CN115160854B - Shoe material light-sensitive ink, preparation method and application thereof - Google Patents

Shoe material light-sensitive ink, preparation method and application thereof Download PDF

Info

Publication number
CN115160854B
CN115160854B CN202210741875.1A CN202210741875A CN115160854B CN 115160854 B CN115160854 B CN 115160854B CN 202210741875 A CN202210741875 A CN 202210741875A CN 115160854 B CN115160854 B CN 115160854B
Authority
CN
China
Prior art keywords
parts
shoe material
photosensitive
weight
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210741875.1A
Other languages
Chinese (zh)
Other versions
CN115160854A (en
Inventor
黄景柱
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Sanqi New Material Technology Co ltd
Original Assignee
Guangdong Sanqi New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Sanqi New Material Technology Co ltd filed Critical Guangdong Sanqi New Material Technology Co ltd
Priority to CN202210741875.1A priority Critical patent/CN115160854B/en
Publication of CN115160854A publication Critical patent/CN115160854A/en
Application granted granted Critical
Publication of CN115160854B publication Critical patent/CN115160854B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The application relates to the technical field of shoe material printing ink, in particular to shoe material light-sensitive printing ink, a preparation method and application thereof. The shoe material light-sensitive ink is prepared from the following raw materials in parts by weight: 30-50 parts of photosensitive copolymer emulsion, 10-15 parts of photosensitive powder, 15-25 parts of liquid paraffin, 10-15 parts of solid filler, 20-25 parts of thickener, 10-15 parts of tackifier, 1-2 parts of defoamer, 0.1-0.5 part of coupling agent, 0.1-0.2 part of accelerator and 0.1-1.5 part of curing agent, wherein each part of photosensitive copolymer emulsion is obtained by mixing epoxy resin emulsion and phenolic resin emulsion. The shoe material light-sensitive ink is prepared by uniformly mixing the raw materials, and has good water resistance, oil resistance, weather resistance and light fatigue resistance.

Description

Shoe material light-sensitive ink, preparation method and application thereof
Technical Field
The application relates to the technical field of shoe material printing ink, in particular to shoe material light-sensitive printing ink, a preparation method and application thereof.
Background
With the gradual improvement of living conditions, people pursue beauty more and more, have higher requirements on wearing in daily life, and the higher the color requirement is. Such as shoes, the prior shoes only have fixed colors and cannot make the colors dynamically changed. Along with the development of scientific technology, people find photosensitive powder, the photosensitive powder is used for preparing shoe material light-sensitive ink, and then the shoe material light-sensitive ink is printed on the surface of the shoe material, so that the surface of the shoe material can become another color in sunlight, and the color of the surface of the shoe material shows dynamic change.
However, shoes worn by people are exposed to air for a long time, so that the light-sensitive ink is also exposed to the environment for a long time and is corroded by sunlight exposure, outside water and acid-base substances, the structure of the light-sensitive ink is damaged, light fatigue is generated, and the glossiness of the light-sensitive ink is reduced.
Disclosure of Invention
In order to solve the problem of light fatigue of the light-sensitive ink, the application provides the light-sensitive ink for the shoe material and a preparation method thereof.
In a first aspect, the application provides a shoe material light-sensitive ink, which adopts the following technical scheme:
the shoe material light-sensitive ink is prepared from the following raw materials in parts by weight:
30-50 parts of photosensitive copolymer emulsion
10 to 15 parts of photosensitive powder
15-25 parts of liquid paraffin
10-15 parts of solid filler
20-25 parts of thickening agent
10-15 parts of tackifier
1-2 parts of defoaming agent
0.1 to 0.5 part of coupling agent
0.1 to 0.2 part of accelerator and 0.1 to 1.5 parts of curing agent
Each photosensitive copolymer emulsion is obtained by mixing epoxy resin emulsion and phenolic resin emulsion resin.
By adopting the technical scheme, the prepared shoe material light-sensitive ink has good light fatigue resistance, weather resistance and water and oil resistance. According to the application, the photosensitive ink for the shoe material is obtained by mixing and grinding the photosensitive polymer, the photosensitive powder, the liquid paraffin, the solid filler, the thickener, the tackifier, the coupling agent, the defoamer and the curing agent, so that the photosensitive powder is uniformly distributed in the system, and the photosensitive ink forms a photosensitive ink layer after curing, and the photosensitive ink layer has good light fatigue resistance, weather resistance, water resistance and oil resistance.
