TWI777413B - Light-cured anti-slip structure for shoe sole and method of making the same - Google Patents

Abstract

A light-cured anti-slip structure includes an anti-slip layer fixed on the surface of a substrate. The anti-slip layer is composed of a photocurable composition, which includes 50 wt% to 100 wt% of a photocurable material, 0.5 wt% to 20 wt% of a photocurable initiator, and 5 wt% of the photocurable composition. ~50 wt% of the thermal curing material and less than or equal to 5 wt% of the thermal curing initiator are mixed with each other to form a photocurable composition; the photocurable initiator receives light energy, catalyzes the photocurable material to carry out the photocuring reaction, and at the same time The thermal curing initiator is activated by exothermic heat of the photocuring initiator, and the thermal curing initiator catalyzes the curing reaction of the thermal curing material and the photocuring material to form an anti-slip layer. The light-curing anti-slip structure provided by the present invention can be quickly cured on the surface of the substrate, and can greatly reduce material cost and man-hours. A manufacturing method of the light-cured anti-slip structure is also provided herein.

Description

Light-cured anti-slip structure for shoe sole and method of making the same

The invention relates to a light-cured anti-slip structure for shoe soles; in particular, it refers to a light-cured anti-slip structure for shoe soles and a manufacturing method thereof.

With the advancement of science and technology, the use of foam materials to make lightweight products has become more and more widely used; for example, toys, daily necessities and sports goods can be made of foam materials to make lightweight products. Among them, taking sports goods as an example, components such as helmet linings, protective gear, shoe midsole, and components of composite materials can be made of foamed materials.

However, due to the poor anti-slip properties of the existing foamed materials, products with foamed materials and anti-slip properties cannot directly design the foamed materials as contact parts exposed to the outside; in order to solve the above problems For the problem of poor anti-slip properties of foam materials, there are existing products that additionally attach a rubber substrate to the outer surface of the foam materials to meet the needs of products with foam materials and anti-slip properties.

The rubber substrate itself is a thermosetting material, which requires a strict temperature-controlled heating and baking step to complete the thermal curing reaction. Therefore, for anti-slip products, the preparation of the rubber substrate requires a lot of man-hours and materials. On the other hand, in the above-mentioned anti-slip product with a rubber substrate and a foamed material, an additional adhesive is usually required between the rubber substrate and the foamed material, so that the rubber substrate can be adhered to the outer surface of the foamed material. surface; when the adhesive ages and hardens, the rubber substrate will fall off the outer surface of the foamed material. It can be seen from this that the structural reliability and durability of the anti-slip product with the rubber substrate and the foamed material are not good.

In addition, the above-mentioned anti-slip product with rubber substrate and foamed material provides anti-slip effect by adhering the rubber substrate to the outer surface of the foamed material. There is obvious thickness in the product, and the anti-slip product with thin structure cannot be provided.

To sum up, there is an urgent need for a novel light-cured anti-slip structure and a manufacturing method thereof, so as to effectively improve the production efficiency of the light-cured anti-slip structure and to manufacture anti-slip products with relatively thin and light structures, and to improve product reliability and reliability. Durability.

In view of this, the object of the present invention is to provide a light-curing anti-slip structure, which comprises a light-curing composition comprising a light-curing material, a light-curing initiator, a thermal-curing material and a thermal-curing initiator mixed with each other, and utilizes The irradiation step induces an exothermic photocuring reaction and a chain thermal curing reaction. In this way, an anti-slip product with a light and thin anti-slip layer can be made on the surface of the substrate by coating the liquid photocurable composition, so as to greatly shorten the overall manufacturing time of the traditional anti-slip product with a rubber substrate and a foamed material, and thus effectively The production efficiency of the light-cured anti-slip structure is greatly improved and the anti-slip product with a relatively light and thin structure is produced, and the reliability and durability of the product are improved; wherein, the anti-slip layer formed by the light-cured composition is directly fixed on the base. On the surface of the material, and there is no intermediate or adhesive between the anti-slip layer and the surface of the substrate.

