CN115160854A - Shoe material light-sensitive ink, preparation method and application thereof - Google Patents

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

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Publication number
CN115160854A
CN115160854A CN202210741875.1A CN202210741875A CN115160854A CN 115160854 A CN115160854 A CN 115160854A CN 202210741875 A CN202210741875 A CN 202210741875A CN 115160854 A CN115160854 A CN 115160854A
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ink
parts
shoe material
photosensitive
weight
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CN115160854B (en
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黄景柱
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Guangdong Sanqi New Material Technology Co ltd
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Guangdong Sanqi New Material Technology Co ltd
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    • 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

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  • 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 sensation printing ink, a preparation method and application thereof. The shoe material light sensation 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 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 and 0.1-1.5 parts of curing agent, wherein each part of the photosensitive copolymer emulsion is prepared by mixing epoxy resin emulsion and phenolic resin emulsion. The shoe material light sensation 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 sensation printing ink, a preparation method and application thereof.
Background
Along with the gradual change of living conditions, the pursuit of beauty for people is higher and higher, the wearing requirement in daily life is higher, and the requirement for color is higher originally. For example, shoes, which have fixed colors, cannot dynamically change the colors. With the development of science and technology, people find the photosensitive powder, prepare the shoe material light-sensitive ink by using the photosensitive powder, and print the shoe material light-sensitive ink on the surface of the shoe material, so that the surface of the shoe material can be changed into another color in the sun, and the color on the surface of the shoe material is dynamically changed.
However, shoes worn by people are exposed to the air for a long time, so that the light-sensitive ink is also exposed to the environment for a long time, and the structure of the light-sensitive ink is damaged due to the exposure of sunlight, the erosion of external water and the corrosion of some acid and alkali substances, so that the light fatigue property 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 sensation ink, the application provides the shoe material light sensation ink and a preparation method thereof.
In a first aspect, the application provides a shoe material light sensation ink, which adopts the following technical scheme:
the shoe material light sensation ink is prepared from the following raw materials in parts by weight:
30 to 50 portions of photosensitive copolymer emulsion
10 to 15 portions of photosensitive powder
15 to 25 portions of liquid paraffin
10 to 15 portions of solid filler
20 to 25 portions of thickening agent
10 to 15 portions of tackifier
1 to 2 portions of defoaming agent
0.1 to 0.5 portion of coupling agent
0.1 to 0.2 portion of accelerant and 0.1 to 1.5 portions of curing agent
Each part of the 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 sensation ink has good light fatigue resistance, weather resistance, water resistance and oil resistance. The light sensitive powder is uniformly distributed in a system, the light sensitive ink forms a layer of light sensitive ink layer after being cured, and the light sensitive ink layer has good light fatigue resistance, weather resistance and waterproof and oilproof performance.
The epoxy resin emulsion and the phenolic resin emulsion can be crosslinked and interpenetrated to form a three-dimensional network structure under the action of the curing agent, so that the stable structure of the light sensitive ink is enhanced, the light sensitive powder can be attached to the three-dimensional network structure, the contact between the light sensitive powder and the outside is reduced, the service life of the light sensitive 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.
Accelerant and curing agent do not play a role at the in-process of storing in light sense printing ink in this application, can heat when light sense printing ink is printed, and curing agent play a role this moment for epoxy resin emulsion and phenolic resin emulsion solidification form network structure, thereby form light sense printing ink layer.
On one hand, the liquid paraffin is used as a lubricant, so that the flowability of epoxy resin emulsion, phenolic resin emulsion, photosensitive powder, solid filler and a thickening agent is improved, the raw materials can be uniformly distributed in a system for preparing the shoe material photosensitive ink, the shoe material photosensitive ink is more stable in structure, and the light fatigue resistance of the shoe material photosensitive ink is improved; on the other hand, the liquid paraffin can reduce the surface energy of the light-sensitive printing ink surface of the shoe material, and reduce the stains adhered to the light-sensitive printing ink surface of the shoe material, thereby reducing the influence of the external environment on the light-sensitive printing ink of the shoe material.
The tackifier and the thickener increase the adhesion degree of the photosensitive polymer, the photosensitive powder, the liquid paraffin and the solid filler, so that the structure of the shoe material photosensitive ink is more stable.
The defoaming agent can reduce the generation of bubbles in the curing of the epoxy resin emulsion and the phenolic resin emulsion, so that the epoxy resin emulsion and the phenolic resin emulsion form a three-dimensional network structure in the cross-linking and interpenetrating 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 present application is 30 to 50nm.
The curing agent in the present application may be hexamethylenetetramine, divinyltriamine, 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 or a borate coupling agent and the like.
The accelerator is DMP-30, BDMA, N- (4-chloro-2-hydroxybenzene) -N ', N' -dimethyl urea, 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 ℃, dropwise adding 15-20 parts by weight of sodium hydroxide solution with the mass fraction of 10-15%, and reacting for 30-60 min to obtain the phenolic resin emulsion.
The cured phenolic resin emulsion is darker in color, generally between brown and black, which affects the gloss of the light-sensitive ink. By adopting the technical scheme to prepare the modified phenolic resin emulsion, the modified phenolic resin emulsion has lighter color and less influence on the glossiness of the photosensitive ink, and the glossiness retention time of the photosensitive ink can be prolonged.
The epoxidized soybean oil is added in the process of preparing the modified phenolic resin emulsion and participates in the reaction, so that the weather resistance of the modified phenolic resin emulsion is improved, and when the epoxidized soybean oil is used for preparing the photosensitive ink, the light fatigue resistance of the photosensitive ink can be effectively improved, and the influence on the glossiness of the photosensitive ink is small.
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 fluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and benzoic acid-phenanthroline-europium ternary complex.
By adopting the photosensitive powder, the photosensitive ink shows a dynamic reaction, so that the shoe material can show another color on a bright place. And the photosensitive powder, the photosensitive copolymer emulsion, the liquid paraffin, the solid filler, the thickening agent, the defoaming agent, the tackifier and the curing agent are used together, so that the light fatigue resistance of the photosensitive powder can be improved, and the service life of the photosensitive powder can be prolonged.
Preferably, each part of the thickening agent is prepared from sodium alginate, carboxymethyl cellulose and purified water according to the weight ratio of (1-5): (1-5) and (10) mixing.
Light sense printing ink in this application is the solid-liquid mixture body, mixes the phenomenon that solid-liquid separation probably appears in the in-process of stewing, leads to the printing effect poor, adds thickener in this application through this application for photosensitive copolymer emulsion, sensitization powder, liquid paraffin, solid filler, tackifier can evenly distributed in the system in the light sense printing ink system, and can maintain each raw materials evenly distributed in the system when stewing extremely, improves the printing effect.
Preferably, each part of the tackifier is prepared by mixing acrylic acid and absolute ethyl alcohol according to the weight part ratio of (5-10): 10.
Most cloth, genuine leather or synthetic leather of shoes material generally print light sense printing ink to its surface after, drop easily, in order to increase light sense printing ink and shoes material bonding stability, use acrylic acid, methacrylic acid and absolute ethyl alcohol preparation tackifier in this application, the adhesion of this tackifier is strong, is used for preparing shoes material light sense printing ink, can improve the adhesion of shoes material light sense printing ink for shoes material light sense printing ink is difficult for droing.
Most of cloth, genuine leather or synthetic leather on the surface of the shoe material, the surface of the shoe material contains hydroxyl, and carboxyl of acrylic acid and methylacrylic acid can react with the hydroxyl on the surface of the shoe material, so that the light-sensitive ink is stably attached to the surface of the shoe material.
The anhydrous ethanol dissolves the acrylic acid and the methacrylic acid, so that the acrylic acid and the methacrylic acid can be uniformly dispersed in a system, and 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 curing process of the light-sensitive ink 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 sensation ink also comprises 2-5 parts by weight of a softening agent, and each part of the 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 softener.
Because the epoxy resin emulsion is added in the application, the brittleness of the molded light-sensitive ink is increased, and the molded light-sensitive ink is easy to crack if being used for a plurality of times of bending. The softening agent is added in the application, so that the brittleness of the light-sensitive ink is reduced, and the light-sensitive ink is not easy to crack in use.
When the light-sensitive ink is cured, the polyethylene glycol reacts with the epoxy resin emulsion, so that the brittleness of the epoxy resin emulsion is reduced, the flexibility of the molded light-sensitive ink is increased, and the molded light-sensitive ink is not easy to crack in the using 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, the polyethylene glycol can fully react with the epoxy resin emulsion, and the brittleness is reduced.
The molecular weight of the polyethylene glycol is 10000-25000.
In a second aspect, the application provides a preparation method of shoe material light sensation ink, which adopts the following technical scheme:
a method for preparing shoe material light-sensitive ink. The preparation method of the shoe material light sensation ink comprises the following preparation steps:
uniformly mixing the solid filler and the photosensitive powder according to the parts by weight, adding the tackifier, the liquid paraffin, the thickening agent, the defoaming agent, the coupling agent, the accelerator, the curing agent and the photosensitive copolymer emulsion, stirring at the temperature of 10-40 ℃, grinding, and filtering to obtain the shoe material photosensitive ink.
The preparation method is simple in operation and convenient for production. The raw materials are mixed firstly. After being mixed, the mixture is ground and filtered, so that the light sensation printing ink is more exquisite and is convenient to print.
Preferably, the stirring speed is 200-300 r/min, and the mixture is ground and 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, and the shoe material photosensitive ink with better light fatigue resistance, weather resistance and flexibility is obtained.
In a third aspect, the application provides an application of the shoe material light sensation ink, which adopts the following technical scheme:
the shoe material light sensation ink is applied to printing on the surface of a shoe material, is prepared by the preparation method of the shoe material light sensation ink in the first aspect and is prepared by the preparation method of the shoe material light sensation ink in 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 good softness.
Wherein the shoe material is genuine leather shoe material, cloth shoe material, synthetic leather shoe material, etc.
In order to stably print the light-sensitive ink on the surface of the shoe material and print the light-sensitive ink on the surface of the shoe material, the shoe material needs to be pretreated, and the method comprises the following specific steps: firstly, heating the shoe material at 50-60 ℃, then coating acrylic acid on the surface of the shoe material, cooling to 10-35 ℃, shaping, and then printing the light-sensitive ink on the surface of the shoe material.
In order to better cure and form the light-sensitive ink, the printing temperature of the light-sensitive ink is 50-60 ℃, and after printing is finished, the printed shoe material needs to be dried under ultraviolet light at the temperature of 90-120 ℃.
In summary, the present application has the following beneficial effects:
1. the light sensitive ink for the shoe material is obtained by mixing and grinding a photosensitive polymer, photosensitive powder, liquid paraffin, a solid filler, a thickening agent, a defoaming agent, a tackifier, a coupling agent, an accelerant and a curing agent, and has good light fatigue resistance, weather resistance, water resistance and oil resistance. Mix the grinding with above-mentioned raw materials and make shoes material light sense printing ink in this application, the in-process temperature that prints risees, the curing agent takes place the effect for epoxy resin emulsion and phenolic resin emulsion solidification form network structure, and the stable in structure of reinforcing light sense printing ink, and the sensitization powder can depend on in three-dimensional network column structure, reduces the contact of sensitization powder and external world, prolongs the life of sensitization powder, improves light sense printing ink weatherability, waterproof grease proofing and antifatigue.
2. According to the preparation method, the modified phenolic resin emulsion is improved in 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, and can be used for preparing the photosensitive ink, so that the light fatigue resistance of the photosensitive ink can be effectively improved, and the influence on the glossiness of the photosensitive ink is small.
3. According to the method, the softener is prepared from the diester propyl quaternary ammonium salt, the purified water and the polyethylene glycol, and the light sensitive ink is prepared from the softener, 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
Phenol resin emulsion preparation examples 1 to 3
Preparation example 1
A phenolic resin emulsion is prepared by the following method:
mixing 0.6Kg of epoxidized soybean oil, 1Kg of formaldehyde solution with the mass fraction of 8% and 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 dropwise adding 0.15Kg of sodium hydroxide solution with the mass fraction of 10%, reacting for 30min, and filtering to obtain the phenolic resin emulsion.
Preparation examples 2 and 3 differed from preparation example 1 in that: the kinds, amounts and test 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
Figure BDA0003718347910000061
Examples
Example 1
A light-sensitive ink is prepared by the following steps:
0.1Kg of solid filler (titanium dioxide) and 0.1Kg of photosensitive powder (3-diethylamino-6-methyl-7-phenylaminofluorane) are uniformly mixed, then 0.1Kg of tackifier (0.03 Kg of acrylic acid and 0.07Kg of absolute ethyl alcohol), 0.15Kg of liquid paraffin, 0.2Kg of thickener (0.017 Kg of sodium alginate, 0.017 of carboxymethylcellulose and 0.167Kg of water), 0.01Kg of antifoaming agent, 0.001Kg of coupling agent (titanate coupling agent), 0.001Kg of accelerator (BDMA), 0.001Kg of curing agent (hexamethylene tetramine) and 0.3Kg of photosensitive copolymer emulsion (0.1 Kg of epoxy resin emulsion and 0.2Kg of commercially available phenolic resin emulsion) are added, and the mixture is stirred at the temperature of 10 ℃ and the stirring speed of 200r/min, ground and sieved by a 50-mesh sieve to obtain the photosensitive ink for shoes.
The photosensitive copolymer emulsion in the embodiment is epoxy phenolic resin emulsion, and the average molecular weight of the epoxy phenolic resin emulsion is 200-10000.
A commercially available phenolic resin emulsion was purchased from Jining Sanshi Biotechnology Ltd under model number SH.
Examples 2 to 5 differ from example 1 in that: the species, the amounts and the experimental parameters of some raw materials were different, and the experimental procedures were the same as those of example 1. The kinds, amounts and experimental parameters of the respective raw materials in examples 1 to 5 are shown in Table 2:
TABLE 2 kinds and amounts of raw materials and experimental parameters of examples 1 to 5
Figure BDA0003718347910000071
Figure BDA0003718347910000081
Example 6
A photosensitive ink, which is different from example 2 in that: in this example, 0.02Kg of softening agent was added after mixing the solid filler and the photosensitive powder, and the types, amounts and experimental procedures of the other raw materials were the same as those of example 1.
The softening agent 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
A photo-sensitive ink, differing from example 2 in that: in this example, 0.05Kg of softening agent was added after mixing the solid filler and the photosensitive powder, and the types, amounts and experimental procedures of the other raw materials were the same as those of example 1.
The softening agent 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
This example is different from example 1 in that: the same amount of polyamide resin was used instead of the same amount of phenolic resin emulsion and the type, amount and experimental procedure of the remaining raw materials were identical to those of example 1.
The molecular weight of the polyurethane in this comparative example is 1000 to 10000.
Comparative example 2
This example is different from example 1 in that: the same amount of polyamide resin was used instead of the same amount of epoxy resin emulsion, and the kinds, amounts and experimental procedures of the remaining raw materials were the same as those of example 1.
The molecular weight of the polyurethane in this comparative example is 1000 to 10000.
Comparative example 3
This example differs from example 1 in a light-sensitive ink: purified water was used instead of an equal amount of thickener, and the kinds, amounts and experimental procedures of the remaining raw materials were identical to those of example 1.
Comparative example 4
This example is different from example 1 in that: anhydrous ethanol was used instead of an equivalent amount of tackifier, and the type, amount and experimental procedure of the remaining raw materials were identical to those of example 1.
Comparative example 5
This example differs from example 1 in a light-sensitive ink: 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 those of example 1.
Comparative example 6
This example is different from example 6 in that: the softening agent is not added with diester propyl quaternary ammonium salt, and the types, the use amounts and the experimental steps of the other raw materials are all consistent with those of the embodiment 1.
Application example
In the application example, the shoe material was nylon shoe material, and the light-sensitive inks obtained 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 steps:
firstly heating the nylon shoe material at 50 ℃, then coating acrylic acid on the surface of the nylon shoe material, wherein the moisture content of the coating is 4g/m 2 Cooling to 35 deg.C, shaping, and printing the photosensitive ink on the surface of shoe material.
The light-sensitive ink prepared in the embodiment 1 is placed in a shoe printing machine, the printing machine is purchased from a Boplo dream mechanical equipment factory in the Longhua region of Shenzhen, the brand is Sanjie digital, the resolution is 2880dpi 1440dpi, the printing temperature of the light-sensitive ink is 50 ℃, then printing is carried out, and after printing, the light-sensitive ink is placed in an ultraviolet lamp for drying, so that the light-sensitive shoe material is obtained.
Application examples 2 to 13 are different from application example 1 in that: the photosensitive inks were derived from different sources, and the rest of the experimental steps and parameters were the same as those in 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 1-13
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 obtained in examples 1 to 7 and comparative examples 1 to 6 were subjected to mechanical stability analysis; the yellowing resistance, aging resistance and flexibility tests were carried out in application examples 1 to 13.
Detection method/test method
Yellowing resistance: performing anti-yellowing test by using anti-yellowing tester (model GT-7035-UA of Taiwan high-speed railway in China), setting temperature at 50 deg.C, UV light source UV300W bulb, and ultraviolet intensity (25 + -0.4) W/M 2 Placing the light-sensitive shoe materials prepared in the application examples 1-13 in a yellowing resistance tester, placing for 24h, and judging the yellowing resistance grade of the application examples 1-13.
Aging resistance test: the light-sensitive shoe materials prepared in application examples 1-13 are placed in an ultraviolet light aging test box (BD/ZN-P) (consisting of 8 fluorescent ultraviolet lamp tubes, a heating tank, a sample frame, a control system, an irradiation control system and a temperature system, and can perform fluorescent ultraviolet and condensation cycles, wherein the light adopts a UVA-340 light source, the test conditions adopt that 60 ℃, 8h of fluorescent ultraviolet irradiation and 50 ℃, 4h of condensation exposure are alternately circulated, and oil water is sprayed every 4 hours. Irradiance is 0.89W/m 2 Nm, test time 130h, and observing the change of glossiness of the light-sensitive shoe material after the color change in the sun (measured by using a glossiness meter, model DK-P60 (glossiness meter)). The less change in gloss indicates the better light-fatigue property of the light-sensitive ink.
Flexibility: the light-sensitive shoe materials prepared in application examples 1 to 13 were divided into two groups, and one group was folded in half and repeatedly folded in half 500 times to observe whether the light-sensitive shoe materials had cracks.
The light-sensitive shoe materials prepared in examples 1 to 13 were treated according to the aging test, and then a folding test was performed to see whether or not the light-sensitive shoe material had cracks. The test results of the aging test and the flexibility test are shown in table 4:
TABLE 4 test results of aging test and flexibility test
Figure BDA0003718347910000111
By applying examples 1 to 13 in combination with table 4, it is understood that the yellowing resistance, weather resistance, photo-fatigue resistance, and 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 defoamer, the tackifier, the coupling agent, the accelerator, and the curing agent in combination.
Application example 1 in comparison with application examples 8 and 9, it is shown that by preparing a photosensitive ink using the formulation of the present application, the photosensitive ink has improved resistance to yellowing, weather resistance and photo-fatigue after curing.
Application example 1 and application example 2 show that the phenolic resin emulsion prepared by the preparation method in the present application can improve the yellowing resistance, weather resistance and light fatigue resistance of the photosensitive ink.
Compared with application examples 1 and 6, the softening agent in the application can be added to effectively improve the flexibility of the cured photosensitive ink, so that the cured photosensitive ink can be used for a long time.
And (3) analyzing mechanical stability, namely placing the photosensitive printing ink of the examples 1-7 and the photosensitive printing ink of the comparative examples 1-5 into a centrifugal tube respectively, centrifuging the printing ink for 20min at 8000r/min by using a centrifuge, standing the printing ink for 5h, and observing whether layering occurs or not.
And (3) measuring the adhesive force: the test was carried out according to the method of GB/T9286-1998. The results of the stability test and the adhesion measurement are shown in Table 5
TABLE 5 measurement results of stability test
Examples of the embodiment or application Mechanical stability test Adhesion measurement
Example 1 Not layering 0
Example 2 Not layering 0
Example 3 Without delamination 0
Example 4 Without delamination 0
Example 5 Without delamination 0
Example 6 Without delamination 0
Example 7 Not layering 0
Comparative example 1 Not layering 1
Comparative example 2 Without delamination 1
Comparative example 3 Layering 0
Comparative example 4 Layering 1
Comparative example 5 Not layering 0
Comparative example 6 Not layering 1
From examples 1 to 7 and comparative examples 1 to 6 in combination with table 5, it is understood that the mechanical stability and adhesion of the steel photo-sensitive ink can be increased by using the thickener and tackifier in the present application.
Example 1 compares with comparative example 3, and illustrates that the thickener in the present application can make the photosensitive copolymer emulsion, photosensitive powder, liquid paraffin, and solid filler uniformly distributed in the photosensitive ink system, and can maintain the uniform distribution of each raw material in the system when standing still.