The epoxy resin emulsion and the phenolic resin emulsion can crosslink and interpenetrate under the action of the curing agent to form a three-dimensional network structure, so that the structural stability of the photosensitive ink is improved, the photosensitive powder can be attached to the three-dimensional network structure, the contact between the photosensitive powder and the outside is reduced, the service life of the photosensitive powder is prolonged, and the weather resistance, the water resistance, the oil resistance and the light fatigue resistance of the photosensitive ink are improved.
The accelerator and the curing agent in the photosensitive ink do not play a role in the storage process, and when the photosensitive ink is heated during printing, the curing agent plays a role at the moment, so that the epoxy resin emulsion and the phenolic resin emulsion are cured to form a network structure, and a photosensitive ink layer is formed.
The liquid paraffin is used as a lubricant, so that the fluidity of the epoxy resin emulsion, the phenolic resin emulsion, the photosensitive powder, the solid filler and the thickener is improved, the raw materials can be uniformly distributed in a system in the preparation of the shoe material photosensitive ink, the structure of the shoe material photosensitive ink is more stable, and the light fatigue resistance is improved; on the other hand, the liquid paraffin can reduce the surface energy of the light-sensitive ink surface of the shoe material, reduce the adhesion of stains on the light-sensitive ink surface of the shoe material, and further reduce the influence of external environment on the light-sensitive ink of the shoe material.
The adhesion degree of the photosensitive polymer, the photosensitive powder, the liquid paraffin and the solid filler is increased by the tackifier and the thickener, so that the structure of the shoe material photosensitive ink is more stable.
The defoamer can reduce the generation of bubbles of the epoxy resin emulsion and the phenolic resin emulsion in the curing process, so that the epoxy resin emulsion and the phenolic resin emulsion form a three-dimensional network structure in the cross-linking and cross-passing process.
The weight ratio of the epoxy resin emulsion to the phenolic resin emulsion is (0.5-0.8): 1.
The solid filler in the application can be silicon dioxide, talcum powder, titanium dioxide, kaolin and the like.
The average particle size of the solid filler in the application is 30-50 nm.
The curing agent in the present application may be hexamethylenetetramine, divinyl triamine, 1, 2-diaminocyclohexane, isophorone diamine or the like.
The coupling agent can be a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, a phosphate coupling agent, a borate coupling agent, or the like.
The promoter is DMP-30, BDMA, N- (4-chloro-2-hydroxyphenyl) -N ', N' -dimethylurea, resorcinol or o-cresol, etc.
Preferably, the phenolic resin emulsion is a modified phenolic resin emulsion, and the modified phenolic resin emulsion is prepared by the following method:
mixing 60-70 parts by weight of epoxidized soybean oil, 100-130 parts by weight of formaldehyde solution and 20-30 parts by weight of anhydrous acetic acid solution, heating to 50-60 ℃, dropwise adding 0.1-0.2 part by weight of catalyst, and reacting for 1-2 hours to obtain a mixture; heating to 70-80 ℃, adding 80-90 parts by weight of diphenyl ether into the mixture, reacting for 30-60 min, heating to 150-170 ℃, dripping 15-20 parts by weight of 10-15% sodium hydroxide solution, and reacting for 30-60 min to obtain the phenolic resin emulsion.
The phenolic resin emulsion is relatively dark in color, typically between brown and black, after curing, which can affect the gloss of the photoinduced ink. By adopting the technical scheme to prepare the modified phenolic resin emulsion, the color of the modified phenolic resin emulsion is lighter, the influence on the glossiness of the photosensitive ink is smaller, and the glossiness retention time of the photosensitive ink can be improved.
The epoxy soybean oil is added in the process of preparing the modified phenolic resin emulsion, and the epoxy soybean oil participates in the reaction, so that the weather resistance of the modified phenolic resin emulsion is improved, the modified phenolic resin emulsion is used for preparing the light-sensitive ink, the light fatigue resistance of the light-sensitive ink can be effectively improved, and the glossiness of the light-sensitive ink is less influenced.
The catalyst can be hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, phenolsulfonic acid and the like.
The mass fraction of the formaldehyde solution in the application is 8-13%.
Preferably, the photosensitive powder is at least one of 3-diethylamino-6-methyl-7-phenylamino fluoran, 2'- (dibenzylamino) -6' - (diethylamino) fluoran and benzoic acid-phenanthroline-europium ternary complex.