In order to achieve the above purpose, a light-curing anti-slip structure provided by the present invention includes an anti-slip layer; the anti-slip layer is fixed on the surface of a substrate, and the anti-slip layer is composed of a light-curing composition, the The photocurable composition includes a photocurable material, a photocurable initiator, a thermal curing material and a thermal curing initiator, wherein the photocurable material accounts for 50 wt% to 100 wt% of the weight of the photocurable composition; The photocuring initiator accounts for 0.5 wt% to 20 wt% of the photocurable composition; the thermal curing material accounts for 5 wt% to 50 wt% of the photocurable composition; the thermal curing initiator accounts for the Less than or equal to 5 wt % by weight of the photocurable composition; wherein, the photocurable material, the photocurable initiator, the thermally curable material and the thermally curable initiator are mixed with each other to form the photocurable composition; the photocurable The initiator receives a light energy, and catalyzes the photocurable material to carry out a photocuring reaction, and at the same time, the photocurable initiator releases heat to activate the thermal curing initiator, and the thermal curing initiator catalyzes the thermal curing material and the light. The cured material undergoes a curing reaction to form the anti-slip layer.

Another object of the present invention is to provide a method for manufacturing a light-curing anti-slip structure, comprising at least the following steps: providing a light-curing composition, wherein the light-curing composition comprises a light-curing material, a light-curing initiator, a light-curing Mixing the heat-curing material and a heat-curing initiator; coating the photo-curing composition on the surface of a substrate; and providing a light energy to irradiate the photo-curing composition, and the photo-curing initiator receiving the light energy , catalyzes the photocuring material to carry out a photocuring reaction, and at the same time, the photocuring initiator exothermic activates the thermal curing initiator, and the thermal curing initiator catalyzes the curing reaction between the thermal curing material and the photocuring material, forming An anti-slip layer is on the surface of the substrate.

Another object of the present invention is to provide a light-cured anti-slip structure manufactured by the above-mentioned manufacturing method of the light-cured anti-slip structure.

The effect of the present invention is that a light-curing anti-slip structure includes a light-curing composition formed by mixing a light-curing material, a light-curing initiator, a thermal-curing material and a thermal-curing initiator, and the photo-curing step is induced to induce the photo-curing Exothermic reaction and chain thermal curing reaction. In this way, an anti-slip product with a light and thin anti-slip layer can be made on the surface of the substrate by coating the liquid photocurable composition, so as to greatly shorten the overall manufacturing time of the traditional anti-slip product with a rubber substrate and a foamed material, and thus effectively The production efficiency of the light-cured anti-slip structure is greatly improved and the anti-slip product with a relatively light and thin structure is produced, and the reliability and durability of the product are improved; wherein, the anti-slip layer formed by the light-cured composition is directly fixed on the base. On the surface of the material, and there is no intermediate or adhesive between the anti-slip layer and the surface of the substrate.

In order to explain the present invention more clearly, a preferred embodiment is given and described in detail as follows in conjunction with the drawings.

Please refer to FIG. 1 , which is a flow chart of a manufacturing method of a light-curing anti-slip structure according to a preferred embodiment of the present invention; please refer to FIG. 2 and FIG. 3 together, and FIG. 2 is a light-curing structure according to a preferred embodiment of the present invention. A schematic diagram of a method of manufacturing the anti-slip structure 1a; FIG. 3 is a schematic diagram of a method of manufacturing a light-cured anti-slip structure 1b according to another preferred embodiment of the present invention.

The manufacturing method of the light-cured anti-slip structures 1a and 1b of FIG. 1 includes at least the following steps: Step S02, providing a photocurable composition 20, wherein the photocurable composition 20 comprises a photocurable material, a photocurable initiator, a thermal curing material and a thermal curing initiator mixed with each other; Step S04, coating the photocurable composition 20 on the surface 12 of a substrate 10; and Step S06, providing a light energy LE to irradiate the light curing composition 20, the light curing initiator 20 receives the light energy LE, LE1, LE2, catalyzes the light curing material to carry out a photocuring reaction, and at the same time the light curing initiator 20 Exothermic heat activates the thermal curing initiator, and the thermal curing initiator catalyzes the curing reaction of the thermal curing material and the light curing material to form an anti-slip layer 20 a on the substrate surface 12 . In the embodiment of the present invention, step S06 is a chain reaction of photocuring and thermal curing without additional heating, that is, the thermal curing reaction is induced by the exothermic effect of the photocuring reaction without additional heating.

