surface is a metallic luster surface, and comprises one of a glass paperboard surface, a surface of evaporated polyethylene or polyethylene matte film, a surface of alumite film, and a surface of gold or silver paperboard.

Therefore, the invention has the following beneficial effects: (1) the coating adopts photo-initiated curing resin, under the catalytic action of a photoinitiator, epoxy groups in the epoxy resin are subjected to ring-opening reaction to form crosslinking, and the crosslinking is quickly dried on the printing surface, wherein the existing metal powder pigment can generate a rough surface, so that the printed metal-like etching effect is realized; (2) the natural pigment antioxidant is added for antioxidant modification, so that the metal pigment can stably exist in the resin better, the phenomenon that the paint loses metal luster due to oxidation is avoided, and meanwhile, the natural pigment has a color and can endow the resin with a certain color and luster at a proper concentration; (3) by carrying out surface modification on the metal powder pigment, the metal powder can obtain better dispersibility, and the uniformity and stability of the printing effect can be ensured.

Detailed Description

The invention is further described below with reference to specific embodiments. It is to be understood that these examples are suitable for illustrating the basic features and advantages of the invention, and the invention is not to be limited in scope by the following examples; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not noted are generally those used in routine experiments.

Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.

Example 1

(A) Preparation of modified resin:

(1) soaking iron powder with the fineness of 200 meshes in a gamma- (methacryloyloxy) propyl trimethoxy silane solution with the mass fraction of 1% at 60 ℃ for 2 hours, and filtering to obtain modified metal powder;

(2) mixing modified metal powder and lycopene in a nitrogen atmosphere, wherein the mass ratio of the modified metal powder to the lycopene is 3:1, and stirring and reacting for 5 hours at 45 ℃ to obtain modified metal powder of a coupling antioxidant;

(3) adding epoxy resin, wherein the quantity ratio of epoxy functional groups in the epoxy resin to lycopene substances is 10:1, mixing, heating to 70 ℃, reacting for 8h, and removing the solvent to obtain the modified resin.

(B) The preparation of the imitation metal etching coating comprises the following components in parts by weight:

the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of the cyclohexanone to the butyl acetate is 6: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 1 part of acrylic defoaming agent and 1 part of polydimethylsiloxane leveling agent. Dispersing the raw materials according to the weight parts for 2h at 40 ℃ and 300rpm, and canning to obtain the high-stability metal-like etching coating.

(C) Preparing a metal-imitated etching decorative picture: the screen plate with the patterns is manufactured through photosensitive plate manufacturing, the screen plate comprises a screen frame and a silk screen, the screen frame is an aluminum alloy screen frame, and the silk screen is a 200-mesh plain woven screen. And printing the metal-like etching coating on the surface of the glass paperboard through a screen, and irradiating for 3 seconds under ultraviolet rays for curing to obtain the metal-like etching decorative picture.

Example 2

(A) Preparation of modified resin:

(1) soaking copper silver powder with the fineness of 300 meshes in 2% of vinyl trimethoxy silane solution at 40 ℃ for 3h, and filtering to obtain modified metal powder;

(2) mixing modified metal powder and astaxanthin in a nitrogen atmosphere, wherein the mass ratio of the modified metal powder to the astaxanthin is 2:1, and stirring and reacting for 6 hours at 40 ℃ to obtain modified metal powder of the coupling antioxidant;

(3) adding epoxy resin, wherein the mass ratio of epoxy functional groups in the epoxy resin to astaxanthin is 12:1, mixing, heating to 60 ℃, reacting for 10h, and removing the solvent to obtain the modified resin.

the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of the cyclohexanone to the butyl acetate is 8: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 2 parts of acrylic defoaming agent and 2 parts of acrylic flatting agent.

(C) Preparing a metal-imitated etching decorative picture: the screen plate with the pattern is manufactured through photosensitive plate manufacturing, the screen plate comprises a screen frame and a silk screen, the screen frame is an aluminum alloy screen frame, and the silk screen is a 150-mesh plain woven screen. And printing the metal-like etching coating on the surface of the gold card paper through a screen, and irradiating for 5 seconds under ultraviolet rays for curing to obtain the metal-like etching decorative picture.