By adopting the photosensitive powder, the photosensitive ink shows dynamic reaction, so that the shoe material can show another color in a light place. The photosensitive powder is used together with photosensitive copolymer emulsion, liquid paraffin, solid filler, thickener, defoamer, tackifier and curing agent, so that the light fatigue resistance of the photosensitive powder can be improved, and the service time of the photosensitive powder can be prolonged.
Preferably, each part of thickener is prepared from sodium alginate, carboxymethyl cellulose and purified water according to the weight ratio of (1-5): (1-5) 10.
The photosensitive ink is a solid-liquid mixture, solid-liquid separation possibly occurs in the mixing process in a standing process, so that the printing effect is poor.
Preferably, each part of tackifier is prepared by mixing acrylic acid and absolute ethyl alcohol according to the weight ratio of (5-10): 10.
Most of cloth, leather or synthetic leather of the shoe material are easy to fall off after the light-sensitive ink is printed on the surface of the cloth, leather or synthetic leather, and in order to improve the bonding stability of the light-sensitive ink and the shoe material, the adhesion agent is prepared by using the acrylic acid, the methacrylic acid and the absolute ethyl alcohol, and is strong in adhesion, so that the adhesion of the light-sensitive ink of the shoe material can be improved, and the light-sensitive ink of the shoe material is not easy to fall off.
Most of cloth, leather or synthetic leather on the surface of the shoe material contains hydroxyl groups, and carboxyl groups of acrylic acid and methacrylic acid react with the hydroxyl groups on the surface of the shoe material, so that the light-sensitive ink is stably attached to the surface of the shoe material.
The absolute ethyl alcohol dissolves the acrylic acid and the methacrylic acid, so that the acrylic acid and the methacrylic acid can be uniformly dispersed in the system, and the acrylic acid and the methacrylic acid are uniformly mixed with the photosensitive copolymer emulsion, the liquid paraffin, the photosensitive powder and the solid filler, thereby being convenient for printing.
Preferably, the defoaming agent is one of amides, phosphates, silicones, polyethers and fatty acid esters.
By adopting the defoaming agent, the generation of bubbles in the light-sensitive ink in the curing process is reduced, so that the printing of the light-sensitive ink is kept smooth and uniform, and the glossiness is good.
Preferably, the shoe material light-sensitive ink further comprises 2-5 parts by weight of softening agent, wherein each part of softening agent is prepared by the following preparation method:
dissolving 0.1-1 part by weight of diester propyl quaternary ammonium salt in 10-15 parts by weight of purified water to obtain a salt solution, heating to 80-90 ℃, adding 10-20 parts by weight of polyethylene glycol into the salt solution, and stirring until the polyethylene glycol is dissolved to obtain the softening agent.
As the epoxy resin emulsion is added in the application, the brittleness of the formed light-sensitive ink is increased, and if the formed light-sensitive ink is bent for a plurality of times, the formed light-sensitive ink is easy to crack. The softening agent is added to the application, so that the brittleness of the photosensitive ink is reduced, and the photosensitive ink is not easy to crack in use.
When the light-sensitive ink is cured, polyethylene glycol reacts with the epoxy resin emulsion to reduce brittleness of the epoxy resin emulsion, so that flexibility of the formed light-sensitive ink is increased, and the formed light-sensitive ink is not easy to crack in the use process.
In the application, the diester propyl quaternary ammonium salt is dissolved in purified water and then mixed with polyethylene glycol, so that the surface energy of the polyethylene glycol is reduced, and the polyethylene glycol can fully react with the epoxy resin emulsion, thereby reducing brittleness.
The molecular weight of the polyethylene glycol is 10000-25000.
In a second aspect, the application provides a preparation method of shoe material light-sensitive ink, which adopts the following technical scheme:
a preparation method of shoe material light-sensitive ink. The preparation method of the shoe material light-sensitive ink comprises the following preparation steps:
the solid filler and the photosensitive powder are uniformly mixed according to parts by weight, and then tackifier, liquid paraffin, thickener, defoamer, coupling agent, accelerator, curing agent and photosensitive copolymer emulsion are added, stirred, ground and filtered at the temperature of 10-40 ℃ to obtain the shoe material photosensitive ink.
The preparation method is simple in operation and convenient for production. The above raw materials are mixed first. The mixture is ground and filtered, so that the light-sensitive ink is finer and is convenient to print.
