1. A photo-thermal dual-curing photosensitive emulsion is characterized by comprising an oily component A and a water-based component B, wherein,

the component A comprises the following components in percentage by weight: 65-85 wt% of modified acrylate with hydroxyl and vinyl groups, 10-25 wt% of reactive diluent, 1-10 wt% of photoinitiator and 0.1-2 wt% of additive;

the component B comprises the following components in percentage by weight: 5-15 wt% of polyvinyl alcohol polymer, 5-15 wt% of modified polyvinyl acetate resin containing hydroxyl, 0.1-2 wt% of additive and 70-85 wt% of water;

the mass ratio of the component A to the component B is 1: 1.5-2.5.

2. A photo-thermal dual-curable photoresist according to claim 1, wherein said modified acrylate having hydroxyl and vinyl groups in component a is at least one selected from rosin-based urethane acrylate having hydroxyl and vinyl groups and terpene-based urethane acrylate having hydroxyl and vinyl groups.

3. A photo-thermal dual-curing photosensitive resist according to claim 1, wherein said reactive diluent in component a is at least one selected from the group consisting of diol diacrylate, trimethylolpropane triacrylate, propoxylated glycerol triacrylate, isobornyl acrylate, tripropylene glycol diacrylate and pivalate.

4. A photo-thermal dual-curable photosensitive resist according to claim 1, wherein said photoinitiator in component a is selected from at least one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-methyl phenyl propane-1-one, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2, 4-diethyl thioxanthone, isopropyl thioxanthone, and isooctyl p-dimethylaminobenzoate.

5. A photo-thermal dual-curable photoresist according to claim 1, wherein the polyvinyl alcohol polymer in component B is at least one selected from polyvinyl alcohol, polyvinyl alcohol containing SBQ photosensitive groups, and side chain modified polyvinyl alcohol resins containing at least one isocyanate group and at least one acrylic group.

6. A photo-thermal dual-curing photosensitive resist according to claim 1, wherein said modified hydroxyl-containing polyvinyl acetate resin in component B is selected from at least one isocyanate group and at least one acrylic group side chain modified hydroxyl-containing polyvinyl acetate resin.

7. A method for preparing the photo-thermal dual-curing photosensitive resist of any one of claims 1 to 6, comprising the steps of:

(1) providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

8. The method according to claim 7, wherein the mass ratio of the component A, the component B and the pure water is 1:1.5-2.5: 0.5-1.5.

9. A method for using the photo-thermal dual-curing photosensitive resist of any one of claims 1 to 6 or the photo-thermal dual-curing photosensitive resist prepared according to any one of claims 7 to 8, comprising the steps of:

(a) coating and drying treatment: uniformly coating the prepared novel photosensitive emulsion on a polyester screen or a stainless steel screen or other corresponding screens by adopting a blade coating method, a roller coating method or other suitable methods, and then drying at the temperature of not higher than 40 ℃;

(b) and (3) exposure treatment: selecting a proper film sheet to carry out exposure treatment under ultraviolet light on the dried screen printing plate coated with the novel photosensitive resist;

(c) heating treatment: placing the exposed screen plate coated with the novel photosensitive resist in a heater capable of heating the two sides, controlling the temperature at 60-100 ℃ and heating for 2-10 min;

(d) and (3) developing: and developing the heated screen printing plate coated with the novel photosensitive resist by using water, and drying the screen printing plate at the temperature of not higher than 40 ℃ after the development is finished.

10. The method of claim 9, wherein the thickness of the coating film in the coating process is 1-100 μm.

Background

With the development of novel plate-making materials such as diazo resin photosensitive resist, the screen printing technology has been applied to various industries such as clothing, cloth, integrated circuits, ceramics, solar energy and the like. The plate making is the basic and key process of the silk-screen printing, and the performance of the photosensitive resist which is used as the photosensitive material of the plate making determines the quality of the silk-screen printing product.