Example 3

(A) Preparation of modified resin:

(1) soaking aluminum powder with the fineness of 100 meshes in a vinyltriethoxysilane solution with the mass fraction of 0.5% at 80 ℃ for 1h, and filtering to obtain modified metal powder;

(2) mixing modified metal powder and beta-carotene in a nitrogen atmosphere, wherein the mass ratio of the modified metal powder to the beta-carotene is 4:1, and stirring and reacting for 3 hours at 50 ℃ to obtain modified metal powder of a coupling antioxidant;

(3) adding epoxy resin, wherein the mass ratio of epoxy functional groups in the epoxy resin to beta-carotene is 8:1, mixing, heating to 80 ℃, reacting for 3h, and removing the solvent to obtain the modified resin.

the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of the cyclohexanone to the butyl acetate is 4: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 0.5 part of acrylic defoaming agent and 0.1 part of polydimethylsiloxane leveling agent.

(C) Preparing a metal-imitated etching decorative picture: the screen plate with the pattern is manufactured through photosensitive plate manufacturing, the screen plate comprises a screen frame and a silk screen, the screen frame is an aluminum alloy screen frame, and the silk screen is a 300-mesh plain woven screen. And printing the imitation metal etching coating on the surface of the alumite film through a screen, and irradiating for 4s for curing under ultraviolet rays to obtain the imitation metal etching decorative picture.

Example 4

(A) Preparation of modified resin:

(1) soaking gold powder with the fineness of 250 meshes in a solution of gamma- (methacryloyloxy) propyl trimethoxy silane and vinyl triethoxy silane with the mass fraction of 2% at 50 ℃ for 2 hours, wherein the mass ratio of the gamma- (methacryloyloxy) propyl trimethoxy silane to the vinyl triethoxy silane is 1:1, and filtering to obtain modified metal powder;

(2) mixing modified metal powder and astaxanthin in a nitrogen atmosphere, wherein the mass ratio of the modified metal powder to the astaxanthin is 2.5:1, and stirring and reacting for 4 hours at 40 ℃ to obtain modified metal powder of a coupling antioxidant;

(3) adding epoxy resin, wherein the mass ratio of epoxy functional groups in the epoxy resin to astaxanthin is 8:1, mixing, heating to 70 ℃, reacting for 5h, and removing the solvent to obtain the modified resin.

the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of the cyclohexanone to the butyl acetate is 5: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 1 part of acrylic defoaming agent and 2 parts of acrylate leveling agent.

(C) Preparing a metal-imitated etching decorative picture: the screen plate with the pattern is manufactured through photosensitive plate manufacturing, the screen plate comprises a screen frame and a silk screen, the screen frame is an aluminum alloy screen frame, and the silk screen is a 220-mesh plain woven screen. And printing the metal-like etching coating on the surface of the evaporated polyethylene through a screen, and irradiating for 5s under ultraviolet rays for curing to obtain the metal-like etching decorative picture.

Comparative example 1

The comparative example is different from example 1 only in that the raw material adopts unmodified epoxy resin, and the preparation of the metal-like etching coating comprises the following components in parts by weight:

Comparative example 2

This comparative example differs from example 1 only in that the modified resin was prepared by the method comprising:

(2) adding epoxy resin, wherein the mass ratio of epoxy functional groups in the epoxy resin to the modified metal powder is 3:1, mixing, heating to 70 ℃, reacting for 8h, and removing the solvent to obtain the modified resin.

Comparative example 3

This comparative example differs from example 1 only in that no photoinitiator was added to the preparation of the metal-like etching coating in step (B).

Comparative example 4

The comparative example is different from example 1 only in that the wire mesh during the production of the metal-like etched decorative picture in step (C) is a plain woven mesh of 500 mesh.

The products prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to quality measurement, and the results are shown in table 1 below.