Preferably, the stirring speed is 200-300 r/min, and the mixture is ground and then sieved by a 50-100-mesh sieve.
By adopting the technical scheme, the solid filler, the photosensitive powder, the paraffin wax, the thickening agent, the defoaming agent and the photosensitive copolymer emulsion can be uniformly mixed to prepare homogeneous mixed liquid, so that the shoe material light-sensitive ink with better light fatigue resistance, weather resistance and softness is obtained.
In a third aspect, the application provides an application of the shoe material light-sensitive ink, which adopts the following technical scheme:
the shoe material light-sensitive ink is applied to shoe material surface printing, the shoe material light-sensitive ink is the shoe material light-sensitive ink of the first aspect, and the shoe material light-sensitive ink is prepared by the preparation method of the shoe material light-sensitive ink of the second aspect.
By adopting the technical scheme, the color of the surface of the shoe material can be changed along with the change of light, and the shoe material has good light fatigue resistance, good glossiness, good water and oil resistance and softness.
Wherein the shoe material is leather shoe material, cloth shoe material, synthetic leather shoe material, etc.
In order to stably print the photosensitive ink on the surface of the shoe material, the shoe material needs to be pretreated before the photosensitive ink is printed on the surface of the shoe material, and the specific steps are as follows: heating the shoe material at 50-60 ℃, coating acrylic acid on the surface of the shoe material, cooling to 10-35 ℃, shaping, and printing light-sensitive ink on the surface of the shoe material.
In order to better solidify and shape the light sensitive ink, the printing temperature of the light sensitive ink is 50-60 ℃, and after the printing is finished, the printed shoe material is required to be dried under the ultraviolet light with the temperature of 90-120 ℃.
In summary, the application has the following beneficial effects:
1. the shoe material light-sensitive ink is prepared by mixing and grinding the photosensitive polymer, the photosensitive powder, the liquid paraffin, the solid filler, the thickening agent, the defoaming agent, the tackifier, the coupling agent, the accelerator and the curing agent, and has good light fatigue resistance, weather resistance, water resistance and oil resistance. According to the application, the raw materials are mixed and ground to prepare the shoe material light-sensitive ink, the temperature is increased in the printing process, and the curing agent acts to enable the epoxy resin emulsion and the phenolic resin emulsion to be cured to form a network structure, so that the structural stability of the light-sensitive ink is enhanced, the photosensitive powder can be attached to a three-dimensional network structure, the contact between the photosensitive powder and the outside is reduced, the service life of the photosensitive powder is prolonged, and the weather resistance, the water resistance, the oil resistance and the light fatigue resistance of the light-sensitive ink are improved.
2. According to the application, the modified phenolic resin emulsion has improved weather resistance by using the epoxidized soybean oil, the formaldehyde solution, the anhydrous acetic acid, the catalyst, the diphenyl ether and the sodium hydroxide solution, is used for preparing the photosensitive ink, can effectively improve the light fatigue resistance of the photosensitive ink, and has less influence on the glossiness of the photosensitive ink.
3. According to the application, the softening agent is prepared from the diester propyl quaternary ammonium salt, purified water and polyethylene glycol, and the light-sensitive ink is prepared from the softening agent, so that the brittleness of the light-sensitive ink is reduced, the flexibility of the formed light-sensitive ink is increased, and the formed light-sensitive ink is not easy to crack in use.
Detailed Description
Preparation examples 1 to 3 of phenolic resin emulsion
Preparation example 1
A phenolic resin emulsion is prepared by the following method:
mixing 0.6Kg of epoxidized soybean oil and 1Kg of formaldehyde solution with the mass fraction of 8% with 0.2Kg of anhydrous acetic acid solution, heating to 50 ℃, dropwise adding 0.001Kg of catalyst (hydrochloric acid), and reacting for 1h to obtain a mixture;
heating to 70 ℃, adding 0.8Kg of diphenyl ether into the mixture, reacting for 30min, heating to 150 ℃, then dripping 0.15Kg of 10% sodium hydroxide solution, reacting for 30min, and filtering to obtain the phenolic resin emulsion.