In step S02, the weight ratio of the photocurable material to the thermally curable material ranges from 5:5 to 20:1; the weight ratio of the photocurable material to the photocurable initiator ranges from 5:1 to 20:1 ; The weight ratio of the thermal curing material to the thermal curing initiator ranges from 10:1 to 50:1.

In step S02, the photocurable material is composed of one or more than two acrylate monomers, the acrylate monomers have at least one double bond, and the acrylate monomers have urethane group (urethane), epoxy group (epoxy), amine group (amine), polyester group (polyester) or a combination thereof, but not limited thereto. In the embodiment of the present invention, the photocurable material includes Full Acrylate Resin, 2-Phenoxy Ethyl Acrylate, Polyethylene Glycol (600) 600) Diacrylate), Ditrimethylolpropane Tetraacylate, Aliphatic Urethane Acrylate, Aromatic Urethane Acrylate, Modified Bisphenol A Epoxy Modified Bisphenol A Epoxy Diacrylate, Amine Modified Polyether Acrylate, Polyester Acrylate, or a combination thereof.

The photocuring initiator includes benzophenones, phosphine oxides, quinone compounds, titanocene compounds or combinations thereof. The photo-curing initiator of benzophenone can be, for example, 2-Hydroxy-2-methylpropiophenone (2-Hydroxy-2-methylpropiophenone), Methylbenzoyl formate, 1-hydroxycyclohexyl 1-Hydroxycyclohexyl Phenyl Ketone or a combination thereof, but not limited thereto. The photocuring initiator of phosphine oxide can be, for example, Diphenyl-(2,4,6-Trimethylbenzoyl)-Phosphine Oxide , bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) or a combination thereof, but not limited thereto. The photocuring initiator of the quinone compound can be, for example, DL-Camphorquinone, but not limited thereto. The photocuring initiator of the titanocene compound can be, for example, bis(2,6-difluoro-3-pyrrolephenyl titanocene)-bis(2,6-difluoro-3-[pyrrol- 1-yl]-phenyl)titanium), but not limited thereto.

In the embodiment of the present invention, the absorption wavelength range of the above-mentioned photocuring initiator includes ultraviolet light and visible light wavelength, and each is: The absorption wavelength range of 2-hydroxy-2-methylacetophenone is 246 nm to 333 nm; The absorption wavelength range of benzoate methylformate is 255 nm to 325 nm; The absorption wavelength range of 1-hydroxycyclohexyl phenyl ketone is 245 nm to 331 nm; The absorption wavelength range of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide is 295 nm to 393 nm; The absorption wavelength range of bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide is 295 nm to 370 nm; The absorption wavelength range of DL-camphorquinone is 470nm; The absorption wavelength range of bis-2,6-difluoro-3-pyrrolephenyl titanocene is 398 nm to 470 nm.

In step S06, the wavelength range of the light energy is 100 nm to 600 nm; the irradiation time of the light energy is 1 second to 60 seconds; the power range of the light energy is 0.1 joules/cm2 to 10 joules/cm2. In FIGS. 2 and 3 , the light energies LE, LE1 and LE2 are generated by a light curing device 30 .

The heat-curable material includes, but is not limited to, rubber materials, urethanes, epoxys, or combinations thereof. In the embodiment of the present invention, the rubber material needs to be in a flowable state, so the rubber material can be, for example, liquid rubber, rubber monomer, rubber dissolved in a solvent, or a combination thereof, so that the rubber can be in a liquid state and a liquid state. The light-cured material is uniformly mixed. It is worth mentioning that as long as the rubber material can be made into a liquid state, it is a rubber material suitable for use in the embodiments of the present invention.