TABLE 1 quality determination results of high-stability metal-like etching coating

Group of	Solid content (%)	Tinting strength (%)	Adhesion force
				Example 1	68	101	First stage
Example 2	66	102	First stage
				Example 3	74	99	First stage
Example 4	63	97	First stage
				Comparative example 1	45	76	First stage
Comparative example 2	60	80	First stage
				Comparative example 3	67	93	Second stage
Comparative example 4	65	69	Second stage

The high-stability metal-like etching coating prepared in examples 1 to 4 has a solid content meeting the standard, a standard tinting strength, a strong adhesive force, and a stable effect. The metallic powder pigment was not modified in comparative example 1, and thus its dispersibility in a resin matrix was poor, thereby causing a significant decrease in solid content and tinting strength. In comparative example 2, no natural pigment antioxidant was added to copolymerize with the resin monomer during the resin modification, which also affected the tinting strength of the coating. In addition, in the subsequent use process, the gloss of the coating of the comparative example 1 and the coating of the comparative example 2 are obviously reduced after a period of time (weeks), and the effect of metal-like etching cannot be achieved, which is probably because the protection of natural pigment antioxidants is lacked and the oxidation speed of the metal powder is accelerated. In the comparative example 3, no photoinitiator is added in the preparation process of the metal-like etching coating, so that the coating needs longer time to be cured in the subsequent curing process, the production efficiency is influenced, and the adhesive force is reduced. In comparative example 4, a screen having a higher mesh size was used, and the difficulty of penetration of the metal-like etching coating became high due to the excessively high mesh size, and particularly, the metal powder particles therein were large and difficult to pass through the screen, resulting in a significant decrease in tinting strength and adhesion.

Claims

1. A metal-like etching decorative picture is characterized in that the preparation method comprises the following steps: and printing the metal-imitation etching coating on the printing surface through a screen with patterns, and irradiating for 3-5 seconds under ultraviolet rays for curing to obtain the metal-imitation etching decorative picture.

2. The metal-like etching decorative picture as claimed in claim 1, wherein the metal-like etching coating comprises the following components in parts by weight:

40-70 parts of modified epoxy resin

15-25 parts of solvent

1-6 parts of photoinitiator

1-2 parts of a processing aid.

3. The metal-like etched decorative picture as claimed in claim 2, wherein the modified resin is prepared by the following steps:

(1) soaking metal powder in a silane coupling agent solution containing double bonds and having a mass fraction of 0.5-2% at 40-80 ℃ for 1-3 h, and filtering to obtain modified metal powder;

(3) adding epoxy resin, wherein the mass ratio of epoxy functional groups in the epoxy resin to natural pigment antioxidants is 8-12: 1, mixing, heating to 60-80 ℃, reacting for 3-10 h, and removing the solvent to obtain the modified resin.

4. The metal-like etched decorative picture as claimed in claim 3, wherein the metal powder is one or a combination of gold, silver, copper, titanium, iron and aluminum, and the fineness is 100-300 meshes.

5. The metal-like etched decorative picture as claimed in claim 3, wherein the double bond-containing silane coupling agent is one or a combination of γ - (methacryloyloxy) propyl trimethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane; the natural pigment antioxidant is one of lycopene, beta-carotene and astaxanthin.

6. The metal-like etching decorative picture as claimed in claim 2, wherein the solvent is a mixture of cyclohexanone and butyl acetate, and the mass ratio of cyclohexanone to butyl acetate is 4-8: 1; the photoinitiator is a cationic photoinitiator; the processing aid comprises the following raw materials in parts by weight: 0.1-2 parts of defoaming agent and 0.1-2 parts of flatting agent; the defoaming agent is an acrylic defoaming agent; the leveling agent is one or the combination of polydimethylsiloxane or acrylic ester leveling agent.

7. The metal-like etching decorative picture as claimed in claim 1, wherein said screen plate comprises a screen frame and a silk screen, and said screen frame is an aluminum alloy screen frame.

8. The metal-like etched decorative picture as claimed in claim 7, wherein said screen is a plain woven mesh, and the mesh number of the plain woven mesh is 150-300 mesh.

9. The etched metal-like decorative drawing as claimed in claim 1, wherein said printing surface is a metallic luster surface.