Preparation 2 and preparation 3 differ from preparation 1 in that: the types, amounts and experimental parameters of some raw materials were different, and the experimental procedure was identical to that of preparation example 1. The materials and amounts used in preparation examples 1 to 3 are shown in Table 1:
TABLE 1 materials and amounts used in preparation examples 1 to 3
Examples
Example 1
A photosensitive ink, prepared by the method of:
mixing 0.1Kg of solid filler (titanium white) and 0.1Kg of photosensitive powder (3-diethylamino-6-methyl-7-phenylaminofluoran), adding 0.1Kg of tackifier (0.03 Kg of acrylic acid, 0.07Kg of absolute ethyl alcohol), 0.15Kg of liquid paraffin, 0.2Kg of thickener (0.017 Kg of sodium alginate, 0.017Kg of carboxymethyl cellulose, 0.167Kg of water), 0.01Kg of defoamer, 0.001Kg of coupling agent (titanate coupling agent), 0.001Kg of accelerator (BDMA), 0.001Kg of curing agent (hexamethylenetetramine) and 0.3Kg of photosensitive copolymer emulsion (epoxy resin emulsion is 0.1Kg and commercial phenolic resin emulsion is 0.2 Kg), stirring at 10 ℃, stirring at a stirring speed of 200r/min, grinding, and sieving with a 50-mesh sieve to obtain the shoe material photosensitive ink.
In this embodiment, the photosensitive copolymer emulsion is an epoxy phenolic resin emulsion, and the average molecular weight thereof is 200-10000.
Commercial phenolic resin emulsion is purchased from Jining Sanshi biotechnology Co., ltd, model number SH.
Examples 2 to 5 differ from example 1 in that: the experimental procedure was identical to example 1, except for the types of the partial raw materials, the amounts of the raw materials and the experimental parameters. The types and amounts of the raw materials and experimental parameters in examples 1 to 5 are shown in Table 2:
table 2 kinds, amounts and experimental parameters of the respective raw materials of examples 1 to 5
Example 6
The difference between the photosensitive ink and the example 2 is that: in this example, after the solid filler and the photosensitive powder were mixed, 0.02Kg of softener was added, and the types, amounts and experimental procedures of the remaining raw materials were the same as those in example 1.
The softener is prepared by the following preparation method:
dissolving 0.01Kg of diester propyl quaternary ammonium salt in 1Kg of purified water to obtain a salt solution, heating to 80 ℃, adding 1Kg of polyethylene glycol into the salt solution, and stirring until the polyethylene glycol is dissolved to obtain the softener.
Example 7
The difference between the photosensitive ink and the example 2 is that: in this example, after the solid filler and the photosensitive powder were mixed, 0.05Kg of softener was added, and the types, amounts and experimental procedures of the remaining raw materials were the same as those in example 1.
The softener is prepared by the following preparation method:
dissolving 0.1Kg of diester propyl quaternary ammonium salt in 1.5Kg of purified water to obtain a salt solution, heating to 90 ℃, adding 2Kg of polyethylene glycol into the salt solution, and stirring until the polyethylene glycol is dissolved to obtain the softener.
Comparative example
Comparative example 1
The photosensitive ink of this example is different from that of example 1 in that: the same amount of polyamide resin was used instead of the same amount of phenolic resin emulsion, and the types, amounts and experimental procedures of the remaining raw materials were the same as in example 1.
The molecular weight of the polyurethane in this comparative example is 1000 to 10000.
Comparative example 2
The photosensitive ink of this example is different from that of example 1 in that: the same amount of polyamide resin was used instead of the same amount of epoxy resin emulsion, and the types, amounts and experimental procedures of the remaining raw materials were the same as in example 1.
The molecular weight of the polyurethane in this comparative example is 1000 to 10000.
Comparative example 3
The photosensitive ink of this example is different from that of example 1 in that: purified water was used instead of the same amount of thickener, and the kinds, amounts and experimental procedures of the remaining raw materials were the same as in example 1.
Comparative example 4
The photosensitive ink of this example is different from that of example 1 in that: the same amount of tackifier was replaced with absolute ethanol, and the types, amounts and experimental procedures of the remaining raw materials were the same as in example 1.
Comparative example 5
The photosensitive ink of this example is different from that of example 1 in that: the same amount of acrylic acid was used instead of the same amount of liquid paraffin, and the kinds, amounts and experimental procedures of the remaining raw materials were the same as in example 1.
Comparative example 6
The difference between this example and example 6 is that: the softener was not added with the diester-based propyl quaternary ammonium salt, and the types, amounts and experimental procedures of the remaining raw materials were the same as those of example 1.
Application example
In the application examples, nylon shoe materials were used, and the photosensitive inks prepared in examples 1 to 7 and comparative examples 1 to 6 were used for printing.