Currently, the photoresists used for screen printing products include diazo two-component photoresists and SBQ single-component photoresists. However, diazo double-component photosensitive glue needs to be used in situ, has poor thermal stability, short preservation time of the mixed glue, dark reaction phenomenon and low pattern resolution, and cannot meet the requirements of high precision and fine lines. The SBQ single-component photosensitive adhesive solves the problem of colloid storage to a certain extent, greatly improves the light sensitivity, but has a certain bottleneck on the printing resistance because of the limited grafting quantity of the SBQ, and can not meet the requirements of industries such as ceramic components, solar printing and the like. Therefore, how to provide a photosensitive film with high resolution, strong adhesion, good flexibility, high precision and fine lines and better printing resistance is a problem to be solved urgently.

Disclosure of Invention

The invention aims to provide a photo-thermal dual-curing photosensitive adhesive, a preparation method and a using method thereof, which overcome the defects that high-precision fine lines are not met and the printing resistance is low in the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the photo-thermal dual-curing photosensitive emulsion comprises an oily component A and a water-based component B, wherein,

the component A comprises the following components in percentage by weight: 65-85 wt% of modified acrylate with hydroxyl and vinyl groups, 10-25 wt% of reactive diluent, 1-10 wt% of photoinitiator and 0.1-2 wt% of additive;

the component B comprises the following components in percentage by weight: 5-15 wt% of polyvinyl alcohol polymer, 5-15 wt% of modified polyvinyl acetate resin containing hydroxyl, 0.1-2 wt% of additive and 70-85 wt% of water;

the mass ratio of the component A to the component B is 1: 1.5-2.5.

Alternatively, the lower limit of the mass fraction of the modified acrylate having hydroxyl and vinyl groups in the component A is selected from 65 wt%, 70 wt%, 75 wt%, 80 wt%; the upper limit of the mass fraction of the modified acrylate with hydroxyl and vinyl groups in the component A is selected from 70 wt%, 75 wt%, 80 wt% and 85 wt%.

Optionally, the upper limit of the mass fraction of reactive diluent in the component A is selected from 15 wt%, 20 wt%, 25 wt%; the lower limit of the mass fraction of the reactive diluent in the component A is selected from 10 wt%, 15 wt% and 20 wt%.

Optionally, the upper limit of the mass fraction of the photoinitiator in component A is selected from 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%; the lower limit of the mass fraction of the photoinitiator in the component A is selected from 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%.

Optionally, the upper limit of the mass fraction of the additive in component a is selected from 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%; the lower limit of the mass fraction of the additive in the component A is selected from 0.1 wt%, 0.5 wt%, 1.0 wt% and 1.5 wt%.

Optionally, the additive in component a is selected from at least one of a catalyst and a polymerization inhibitor.

Optionally, the upper limit of the mass fraction of the polyvinyl alcohol polymer in the component B is selected from 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; the lower limit of the mass fraction of the polyvinyl alcohol polymer in the component B is selected from 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt% and 14 wt%.

Optionally, the upper limit of the mass fraction of the modified hydroxyl-containing polyvinyl acetate resin in the component B is selected from 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; the lower limit of the mass fraction of the modified hydroxyl-containing polyvinyl acetate resin in the component B is selected from 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt% and 14 wt%.

Optionally, the upper limit of the mass fraction of the additive in component B is selected from 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%; the lower limit of the mass fraction of the additive in the component B is selected from 0.1 wt%, 0.5 wt%, 1.0 wt% and 1.5 wt%.

Optionally, the additive in the component B is selected from at least one of a defoaming agent, a leveling agent, a color paste, a preservative and a plasticizer.

Optionally, the mass ratio of component a to component B is 1: 1.5.

Optionally, the mass ratio of component a to component B is 1: 2.0.

Optionally, the mass ratio of component a to component B is 1: 2.5.

Optionally, the modified acrylate having hydroxyl and vinyl groups in component a is at least one selected from rosin-based urethane acrylates having hydroxyl and vinyl groups and terpene-based urethane acrylates having hydroxyl and vinyl groups.

Optionally, the reactive diluent in component a is selected from at least one of glycol diacrylate, trimethylolpropane triacrylate, propoxylated glycerol triacrylate butyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, and pivalate.

Optionally, the photoinitiator in component a is selected from at least one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-methylphenyl propane-1-one, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2, 4-diethyl thioxanthone, isopropyl thioxanthone, and isooctyl p-dimethylaminobenzoate.