Example 1 and comparative example 4 show that the tackifier can enhance the adhesion of the photosensitive ink and increase the bonding stability of the photosensitive ink and the shoe material.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The shoe material light sensation ink is characterized by being prepared from the following raw materials in parts by weight:
30 to 50 parts of photosensitive copolymer emulsion
10 to 15 parts of photosensitive powder
15 to 25 parts of liquid paraffin
10 to 15 parts of solid filler
20 to 25 parts of thickening agent
10 to 15 parts of tackifier
1 to 2 portions of defoaming agent
0.1 to 0.5 portion of coupling agent
0.1 to 0.2 portion of accelerator
0.1 to 1.5 parts of curing agent, wherein each part of the photosensitive copolymer emulsion is obtained by mixing epoxy resin emulsion and phenolic resin emulsion.
2. The shoe material photosensitive ink as claimed in claim 1, wherein the phenolic resin emulsion is a modified phenolic resin emulsion, and the modified phenolic resin emulsion is prepared by the following method:
dissolving 60 to 70 parts by weight of epoxidized soybean oil and 100 to 130 parts by weight of formaldehyde into 20 to 30 parts by weight of acetic acid solution, heating to 50 to 60 ℃, dropwise adding 1 to 2 parts by weight of catalyst, and reacting for 1 to 2h to obtain a mixture;
heating to 70-80 ℃, adding 80-90 parts by weight of diphenyl ether into the mixture, reacting for 30-60min, cooling to 40-50 ℃, dropwise adding 15-20 parts by weight of sodium bicarbonate solution with the mass fraction of 10-15%, reacting for 30-60min, and filtering to obtain the modified phenolic resin emulsion.
3. The shoe material light sensation ink as claimed in claim 2, wherein: the photosensitive powder is at least one of 3-diethylamino-6-methyl-7-phenylamino fluorane, 2'- (dibenzylamino) -6' - (diethylamino) fluorane and benzoic acid-o-phenanthroline-europium ternary complex.
4. The shoe material photosensitive ink as claimed in claim 3, wherein each part of the thickener is prepared from sodium alginate, carboxymethyl cellulose and purified water according to a weight ratio of (1 to 5): (1 to 5) and (10) mixing.
5. The shoe material photosensitive ink as claimed in claim 4, wherein each part of the tackifier is prepared from acrylic acid and absolute ethyl alcohol according to a weight part ratio of (5-10): 10 are mixed to obtain the product.
6. The shoe material light sensation ink as claimed in claim 5, wherein: the defoaming agent is one of amides, phosphates, organic silicon, polyethers and fatty acid esters.
7. The shoe material light sensation ink as claimed in claim 1, wherein: the shoe material light sensation ink also comprises 2-5 parts by weight of a softening agent, and each part of the softening agent is prepared by the following preparation method:
dissolving 0.1 to 1 part by weight of diester propyl quaternary ammonium salt in 10 to 15 parts by weight of purified water to obtain a salt solution, heating to 80 to 90 ℃, adding 10 to 20 parts by weight of polyethylene glycol into the salt solution, and stirring until the polyethylene glycol is dissolved to obtain the softener.
8. A method for preparing a shoe material light sensitive ink as claimed in any one of claims 1 to 7, wherein:
uniformly mixing the solid filler and the photosensitive powder in parts by weight, adding the tackifier, the liquid paraffin, the thickener, the defoamer, the coupling agent, the accelerator, the curing agent and the photosensitive copolymer emulsion, stirring at the temperature of 10-40 ℃, grinding and filtering to obtain the shoe material photosensitive ink.
9. The preparation method of the shoe material photosensitive ink according to claim 8, wherein the stirring speed is 200 to 300r/min, and the mixture is ground and sieved by a sieve of 50 to 100 meshes.
10. The application of the shoe material light sensation ink is characterized in that: the shoe material light-sensitive ink is applied to printing on the surface of a shoe material, the shoe material light-sensitive ink is the shoe material light-sensitive ink in any one of claims 1 to 7, and the shoe material light-sensitive ink is prepared by a preparation method of the shoe material light-sensitive ink in any one of claims 8 to 9.
CN202210741875.1A 2022-06-28 2022-06-28 Shoe material light-sensitive ink, preparation method and application thereof Active CN115160854B (en)

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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 (1)

* Cited by examiner, † Cited by third party
Title
"《石棉摩擦材料的结构与性能》", 中国建筑工业出版社, pages: 138 - 189 *

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