Application example 1
A light-sensitive shoe material is prepared by the following method:
heating nylon shoe material at 50deg.C, and coating acrylic acid on the surface of nylon shoe material with a coating wet weight of 4g/m 2 Cooling to 35 ℃, shaping, and printing the light-sensitive ink on the surface of the shoe material.
The light-sensitive ink prepared in the embodiment 1 is placed in a shoe printer, the printer is purchased in Shenzhen dragon Hua Oubo dream magic mechanical equipment factory, the brand is Sanjie digital, the resolution is 2880dpi x 1440dpi, the printing temperature of the light-sensitive ink is 50 ℃, then printing is carried out, and the printed light-sensitive ink is placed in ultraviolet light for drying, so that the light-sensitive shoe material is obtained.
The application examples 2 to 13 are different from the application example 1 in that: the light sensitive ink was different in source, and the rest of the experimental steps and parameters were the same as those of application example 1. The sources of the photosensitive inks in application examples 1 to 11 are shown in table 3:
TABLE 3 sources of photosensitive inks in application examples 1 to 13
Application example Light sensitive ink source
Application example 1 Example 1
Application example 2 Example 2
Application example 3 Example 3
Application example 4 Example 4
Application example 5 Example 5
Application example 6 Example 6
Application example 7 Example 7
Application example 8 Comparative example 1
Application example 9 Comparative example 2
Application example 10 Comparative example 3
Application example 11 Comparative example 4
Application example 13 Comparative example 5
Application example 13 Comparative example 6
Performance test the photosensitive inks prepared in examples 1 to 7 and comparative examples 1 to 6 were subjected to mechanical stability analysis; application examples 1 to 13 were subjected to yellowing resistance test, aging resistance test and softness test.
Detection method/test method
Yellowing resistance: the yellowing resistance test was carried out using a yellowing resistance tester (brand name: taiwan high iron, model GT-7035-UA), the temperature was set to 50 ℃, and the UV light source was a UV300W bulb, ultraviolet intensity (25.+ -. 0.4) W/M 2 The light-sensitive shoe materials prepared in application examples 1 to 13 were placed in a yellowing resistance tester and left for 24 hours, and the yellowing resistance level of application examples 1 to 13 was determined.
Ageing resistance test: the light-sensitive shoe materials prepared in application examples 1 to 13 are placed in an ultraviolet aging test box (BD/ZN-P) (which is composed of 8 fluorescent ultraviolet lamp tubes, a heating tank, a sample rack, a control system, an irradiation control system and a temperature system, and can perform fluorescent ultraviolet and condensation circulation), the test conditions adopt a UVA-340 light source, the test conditions adopt alternating circulation of 60 ℃ fluorescent ultraviolet irradiation and 50 ℃ condensation exposure for 4 hours, and the test conditions comprise thatThe oil and water were sprayed every 4 hours. Irradiance of 0.89W/m 2 Nm, the test time is 130h, and whether the glossiness of the light-sensitive shoe material changes after the light-sensitive shoe material changes color in sunlight is observed (the light-sensitive shoe material is tested by using a gloss meter, and the model is DK-P60 (gloss meter)). The less the change in gloss, the better the light-sensitive ink's light fatigue.
Softness: the photosensitive shoe materials prepared in application examples 1 to 13 were divided into two groups, and the photosensitive shoe materials were repeatedly folded in half for 500 times to examine whether or not there were cracks.
The photosensitive shoe materials prepared in application examples 1 to 13 were treated in accordance with the above-mentioned aging test, and whether or not the photosensitive shoe materials had cracks was observed in the folding test. The test results of the aging test and the softness test are shown in table 4:
TABLE 4 test results of aging test and softness test
By using examples 1 to 13 in combination with Table 4, it was found that yellowing resistance, weather resistance, light fatigue resistance, water and oil repellency of the photosensitive ink for shoe materials can be improved by using the photosensitive copolymer emulsion, the photosensitive powder, the liquid paraffin, the solid filler, the thickener, the antifoaming agent, the tackifier, the coupling agent, the accelerator and the curing agent in combination in the present application.
Application example 1 shows that the yellowing resistance, weather resistance and light fatigue resistance of the light-sensitive ink after curing are improved by preparing the light-sensitive ink using the formulation of the present application, as compared with application examples 8 and 9.
Application example 1 and application example 2 show that the phenolic resin emulsion prepared by the preparation method of the present application can improve yellowing resistance, weather resistance and light fatigue resistance of the light-sensitive ink.