Thermal curing initiators include peroxides. Peroxide can be, for example, benzyl peroxide (Benzoyl Peroxide; BPO), dicumyl peroxide (dicumyl peroxide; DCP), di-t-butyl peroxide (Di-t-butyl peroxide; DTBP), 1,1-Bis(tert-butylperoxy)-3,3,5 trimethylcyclohexane peroxide (1,1-Bis(tert-butylperoxy)-3,3,5 trimethylcyclohexane Peroxide; TMCH), Bis (t-butylperoxy Isopropyl) Benzene Peroxide (Bis (t-butylperoxy Isopropyl) Benzene Peroxide; BIPB) or a combination thereof, but not limited thereto.

Step S06 is a chain reaction of photocuring and thermal curing without additional heating, that is, the thermal curing reaction is induced by the exothermic effect of the photocuring reaction without additional heating. In detail, the photoinitiator receives the light energy LE, LE1, LE2 and then releases heat, so that the photocurable composition rises to an exothermic temperature, and the thermal initiator is activated at a thermal initiation temperature, when When the exothermic temperature is greater than or equal to the thermal initiation temperature, the thermal initiator is activated and catalyzes the curing reaction of the thermally curable material and the photocurable material. In the embodiment of the present invention, the exothermic temperature of the photocuring initiator in the photocuring reaction is greater than or equal to 60°C; the thermal initiation temperature of the above-mentioned thermal curing initiator is all greater than or equal to 60°C.

In FIG. 2, the anti-slip layer 20a has a maximum thickness T1 of less than or equal to 3 mm, preferably less than or equal to 0.1 mm. It can be seen that, in the embodiment of the present invention, the anti-slip layer 20a may have a maximum thickness of less than or equal to 0.1 mm, which is a thickness of the anti-slip layer that is technically unattainable for traditional anti-slip products attached to a rubber substrate.

In FIG. 3, the anti-slip layer 20b has a maximum thickness T2 that is less than or equal to 3 mm and greater than or equal to 0.3 mm; in the embodiment of the present invention, since the maximum thickness of the anti-slip layer 20b is greater than or equal to 0.3 mm Therefore, it is difficult to completely cure the anti-slip layer 20b with light energy in a single wavelength range. For example, the anti-slip layer 20b is defined to have an inner layer 201 and a surface layer 202 disposed on the inner layer 201 . Then the surface layer 202 has been cured due to the weak penetrating power of the light energy LE1, but the inner layer 201 is not completely cured; on the contrary, if the light energy LE2 with a longer wavelength range (280 nm-400 nm) is used for light curing After the reaction, the inner layer 201 has been cured due to the strong penetrating power of the light energy LE2, but the surface layer 202 is not completely cured.

Therefore, in the embodiment of the present invention, as shown in FIG. 3 , the light energy LE1 and LE2 include a first wavelength range corresponding to the light energy LE1 and a second wavelength range corresponding to the light energy LE2. The first wavelength range is 280 nm to 600 nm, and the second wavelength range is 100 nm to 400 nm; wherein, the light energy LE1 in the first wavelength range is used to cure the photocurable material of the inner layer 201, and the second wavelength range is The light energy LE2 in the wavelength range is used to cure the photocurable material of the surface layer 202 .

Next, please refer to FIG. 4A and FIG. 4B together, in step S04: before coating the photocurable composition on the surface of the substrate, a hollow mold 40 is detachably disposed on the surface of the substrate 12 Then, the photocurable composition 20 is filled in the plurality of holes 41 of the hollow mold 40 which are connected to each other, as shown in FIG. 4A .

Then, the hollow mold 40 is detached to expose the photocurable composition 20 to the outside, and the photocurable composition 20 is irradiated with the light energy LE1 and LE2 for curing reaction to form the anti-slip layer 20c on the substrate surface 12 . In the embodiment of the present invention, according to the distribution of the holes 41 communicating with each other in the hollow mold 40, the anti-slip layer 20c is formed with a connecting layer 203 and a plurality of bumps 204, and the bumps 204 are disposed on the connecting layer 203 , and the bumps 204 can present a pattern of the hollow mold 40 on the connection layer 203 (not shown). It is worth mentioning that if the maximum thickness T3 of the anti-slip layer 20c is less than 0.3 mm, the photocurable composition 20 can be irradiated with light energy LE in a single wavelength range as shown in FIG. Two groups of light energies LE1 and LE2 in different wavelength ranges.

In step S04, the photocurable composition 20 is directly coated on the surface 12 of the substrate 10, so there is no other intermediate between the cured anti-slip layers 20a, 20b, 20c and the surface 12 of the substrate. In the embodiment of the present invention, the anti-slip layers 20a, 20b, 20c and the substrate surface 12 do not need to be additionally bonded with an adhesive, so the material cost can be saved, and the formed light-cured anti-slip structure can be more for a thin thickness.

In the embodiment of the present invention, the light-cured anti-slip structures 1a, 1b, and 1c can all provide a better anti-slip effect. As shown in Table 1 below, the higher the wet grip value, the better the anti-slip ability.

Table 1. The relationship between sole type and wet grip Sole type wet grip General foam sole 0.41 Foam sole with anti-slip layer 0.5 Rubber outsole 0.55 Rubber outsole for wet grip 0.7

Next, the present invention provides several examples and comparative examples to prove that the light-cured anti-slip structures provided by the examples of the present invention have better wet grip values and effects.

Comparative Example 1: 10 parts by weight of all-acrylic resin, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of 2-hydroxy-2-methylstyrene The ketone and 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide are uniformly mixed, and then subjected to a photocuring reaction to form the anti-slip structure of Comparative Example 1, which has a wet grip. The ground force value is 0.22.

Comparative Example 2: 10 parts by weight of polyether acrylate modified with amine group, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of 2-hydroxyl -2-Methylacetophenone and 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide were uniformly mixed, followed by photocuring reaction to form Comparative Example 2 Anti-slip structure with a wet grip value of 0.25.

Comparative Example 3: 10 parts by weight of modified bisphenol A epoxy diacrylate, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of 2-hydroxyl -2-Methylacetophenone and 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide were uniformly mixed, and then subjected to photocuring reaction to form Comparative Example 3 Anti-slip structure with a wet grip value of 0.23.

Comparative Example 4: 10 parts by weight of aliphatic urethane diacrylate and 0.5 parts by weight of 2-hydroxy-2-methylacetophenone are uniformly mixed, and then subjected to a photocuring reaction to form the anti-slip structure of Comparative Example 4, which is wet The grip value is 0.38.

Comparative Example 5: 10 parts by weight of aliphatic urethane diacrylate, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of ditrimethylol Propane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, and 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide were uniformly mixed , and then carry out a photocuring reaction to form the anti-slip structure of Comparative Example 5, whose wet grip value is 0.36.

Example 1: 10 parts by weight of aliphatic urethane diacrylate, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of ditrimethylol propane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide, 2 Uniform mixing of liquid rubber (Isoprene) in parts by weight and 0.5 parts by weight of benzyl peroxide, followed by photo-curing and thermal-curing chain reactions without additional heating, to form the anti-slip structure of Example 1, which has a wet grip. The value is 0.52.

Example 2: 10 parts by weight of aliphatic urethane diacrylate, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of ditrimethylol propane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide, 4 Uniform mixing of liquid rubber (Isoprene) in parts by weight and 0.5 parts by weight of benzyl peroxide, followed by photo-curing and thermal-curing chain reactions without additional heating, to form the anti-slip structure of Example 2, which has a wet grip. The value is 0.67.

Experimental example 3: 10 parts by weight of aliphatic urethane diacrylate, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of ditrimethylol propane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide, 3 Uniform mixing of liquid rubber (Isoprene) in parts by weight and 0.5 parts by weight of benzyl peroxide, followed by photo-curing and thermal-curing chain reactions without additional heating, to form the anti-slip structure of Example 3, which has a wet grip. The value is 0.65.

Experimental example 4: 10 parts by weight of UV-curable urethane, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol (600) diacrylate, 0.5 part by weight of ditrimethylol propane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, 0.2 parts by weight of diphenyl-(2,4,6-trimethylbenzyl)-phosphine oxide, 3 Uniform mixing of liquid rubber (Isoprene) in parts by weight and 0.5 parts by weight of benzyl peroxide, followed by photo-curing and thermal-curing chain reactions without additional heating, to form the anti-slip structure of Example 4, which has a wet grip. The value is 0.62.