Optionally, the polyvinyl alcohol polymer in the component B is at least one selected from polyvinyl alcohol, SBQ photosensitive group-containing polyvinyl alcohol, and side chain modified polyvinyl alcohol resin containing at least one isocyanate group and at least one acrylic group.

Optionally, the modified hydroxyl-containing polyvinyl acetate resin in component B is selected from at least one isocyanate group and at least one acrylic group side chain modified hydroxyl-containing polyvinyl acetate resin.

The method for photo-thermal dual-curing photosensitive resist comprises the following steps:

(1) providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5-2.5: 0.5-1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 1.5.

The using method of the photo-thermal dual-curing photosensitive glue comprises the following steps:

(a) coating and drying treatment: uniformly coating the prepared novel photosensitive emulsion on a polyester screen or a stainless steel screen or other corresponding screens by adopting a blade coating method, a roller coating method or other suitable methods, and then drying at the temperature of not higher than 40 ℃;

(b) and (3) exposure treatment: selecting a proper film sheet to carry out exposure treatment under ultraviolet light on the dried screen printing plate coated with the novel photosensitive resist;

(c) heating treatment: placing the exposed screen plate coated with the novel photosensitive resist in a heater capable of heating the two sides, controlling the temperature at 60-100 ℃ and heating for 2-10 min;

(d) and (3) developing: and developing the heated screen printing plate coated with the novel photosensitive resist by using water, and drying the screen printing plate at the temperature of not higher than 40 ℃ after the development is finished.

Optionally, the coating film thickness in the coating treatment is 1 to 100 μm.

Alternatively, the coating film thickness in the coating treatment is 1 μm.

Alternatively, the coating film thickness in the coating treatment is 10 μm.

Alternatively, the coating film thickness in the coating treatment is 20 μm.

Alternatively, the coating film thickness in the coating treatment is 50 μm.

Alternatively, the coating film thickness in the coating treatment is 80 μm.

Alternatively, the coating film thickness in the coating treatment is 100 μm.

Compared with the prior art, the invention has the advantages that: the photo-thermal dual-curing photosensitive adhesive provided by the application adopts photo-curing reaction and thermal cross-linking curing reaction, so that the photosensitive adhesive film is cured more completely, the cross-linking degree of the photo-curing partial adhesive film is increased by controlling the parameters of the thermal curing process, the water solubility of the non-photo-curing partial adhesive film is ensured, and the prepared adhesive film has excellent adhesive force, flexibility and printing resistance. The preparation method of the photo-thermal dual-curing photosensitive emulsion is simple and easy to implement, green, environment-friendly and convenient to use, and can be used for large-scale production.

Detailed Description

In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows. The photo-thermal dual-curing photosensitive emulsion comprises an oily component A and a water-based component B, wherein,

the component A comprises the following components in percentage by weight: 65-85 wt% of modified acrylate with hydroxyl and vinyl groups, 10-25 wt% of reactive diluent, 1-10 wt% of photoinitiator and 0.1-2 wt% of additive;

the component B comprises the following components in percentage by weight: 5-15 wt% of polyvinyl alcohol polymer, 5-15 wt% of modified polyvinyl acetate resin containing hydroxyl, 0.1-2 wt% of additive and 70-85 wt% of water;

the mass ratio of the component A to the component B is 1: 1.5-2.5.

Alternatively, the lower limit of the mass fraction of the modified acrylate having hydroxyl and vinyl groups in the component A is selected from 65 wt%, 70 wt%, 75 wt%, 80 wt%; the upper limit of the mass fraction of the modified acrylate with hydroxyl and vinyl groups in the component A is selected from 70 wt%, 75 wt%, 80 wt% and 85 wt%.

Optionally, the upper limit of the mass fraction of reactive diluent in the component A is selected from 15 wt%, 20 wt%, 25 wt%; the lower limit of the mass fraction of the reactive diluent in the component A is selected from 10 wt%, 15 wt% and 20 wt%.

Optionally, the upper limit of the mass fraction of the photoinitiator in component A is selected from 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%; the lower limit of the mass fraction of the photoinitiator in the component A is selected from 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%.

Optionally, the upper limit of the mass fraction of the additive in component a is selected from 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%; the lower limit of the mass fraction of the additive in the component A is selected from 0.1 wt%, 0.5 wt%, 1.0 wt% and 1.5 wt%.

Optionally, the additive in component a is selected from at least one of a catalyst and a polymerization inhibitor.

Optionally, the upper limit of the mass fraction of the polyvinyl alcohol polymer in the component B is selected from 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; the lower limit of the mass fraction of the polyvinyl alcohol polymer in the component B is selected from 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt% and 14 wt%.

Optionally, the upper limit of the mass fraction of the modified hydroxyl-containing polyvinyl acetate resin in the component B is selected from 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; the lower limit of the mass fraction of the modified hydroxyl-containing polyvinyl acetate resin in the component B is selected from 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt% and 14 wt%.

Optionally, the upper limit of the mass fraction of the additive in component B is selected from 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%; the lower limit of the mass fraction of the additive in the component B is selected from 0.1 wt%, 0.5 wt%, 1.0 wt% and 1.5 wt%.

Optionally, the additive in the component B is selected from at least one of a defoaming agent, a leveling agent, a color paste, a preservative and a plasticizer.

Optionally, the mass ratio of component a to component B is 1: 1.5.

Optionally, the mass ratio of component a to component B is 1: 2.0.

Optionally, the mass ratio of component a to component B is 1: 2.5.

Optionally, the modified acrylate having hydroxyl and vinyl groups in component a is at least one selected from rosin-based urethane acrylates having hydroxyl and vinyl groups and terpene-based urethane acrylates having hydroxyl and vinyl groups.

Optionally, the rosin-based polyurethane acrylate with hydroxyl and vinyl groups is synthesized by reacting an addition product of rosin and acrylic acid, which are renewable resources, with maleic anhydride, neopentyl glycol and pentaerythritol to synthesize a rosin-based unsaturated polyester containing side chain hydroxyl, then carrying out prepolymerization reaction on the rosin-based unsaturated polyester and isophorone diisocyanate, and carrying out end capping by using pentaerythritol triacrylate.

Optionally, the terpene-based polyurethane acrylate with hydroxyl and vinyl groups is synthesized by using cheap forest resources, namely cyclization products of turpentine and maleic anhydride, reacting terpene maleic anhydride, phthalic anhydride, propylene glycol and pentaerythritol to synthesize terpene-based polyester containing side chain hydroxyl, then carrying out prepolymerization reaction on the terpene-based polyester and isophorone diisocyanate, and carrying out end-capping by using pentaerythritol triacrylate.

Optionally, the reactive diluent in component a is selected from at least one of glycol diacrylate, trimethylolpropane triacrylate, propoxylated glycerol triacrylate butyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, and pivalate.

Optionally, the reactive diluent has a small molecular weight and a low viscosity, and not only can provide a concentration of-C ═ C-, but also can effectively reduce the viscosity of the component a, so that the concentration of free radicals and the mobility of double bond groups in a system can be improved, the crosslinking degree can be improved, and the progress of photocuring can be accelerated. The reactive diluent is selected and used in an amount that takes into account the effect on overall film adhesion and flexibility.

Optionally, the photoinitiator in component a is selected from at least one of 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-methylphenyl propane-1-one, 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, 2, 4-diethyl thioxanthone, isopropyl thioxanthone, and isooctyl p-dimethylaminobenzoate.

Optionally, the polyvinyl alcohol polymer in the component B is at least one selected from polyvinyl alcohol, SBQ photosensitive group-containing polyvinyl alcohol, and polyvinyl alcohol resin modified with at least one isocyanate group and at least one group-side acrylic group chain.

Optionally, the modified hydroxyl-containing polyvinyl acetate resin in component B is selected from at least one isocyanate group and at least one acrylic group side chain modified hydroxyl-containing polyvinyl acetate resin.

Alternatively, the side-chain group graft is selected from the group consisting of acrylic acid-2-isocyanate, methacrylic acid-2-isocyanate, diacrylic acid isocyanate and dimethacrylic acid isocyanate.

The method for photo-thermal dual-curing photosensitive resist comprises the following steps:

the blending mass ratio is component A: and B component: pure water 1:1.5-2.5:0.5-1.5

(1) Adding the component A into the component B according to the proportion, and dispersing for 5-10min by a high-speed sand grinding dispersion machine at 1000-1500 rpm;

(2) adding half of the pure water in the calculated proportion, and dispersing for 20-100min by a high-speed sanding dispersion machine at 1500-;

(3) adding the rest pure water, and dispersing for 5-10min by a high-speed sand grinding dispersion machine at 1000-1500 rpm;

(4) and (3) filtering the dispersed material by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photosensitive emulsion for coating and plate making. Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5-2.5: 0.5-1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:1.5: 1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.0: 1.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 0.5.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 1.0.

Optionally, the mass ratio of the component A, the component B and the pure water is 1:2.5: 1.5.

The using method of the photo-thermal dual-curing photosensitive glue comprises the following steps:

(a) coating and drying treatment: the prepared novel photosensitive emulsion is uniformly coated on a polyester screen or a stainless steel screen or other corresponding screens by adopting a blade coating method, a roller coating method or other suitable methods, and then drying treatment is carried out at the temperature of not higher than 40 ℃.

(b) And (3) exposure treatment: selecting a proper film sheet to carry out exposure treatment under ultraviolet light on the dried screen printing plate coated with the novel photosensitive resist;

(c) heating treatment: placing the exposed screen plate coated with the novel photosensitive resist in a heater capable of heating the two sides, controlling the temperature at 60-100 ℃ and heating for 2-10 min;

(d) and (3) developing: and developing the heated screen printing plate coated with the novel photosensitive resist by using water, and drying the screen printing plate at the temperature of not higher than 40 ℃ after the development is finished.

Optionally, the coating film thickness in the coating treatment is 1 to 100 μm.

Alternatively, the coating film thickness in the coating treatment is 1 μm.

Alternatively, the coating film thickness in the coating treatment is 10 μm.

Alternatively, the coating film thickness in the coating treatment is 20 μm.

Alternatively, the coating film thickness in the coating treatment is 50 μm.

Alternatively, the coating film thickness in the coating treatment is 80 μm.

Alternatively, the coating film thickness in the coating process is 100 a.

The application provides a novel photo-thermal dual-curing photosensitive resist, wherein a component A is an oily substance, and a component B is a water-based substance. The component B contains polyvinyl alcohol substances which can be used as nonionic active emulsifying agents, and the oily substances of the component A are reduced to be emulsified and dispersed to form uniform colloid on the premise of high-speed dispersion and stirring. When the high-speed dispersion speed is not enough, the water phase and the oil phase can not be well emulsified and dissolved, and the coating film layer has the defects of particles, blooming and the like; the dispersion speed is too high, colloid demulsification is easy to occur, and the emulsion can not be used.

Both the A and B components contain-C ═ C-active groups, and crosslinking and curing are carried out by light irradiation under the action of a photoinitiator. The photo-curing process selects a proper exposure time according to the selected curing light source and the thickness of the film layer. The modified urethane acrylate of the component A contains active hydroxyl, and can perform crosslinking reaction with isocyanate groups in the component B under the action of a proper reaction temperature and a proper catalyst to form a larger crosslinking network. The temperature for heat curing is 60-100 deg.C, and the heating time is controlled for 2-10 min. The temperature is too low, the heat curing can not be carried out, and the curing efficiency is low; the temperature is too high, the coating and the screen cloth are easy to damage, and the energy consumption is increased. The thermosetting heating time is too short, the further gelation of the coating curing of the photocuring part is not obvious, and the excessive curing of the unexposed part of the adhesive film is caused by too long time, which is not beneficial to development.

The technical solution of the present invention is further explained below with reference to several examples.

Example 1

A photo-thermal dual-curing photosensitive colloid is prepared from A, B components,

the component A comprises: 75g of rosin-based polyurethane acrylate with hydroxyl and vinyl groups, 20g of tripropylene glycol diacrylate, 3g of 2-hydroxy-methylphenylpropane-1-one, 2g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 0.1g of organic tin catalyst;

and B component: 8g of polyvinyl alcohol (with the polymerization degree of 1700 and the alcoholysis degree of 87-89 mol%), 3g of acrylic acid-2-isocyanate modified polyvinyl alcohol resin (with the polymerization degree of 1700 and the alcoholysis degree of 87-89 mol%), 5g of acrylic acid-2-isocyanate modified polyvinyl acetate resin (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 0.15g of blue color paste (Shanghai color raw 8301 color paste), and 84g of water

The blending mass ratio is component A: and B component: water 1:2:1, dispersing into emulsion with uniform distribution at high speed according to blending step, and its preparation method is as follows

(1) Providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Then, a 360-16-22 stainless steel wire net is adopted, photosensitive glue is coated for 10 microns, after ultraviolet exposure, the two sides of the screen are heated for 4min at 80 ℃, the screen can be clearly developed, and the printing resistance of the screen is good.

Example 2

A photo-thermal dual-curing photosensitive colloid is prepared from A, B components,

the component A comprises: 75g of terpene-based polyurethane acrylate with hydroxyl and vinyl groups, 5g of isobornyl acrylate, 15g of tripropylene glycol diacrylate, 3g of 1-hydroxy-cyclohexyl-phenyl ketone, 2g of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and 0.1g of organic tin catalyst;

and B component: 9g of polyvinyl alcohol (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 4g of methacrylic acid-2-isocyanate modified polyvinyl alcohol resin (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 6g of methacrylic acid-2-isocyanate modified polyvinyl acetate resin (with the polymerization degree of 1700 and the alcoholysis degree of 87-89 mol%), 0.15g of blue color paste (Shanghai color raw 8301 color paste) and 81g of water;

the blending mass ratio is component A: and B component: water 1:1.8:1.2, dispersing into emulsion with uniform distribution at high speed according to the blending step, and its preparation method is as follows

(1) Providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Then, a 430-13-20 stainless steel wire screen is adopted, photosensitive glue is coated for 10 mu m, after ultraviolet exposure, the two sides of the screen are heated for 6min at 70 ℃, the screen can be clearly developed, and the printing resistance of the screen is good.

Example 3

A photo-thermal dual-curing photosensitive colloid is prepared from A, B components,

the component A comprises: 35g of terpene-based urethane acrylate having hydroxyl groups and vinyl groups, 50g of rosin-based urethane acrylate having hydroxyl groups and vinyl groups, 15g of trimethylolpropane triacrylate, 3g of 2-hydroxy-methylphenylpropane-1-one, 2g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and 0.1g of an organotin catalyst;

and B component: 9g of polyvinyl alcohol (with the polymerization degree of 2400 and the alcoholysis degree of 87-89 mol%), 4g of methacrylic acid-2-isocyanate modified polyvinyl alcohol resin (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 6g of methacrylic acid-2-isocyanate modified polyvinyl acetate resin (with the polymerization degree of 1700 and the alcoholysis degree of 87-89 mol%), 0.15g of blue color paste (Shanghai color raw 8301 color paste) and 81g of water;

the blending mass ratio is component A: and B component: water 1:1.8:1.3, and dispersing into emulsion with uniform distribution at high speed according to blending steps, and its preparation method is as follows

(1) Providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Then, a 430-13-20 stainless steel wire screen is adopted, photosensitive glue is coated for 10 mu m, the two sides of the screen are heated for 5min at 80 ℃ after ultraviolet exposure, the screen can be clearly developed, and the printing resistance of the screen is good.

Example 4

A photo-thermal dual-curing photosensitive colloid is prepared from A, B components,

the component A comprises: 45g of rosin-based urethane acrylate having hydroxyl groups and vinyl groups, 30g of rosin-based urethane acrylate having hydroxyl groups and vinyl groups, 20g of neopentyl glycol diacrylate, 3g of 2-hydroxy-methylphenylpropane-1-one, 2g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and 0.1g of organic tin catalyst;

and B component: 8g of polyvinyl alcohol (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 4g of SBQ modified polyvinyl alcohol resin (with the polymerization degree of 1700 and the alcoholysis degree of 87-89 mol%), 5g of acrylic acid-2-isocyanate modified polyvinyl acetate resin (with the polymerization degree of 2000 and the alcoholysis degree of 87-89 mol%), 0.15g of blue color paste (Shanghai color raw 8301 color paste), and 83g of water

The blending mass ratio is component A: and B component: water 1:2:1, dispersing into emulsion with uniform distribution at high speed according to blending step, and its preparation method is as follows

(1) Providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Then, a 360-16-22 stainless steel wire net is adopted, photosensitive glue is coated for 10 microns, the two sides of the screen are heated for 3min at 60 ℃ after ultraviolet exposure, the screen can be clearly developed, and the printing resistance of the screen is good.

Example 5

A photo-thermal dual-curing photosensitive colloid is prepared from A, B components,

the component A comprises: 75g of rosin-based polyurethane acrylate with hydroxyl and vinyl groups, 10g of tripropylene glycol diacrylate, 10g of propoxylated glycerol triacrylate, 3g of 2-hydroxy-methylphenylpropane-1-one, 2g of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 0.1g of organic tin catalyst;

and B component: 9g of polyvinyl alcohol (polymerization degree 2000, alcoholysis degree 87-89 mol%), 4g of methacrylic acid-2-isocyanate modified polyvinyl alcohol resin (polymerization degree 2000, alcoholysis degree 87-89 mol%), 5g of acrylic acid-2-isocyanate modified polyvinyl acetate resin (polymerization degree 2000, alcoholysis degree 87-89 mol%), 0.15g of blue color paste (Shanghai color raw 8301 color paste), and 82g of water

The blending mass ratio is component A: and B component: water 1:1.8:1, dispersing into emulsion with uniform distribution at high speed according to blending step, and its preparation method is as follows

(1) Providing a component A and a component B according to a proportion;

(2) adding the component A into the component B, and performing dispersion treatment for 5-10min in a dispersion machine with the rotation speed of 1000-1500rpm to prepare a mixture I;

(3) adding pure water into the mixture I, performing dispersion treatment in a dispersion machine with the rotation speed of 1000-5000rpm for 20-100min, continuously adding pure water after the dispersion treatment, and performing dispersion treatment in a dispersion machine with the rotation speed of 1000-1500rpm for 5-10min to obtain a mixture II;

(4) and filtering the mixture II by adopting a polyester silk screen with more than 300 meshes in a double-layer manner to obtain the photo-thermal dual-curing photosensitive emulsion.

Then, a 360-16-22 stainless steel wire net is adopted, photosensitive glue is coated for 10 microns, after ultraviolet exposure, the two sides of the screen are heated for 6min at 75 ℃, the screen can be clearly developed, and the printing resistance of the screen is good.

Comparative example 1

The rhombus diazo series photosensitive resist H-805 adopts a 360-16-22 stainless steel wire mesh, the photosensitive resist is coated by 10 mu m, and the exposure time is selected to carry out plate making.

Comparative example 2

A Mitsubishi SBQ series photosensitive resist SBQ-S300 is prepared by coating photosensitive resist on a stainless steel wire net of 360-16-22 μm and selecting the optimal exposure time for exposure plate making.

The examples 1 to 5 and comparative examples 1 and 2 were subjected to the halftone testing, and the results are shown in table 1.

TABLE 1

As can be seen from Table 1, the minimum resolution of the lines of the photoresists prepared in examples 1-5 is less than 20 μm and much smaller than the minimum resolution of the lines in the comparative example of more than 70 μm, and the number of times of printing resistance of the photoresists prepared in the present application is much larger than that of the comparative example.

Therefore, the novel photo-thermal dual-curing photosensitive resist prepared by the method has good plate making performance and is convenient to coat; the screen printing plate has the advantages of proper spectrum photosensitive range, good developing performance, high resolution, good stability, capability of adapting to the performance requirements of different types of printing ink by a plate film formed by photosensitive materials, quite printing resistance, capability of bearing scraping of a printing scraper for quite times, good binding capacity with a silk screen, no product demoulding and easy stripping during printing, and contribution to recycling of a screen printing plate.

It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.