In comparison with application example 1 and application example 6, the softening agent of the present application can effectively improve the flexibility of the photosensitive ink after curing, and can be used for a long time.
Mechanical stability analysis, the photosensitive inks of examples 1 to 7 and comparative examples 1 to 5 were placed in a centrifuge tube, centrifuged at 8000r/min for 20min with a centrifuge, and left standing for 5h to see whether delamination occurred.
Determination of adhesion: tested according to the method of GB/T9286-1998. The results of the stability test and the measurement of the adhesion are shown in Table 5
TABLE 5 determination of stability test
Examples or application examples Mechanical stability test Determination of adhesion
Example 1 Non-layering 0
Example 2 Non-layering 0
Example 3 Non-layering 0
Example 4 Non-layering 0
Example 5 Non-layering 0
Example 6 Non-layering 0
Example 7 Non-layering 0
Comparative example 1 Non-layering 1
Comparative example 2 Non-layering 1
Comparative example 3 Layering 0
Comparative example 4 Layering 1
Comparative example 5 Non-layering 0
Comparative example 6 Non-layering 1
From examples 1 to 7 and comparative examples 1 to 6, in combination with Table 5, it is understood that the use of the thickener and tackifier according to the present application can increase the mechanical stability and adhesion of the steel photosensitive ink.
Example 1 compares with comparative example 3, and demonstrates that the thickener of the present application can uniformly distribute the photosensitive copolymer emulsion, the photosensitive powder, the liquid paraffin, and the solid filler in the photosensitive ink system, and can maintain uniform distribution of each raw material in the system when standing still.
Example 1 and comparative example 4 illustrate that the adhesion promoter of the present application enhances the adhesion of the photosensitive ink and increases the adhesion stability of the photosensitive ink to the shoe material.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (2)

1. The shoe material light-sensitive ink is characterized by comprising the following raw materials in parts by weight:
30-50 parts of photosensitive copolymer emulsion
10-15 parts of photosensitive powder
15-25 parts of liquid paraffin
10-15 parts of solid filler
20-25 parts of thickening agent
10-15 parts of tackifier
1-2 parts of defoaming agent
0.1-0.5 part of coupling agent
0.1-0.2 part of accelerator
0.1-1.5 parts of curing agent;
each photosensitive copolymer emulsion is obtained by mixing epoxy resin emulsion and phenolic resin emulsion;
the weight ratio of the epoxy resin emulsion to the phenolic resin emulsion is (0.5-0.8) 1;
the phenolic resin emulsion is modified phenolic resin emulsion, and the modified phenolic resin emulsion is prepared by the following method:
mixing 60-70 parts by weight of epoxidized soybean oil, 100-130 parts by weight of formaldehyde solution and 20-30 parts by weight of anhydrous acetic acid solution, heating to 50-60 ℃, dropwise adding 0.1-0.2 part by weight of catalyst, and reacting for 1-2 hours to obtain a mixture;
heating to 70-80 ℃, adding 80-90 parts by weight of diphenyl ether into the mixture, reacting for 30-60 min, heating to 150-170 ℃, then dropwise adding 15-20 parts by weight of 10-15% sodium hydroxide solution, and reacting for 30-60 min to obtain modified phenolic resin emulsion;
the photosensitive powder is at least one of 3-diethylamino-6-methyl-7-phenylamino fluoran, 2'- (dibenzylamino) -6' - (diethylamino) fluoran and benzoic acid-phenanthroline-europium ternary complex;
each part of thickening agent is prepared from sodium alginate, carboxymethyl cellulose and purified water according to the weight ratio of (1-5): 10 is mixed to prepare the composite material;
each part of tackifier is prepared from acrylic acid and absolute ethyl alcohol according to the weight ratio of (5-10): 10, mixing to obtain the product;
the defoaming agent is one of amides, phosphate esters, organic silicon, polyether and fatty acid esters;
the shoe material light-sensitive ink further comprises 2-5 parts by weight of softening agent, wherein each part of softening agent is prepared by the following preparation method:
dissolving 0.1-1 part by weight of diester propyl quaternary ammonium salt in 10-15 parts by weight of purified water to obtain a salt solution, heating to 80-90 ℃, adding 10-20 parts by weight of polyethylene glycol into the salt solution, and stirring until the polyethylene glycol is dissolved to obtain a softener;
uniformly mixing solid filler and photosensitive powder according to parts by weight, adding tackifier, liquid paraffin, thickener, defoamer, coupling agent, accelerator, curing agent and photosensitive copolymer emulsion, stirring at 10-40 ℃, grinding and filtering to obtain shoe material photosensitive ink;
the stirring speed is 200-300 r/min, and the mixture is ground and then sieved by a sieve with 50-100 meshes.