Experimental example 5: 3 parts by weight of aliphatic urethane diacrylate, 7 parts by weight of UV-curable urethane, 1 part by weight of ethyl 2-phenoxyacrylate, 1 part by weight of polyethylene glycol ( 600) Diacrylate, 0.5 parts by weight of ditrimethylolpropane tetrahydride, 0.5 parts by weight of 2-hydroxy-2-methylacetophenone, 0.2 parts by weight of diphenyl-(2,4,6 - trimethylbenzyl)-phosphine oxide, 3 parts by weight of liquid rubber (Isoprene) and 0.5 parts by weight of benzyl peroxide are uniformly mixed, followed by a chain reaction of photocuring and thermal curing without additional heating, To form the anti-slip structure of Example 5, the wet grip value is 0.63.

As shown in Table 2 below, compared with Comparative Examples 1 to 5, Examples 1 to 5 provided by the present invention have better anti-slip ability.

Table 2. Wet grip of Comparative Examples 1-5 and Examples 1-5 Comparative example Example 1 2 3 4 5 1 2 3 4 5 wet grip 0.22 0.25 0.23 0.38 0.36 0.52 0.67 0.65 0.62 0.63

It can be seen from Comparative Examples 1 to 5 that the anti-slip effect of the anti-slip structure that only undergoes the photocuring reaction is not good, and its wet grip range is between 0.22 and 0.38; however, in Examples 1 to 5 of the present invention, adding liquid Rubber and thermal curing initiators undergo a chain reaction of photocuring and thermal curing without additional heating by light, and the anti-slip ability of the anti-slip structure formed by them is significantly improved, and the wet grip range is 0.52~0.67. In Table 2, Example 2 of the present invention has the best anti-slip ability, its wet grip is 0.67, and the content of the liquid rubber of the light-cured composition in Example 2 of the present invention is the highest, so it can be seen that when the light-cured composition The higher the liquid rubber content of the material, the better the anti-slip ability of the anti-slip structure formed.

Through the design of the present invention, a light-curing anti-slip structure includes a light-curing composition composed of a light-curing material, a light-curing initiator, a thermal-curing material and a thermal-curing initiator mixed with each other, and an irradiation step is used to induce the light-curing Exothermic reaction and chain thermal curing reaction. In this way, an anti-slip product with a light and thin anti-slip layer can be made on the surface of the substrate by coating the liquid photocurable composition, so as to greatly shorten the overall manufacturing time of the traditional anti-slip product with a rubber substrate and a foamed material, and thus effectively The production efficiency of the light-cured anti-slip structure is greatly improved and the anti-slip product with a relatively light and thin structure is produced, and the reliability and durability of the product are improved; wherein, the anti-slip layer formed by the light-cured composition is directly fixed on the base. On the surface of the material, and there is no intermediate or adhesive between the anti-slip layer and the surface of the substrate. In addition, in the present invention, the photocurable composition is subjected to photocuring and thermal curing chain reactions without additional heating, and no additional heating step is required. Different from the traditional thermosetting rubber substrate that needs to be heated and cured, the light-cured anti-slip structure for the sole and the manufacturing method thereof provided by the embodiment of the present invention can quickly complete the curing of the anti-slip layer, thereby significantly shortening the working hours, processes and reducing material waste. .

The above descriptions are only preferred feasible embodiments of the present invention, and any equivalent changes made by applying the description of the present invention and the scope of the patent application should be included in the patent scope of the present invention.

[this invention] 1a, 1b, 1c: light-cured anti-slip structure 10: Substrate 12: Surface 20: Light-curing composition 20a, 20b, 20c: Anti-slip layer 201: inner layer 202: Surface 203: Connection layer 204:Bumps 30: Light Curing Equipment 40: Hollow mold 41: Hole S02, S04, S06: Steps T1, T2, T3: Thickness LE, LE1, LE2: light energy

1 is a flow chart of a manufacturing method of a light-cured anti-slip structure according to a preferred embodiment of the present invention; 2 is a schematic diagram of a manufacturing method of a light-cured anti-slip structure according to a preferred embodiment of the present invention; 3 is a schematic diagram of a manufacturing method of a light-cured anti-slip structure according to another preferred embodiment of the present invention; 4A is a schematic diagram of a manufacturing method of a light-cured anti-slip structure according to another preferred embodiment of the present invention; 4B is a schematic diagram of a manufacturing method of a light-cured anti-slip structure according to another preferred embodiment of the present invention.

S02, S04, S06: Steps

Claims (35)

A light-cured anti-slip structure, comprising: An anti-slip layer, fixed on the surface of a substrate, the anti-slip layer is composed of a photocurable composition, and the photocurable composition includes: A photocurable material, which accounts for 50 wt% to 100 wt% of the photocurable composition weight; A photocuring initiator, which accounts for 0.5 wt% to 20 wt% of the photocurable composition weight; A thermally curable material, which accounts for 5 wt % to 50 wt % of the photocurable composition; and A thermal curing initiator, which accounts for less than or equal to 5 wt% of the photocurable composition weight; Wherein, the photo-curing material, the photo-curing initiator, the thermal-curing material and the thermal-curing initiator are mixed with each other to form the photo-curing composition; the photo-curing initiator receives a light energy to catalyze the photo-curing material The photo-curing reaction is carried out, while the photo-curing initiator exotherms to activate the thermal-curing initiator, and the thermal-curing initiator catalyzes the curing reaction of the thermal-curing material and the photo-curing material to form the anti-slip layer. The photocurable anti-slip structure according to claim 1, wherein the photocurable material is composed of one or more than two acrylic monomers. The photocurable anti-slip structure according to claim 1, wherein the photocurable initiator comprises benzophenones, phosphine oxides, quinone compounds, titanocene compounds or combinations thereof. The light-curing anti-slip structure according to claim 1, wherein the heat-curing material comprises rubber material, urethane, epoxy or a combination thereof. The light-curing anti-slip structure according to claim 1, wherein the thermal curing initiator comprises peroxide. The photocurable anti-slip structure according to claim 1, wherein the photoinitiator emits heat after receiving the light energy, so that the photocurable composition rises to an exothermic temperature during the photocuring reaction, and the thermal initiator is When activated at a thermal initiation temperature, when the exothermic temperature is greater than or equal to the thermal initiation temperature, the thermal initiator is activated and catalyzes the curing reaction of the thermally curable material and the photocurable material. The light-curing anti-slip structure according to claim 6, wherein the exothermic temperature is greater than or equal to 60°C; the thermal initiation temperature is greater than or equal to 60°C. The light-cured anti-slip structure according to claim 1, wherein the wavelength range of the light energy is 100 nm to 600 nm; and the irradiation time of the light energy is 1 second to 60 seconds. The light-cured anti-slip structure according to claim 1, wherein the power of the light energy ranges from 0.1 joules/cm ² to 10 joules/cm ² . The photocurable anti-slip structure according to claim 1, wherein the weight ratio of the photocurable material to the thermal curable material ranges from 5:5 to 20:1. The photocurable anti-slip structure according to claim 1, wherein the weight ratio of the photocurable material to the photocurable initiator ranges from 5:1 to 20:1. The light-curing anti-slip structure according to claim 1, wherein the weight ratio of the thermal curing material to the thermal curing initiator ranges from 10:1 to 50:1. The light-cured anti-slip structure according to claim 1, wherein the anti-slip layer has a maximum thickness of less than or equal to 3 mm. The light-cured anti-slip structure according to claim 13, wherein the anti-slip layer has the maximum thickness less than or equal to 0.1 mm. The light-cured anti-slip structure according to claim 13, wherein when the maximum thickness of the anti-slip layer is greater than or equal to 0.3 mm, the anti-slip layer defines an inner layer and a surface layer disposed on the inner layer, And the light energy includes a first wavelength range and a second wavelength range, the first wavelength range is 280 nm to 600 nm, and the second wavelength range is 100 nm to 400 nm; the light in the first wavelength range The energy is used to cure the photocurable material of the inner layer, and the light energy of the second wavelength range is used to cure the photocurable material of the surface layer. The light-cured anti-slip structure according to claim 1, wherein the anti-slip layer comprises a connecting layer and at least one bump, and the at least one bump is disposed on the connecting layer. The light-cured anti-slip structure according to claim 1, wherein the anti-slip layer is directly fixed on the surface of the substrate, and there is no intermediate between the anti-slip layer and the surface of the substrate. A method for manufacturing a light-cured anti-slip structure, comprising: A photocurable composition is provided, wherein the photocurable composition comprises a photocurable material, a photocurable initiator, a thermal curing material and a thermal curing initiator mixed with each other; coating the photocurable composition on the surface of a substrate; and Provide a light energy to irradiate the photocurable composition, the photocurable initiator receives the light energy, catalyzes the photocurable material to carry out a photocuring reaction, and at the same time, the photocurable initiator exothermic activates the thermal curing initiator, and The thermal curing initiator catalyzes the curing reaction of the thermal curing material and the light curing material to form an anti-slip layer on the surface of the substrate. The manufacturing method of the photocurable anti-slip structure according to claim 18, wherein the photocurable material is composed of one or more than two acrylate monomers. The method for producing a photocurable anti-slip structure according to claim 18, wherein the photocurable initiator comprises benzophenones, phosphine oxides, quinone compounds, titanocene compounds or combinations thereof. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the thermally curable material comprises rubber material, urethane, epoxy or a combination thereof. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the thermal curing initiator comprises peroxide. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the photo-initiator receives the light energy and releases heat, so that the photo-curable composition rises to an exothermic temperature, and the thermal initiator is heated to a heat The thermal initiator is activated at an initial temperature, and when the exothermic temperature is greater than or equal to the thermal initiation temperature, the thermal initiator is activated and catalyzes the curing reaction of the thermally curable material and the photocurable material. The manufacturing method of the light-cured anti-slip structure according to claim 23, wherein the exothermic temperature is greater than or equal to 60 degrees C; the thermal initiation temperature is greater than or equal to 60 degrees C. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the wavelength range of the light energy is 100 nm to 600 nm; and the irradiation time of the light energy is 1 second to 60 seconds. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the power of the light energy ranges from 0.1 joules/cm ² to 10 joules/cm ² . The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the weight ratio of the light-cured material to the heat-cured material is in the range of 5:5 to 20:1. The method for manufacturing a photocurable anti-slip structure according to claim 18, wherein the weight ratio of the photocurable material to the photocurable initiator ranges from 5:1 to 20:1. The method for manufacturing a light-cured anti-slip structure as claimed in claim 18, wherein the weight ratio of the thermal curing material to the thermal curing initiator ranges from 10:1 to 50:1. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the anti-slip layer has a maximum thickness of less than or equal to 3 mm. The method for manufacturing a light-cured anti-slip structure according to claim 30, wherein the anti-slip layer has a maximum thickness of less than or equal to 0.1 mm. The method for manufacturing a light-cured anti-slip structure according to claim 30, wherein when the maximum thickness of the anti-slip layer is greater than or equal to 0.3 mm, the anti-slip layer is defined to have an inner layer and an inner layer disposed on the inner layer. a surface layer, and the light energy includes a first wavelength range and a second wavelength range, the first wavelength range is 100 nm to 600 nm, and the second wavelength range is 100 nm to 400 nm; the first wavelength range The light energy of the second wavelength range is used to cure the photocurable material of the inner layer, and the light energy of the second wavelength range is used to cure the photocurable material of the surface layer. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein before coating the light-cured composition on the surface of the substrate, a hollow mold is detachably disposed on the surface of the substrate, The photo-curable composition is then filled in a plurality of holes connected to each other in the hollow mold, and the photo-curable composition is irradiated with the light energy to perform a curing reaction, and then the hollow mold is detached to form the anti-slip layer on the base. On the surface of the material; according to the distribution of the holes connected to each other in the hollow mold, the anti-slip layer is formed with a connecting layer and a plurality of bumps, and the bumps are arranged on the connecting layer. The method for manufacturing a light-cured anti-slip structure according to claim 18, wherein the light-cured composition is directly coated on the surface of the substrate, so there is no intermediate between the cured anti-slip layer and the surface of the substrate thing. A light-cured anti-slip structure produced by the method for manufacturing a light-cured anti-slip structure according to any one of claims 18 to 34.

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