2. An application of shoe material light-sensitive ink is characterized in that: the shoe material light-sensitive ink is applied to shoe material surface printing, and the shoe material light-sensitive ink is the shoe material light-sensitive ink of claim 1.
CN202210741875.1A 2022-06-28 2022-06-28 Shoe material light-sensitive ink, preparation method and application thereof Active CN115160854B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210741875.1A CN115160854B (en) 2022-06-28 2022-06-28 Shoe material light-sensitive ink, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210741875.1A CN115160854B (en) 2022-06-28 2022-06-28 Shoe material light-sensitive ink, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115160854A CN115160854A (en) 2022-10-11
CN115160854B true CN115160854B (en) 2023-09-19

Family

ID=83486519

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210741875.1A Active CN115160854B (en) 2022-06-28 2022-06-28 Shoe material light-sensitive ink, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115160854B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103725090A (en) * 2013-11-29 2014-04-16 景旺电子科技(龙川)有限公司 Scratch-resistant black heat transfer printing ink and preparation method thereof
CN106188448A (en) * 2016-08-04 2016-12-07 中国西电集团公司 Phenolic resin that a kind of epoxy soybean oil is modified and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103725090A (en) * 2013-11-29 2014-04-16 景旺电子科技(龙川)有限公司 Scratch-resistant black heat transfer printing ink and preparation method thereof
CN106188448A (en) * 2016-08-04 2016-12-07 中国西电集团公司 Phenolic resin that a kind of epoxy soybean oil is modified and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《塑料材料与助剂》.天津大学出版社,2007,第188-189页. *
《石棉摩擦材料的结构与性能》.中国建筑工业出版社,1982,第138页. *

Also Published As

Publication number Publication date
CN115160854A (en) 2022-10-11

Similar Documents

Publication Publication Date Title
CN105401460B (en) A kind of uninanned platform leather and its manufacture method
CN107141880B (en) LED (light-emitting diode) curing UV (ultraviolet) offset printing ink as well as preparation method and application thereof
US8492451B2 (en) Ultraviolet ink for surface printing
CN109722160B (en) High-wear-resistance UV (ultraviolet) photocuring release layer applied to gold stamping material and preparation thereof
CN103254405A (en) Rosinyl epoxy acrylate prepolymer and synthetic method as well as use thereof
CN114108335B (en) Water-based dry-adhered two-layer leather transfer film leather and preparation method thereof
CN100467550C (en) Casein type aqueous ink and method for preparing same
CN115160854B (en) Shoe material light-sensitive ink, preparation method and application thereof
CN107629655A (en) A kind of supporting varnish of large arch dam environment-friendly and high-performance and preparation method thereof
CN112501943A (en) Water-based digital paint paper and preparation method and application thereof
CN108517149A (en) A kind of manufacturing method of noctilucence color ink and wood-based plate noctilucence finishing paper
CN108913012A (en) Ultraviolet light solidifies high resistant matt floor paint and preparation method thereof
US20180087218A1 (en) Method for coating paper mill cylinders and cylinders thus obtained
CN107033765B (en) A kind of fire resistant water-based transfer coatings and preparation method thereof
CN110655861B (en) Epoxy tung oil-based waterborne polyurethane modified raw lacquer and preparation method thereof
CN112724803B (en) Plane powder coating composition and coating thereof
CN114213920A (en) Water-based reverse gloss oil and preparation method thereof
CN114645470B (en) Environment-friendly volleyball leather and preparation method thereof
CN113463404B (en) Production method of mildew-proof water-based leather for sports shoes
CN111334172A (en) Environment-friendly quick-drying low-odor UV-LED gloss oil and preparation method thereof
CN113549371A (en) Environment-friendly water-based printing ink and preparation method thereof
CN115651504B (en) Low-VOC primer and preparation method and application thereof
CN107353825B (en) High-gloss friction-resistant glazing oil and preparation method thereof
CN117210061B (en) High-fidelity anti-counterfeiting water-based ink
CN109504161A (en) A kind of UV metal ink of storage endurance and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant