1. The formula of the high-hardness hot-melt adhesive sheet is characterized in that:

comprises modified petroleum resin, EVA, plasticizer, SBS elastomer, POE elastomer, isocyanate siloxane, rosin resin, nano composite filler, absorbent fiber, silane coupling agent, PP wax and antioxidant.

2. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the modified petroleum resin comprises, by weight, 50-80 parts of modified petroleum resin, 60-100 parts of EVA (ethylene-vinyl acetate copolymer), 10-20 parts of plasticizer, 20-40 parts of SBS elastomer, 20-40 parts of POE (polyolefin elastomer), 5-8 parts of isocyanate siloxane, 10-20 parts of rosin resin, 20-40 parts of nano composite filler, 1-4 parts of absorbent fiber, 1-3 parts of silane coupling agent, 4-8 parts of PP (polypropylene) wax and 1-3 parts of antioxidant.

3. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the modified petroleum resin is prepared from the following components in a mass ratio of 1: 1-1: 2, the alpha-methyl styrene modified petroleum resin and the styrene modified pentadiene petroleum resin are mixed to obtain the product.

4. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the EVA is prepared from the following components in percentage by mass of 1: 3-1: 5 two EVA with different fluidity indexes are mixed.

5. The formulation of a high hardness hot melt adhesive sheet according to claim 4, wherein: the EVA is prepared from the following components in percentage by mass of 1: 3-1: 5 two kinds of EVA with the melting index of about 400 and 60.

6. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the rosin resin is pentaerythritol stearate abietate in specific implementation.

7. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the nano composite filler is prepared from the following raw materials in a mass ratio of 2: 1:1 alpha-Al₂O₃And the hexacyclic ring stone and the attapulgite are obtained by mixing the nanometer powder.

8. The formulation of a high hardness hot melt adhesive sheet according to claim 1, wherein: the absorbent fibers in particular practice employ regenerated cellulose fibers.

9. The method for preparing a high-hardness hot-melt adhesive sheet according to claim 1, comprising the steps of:

(a) uniformly mixing modified petroleum resin, EVA, a plasticizer, an SBS elastomer, a POE elastomer, isocyanate siloxane, rosin resin, a silane coupling agent, PP wax and an antioxidant in proportion, and mixing for 15min at 120 ℃ in an internal mixer;

(b) adding the nano composite filler and the absorbent fiber into an internal mixer, and stirring for 15min at 120 ℃;

(c) extruding and granulating the material obtained in the step (b) in a double-screw extruder at 180 ℃;

(d) and (c) adding the colloidal particles obtained in the step (c) into a hot melt adhesive coating machine, coating the colloidal particles on the surface of cloth, and pressing the cloth into different thicknesses through a cooling pressing wheel.

10. The method for preparing a high-hardness hot-melt adhesive sheet according to claim 9, wherein: the cloth can be fine cloth, cotton cloth or spunlace cloth.

Background

The Hot melt adhesive (English name: Hot Glue) is a plastic adhesive, the physical state of which changes with the temperature within a certain temperature range, but the chemical property is not changed, and the Hot melt adhesive is nontoxic and tasteless, and belongs to an environment-friendly chemical product. The product is solid, so the product is convenient to package, transport and store, and has no solvent, pollution and toxicity; and the production process is simple, the added value is high, the bonding strength is high, the speed is high, and the like.

The hot melt adhesive is usually required to be used in vamp processing, for example, a port and toe cap shaping sheet which take the hot melt adhesive as a main material, the types of shoes are divided into various types according to the application, so that the hot melt adhesive for vamp processing puts forward further performance requirements, for example, the toe cap shaping sheet of a mountaineering shoe has higher requirement on the hardness of the hot melt adhesive, the traditional hot melt adhesive has the hardness which is generally easy to distort and deform, and therefore, the applicant develops the hot melt adhesive with high hardness.

Disclosure of Invention

The invention aims to provide a formula of a high-hardness hot-melt film to solve the problems in the background art.

In order to achieve the purpose, the invention provides a formula of a high-hardness hot-melt film, which comprises modified petroleum resin, EVA, a plasticizer, an SBS elastomer, a POE elastomer, isocyanate siloxane, rosin resin, a nano composite filler, an absorbent fiber, a silane coupling agent, PP wax and an antioxidant.

Preferably, the modified petroleum resin comprises, by weight, 50-80 parts of modified petroleum resin, 60-100 parts of EVA, 10-20 parts of plasticizer, 20-40 parts of SBS elastomer, 20-40 parts of POE elastomer, 5-8 parts of isocyanate siloxane, 10-20 parts of rosin resin, 20-40 parts of nano composite filler, 1-4 parts of absorbent fiber, 1-3 parts of silane coupling agent, 4-8 parts of PP wax and 1-3 parts of antioxidant.

Preferably, the modified petroleum resin is prepared from the following components in a mass ratio of 1: 1-1: 2, the alpha-methyl styrene modified petroleum resin and the styrene modified pentadiene petroleum resin are mixed to obtain the product.

Preferably, the mass ratio of the EVA to the base material is 1: 3-1: 5 two EVA with different fluidity indexes are mixed.

Preferably, the mass ratio of the EVA to the base material is 1: 3-1: 5 two kinds of EVA with the melting index of about 400 and 60.

Preferably, the rosin resin is pentaerythritol stearate abietate in specific implementation.

Preferably, the mass ratio of the nano composite filler is 2: 1:1 alpha-Al₂O₃And the hexacyclic ring stone and the attapulgite are obtained by mixing the nanometer powder.

Preferably, the absorbent fibers employ regenerated cellulose fibers in particular implementations.

In addition, the invention also provides a preparation method of the high-hardness hot melt adhesive sheet, which comprises the following steps:

(a) uniformly mixing modified petroleum resin, EVA, a plasticizer, an SBS elastomer, a POE elastomer, isocyanate siloxane, rosin resin, a silane coupling agent, PP wax and an antioxidant in proportion, and mixing for 15min at 120 ℃ in an internal mixer;

(b) adding the nano composite filler and the absorbent fiber into an internal mixer, and stirring for 15min at 120 ℃;

(c) extruding and granulating the material obtained in the step (b) in a double-screw extruder at 180 ℃;

(d) and (c) adding the colloidal particles obtained in the step (c) into a hot melt adhesive coating machine, coating the colloidal particles on the surface of cloth, and pressing the cloth into different thicknesses through a cooling pressing wheel.

Further, the cloth may be fine cloth, cotton cloth or spunlace cloth.

According to the formula and the preparation method of the high-hardness hot-melt adhesive sheet provided by the invention, the performances such as hardness, tensile strength and the like of the hot-melt adhesive sheet for shoes can be improved, the problems that the hot-melt adhesive sheet for shoes in the prior art is low in hardness and easy to distort and deform are effectively solved, the shaping and protecting capacity of the hot-melt adhesive to vamps can be improved, the formula and the preparation method have practical significance and popularization value, and good economic benefits can be expected to be generated.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 60 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 30 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

Example 2

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 50 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 30 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

Example 3

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 70 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 30 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

Example 4

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 80 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 30 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

Example 5

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 60 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 20 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

Example 6

The formula of the high-hardness hot-melt adhesive sheet comprises, by weight, 60 parts of modified petroleum resin, 80 parts of EVA (ethylene-vinyl acetate copolymer), 15 parts of plasticizer, 30 parts of SBS elastomer, 30 parts of POE (polyolefin elastomer), 6 parts of isocyanate siloxane, 15 parts of rosin resin, 40 parts of nano composite filler, 3 parts of absorbent fiber, 3 parts of silane coupling agent, 6 parts of PP (polypropylene) wax and 3 parts of antioxidant.

The modified petroleum resin is prepared from the following components in a mass ratio of 1: 1-1: 2, the alpha-methyl styrene modified petroleum resin and the styrene modified pentadiene petroleum resin are mixed to obtain the product.

The plasticizer adopts butyl phthalate.

The silica coupling agent adopts a silica coupling agent with the trade name of KH 5301-2.

The EVA is prepared from the following components in percentage by mass of 1: 3-1: 5 two kinds of EVA with the melting index of about 400 and 60.

The rosin resin is abietic acid pentaerythritol stearate.

The nano composite filler is prepared from the following raw materials in a mass ratio of 2: 1:1 alpha-Al₂O₃And the hexacyclic ring stone and the attapulgite are obtained by mixing the nanometer powder.

The antioxidant adopts an antioxidant with the grade of 1010.

The absorbent fiber adopts regenerated cellulose fiber in the specific implementation, the purpose of adding the absorbent fiber is to improve the mechanical property of the hot melt adhesive, and meanwhile, the surface of the absorbent fiber is provided with a plurality of micropores with permeability and mobility, so that the absorbent fiber and the hot melt adhesive have better bonding property.

The specific implementation steps are as follows:

(a) uniformly mixing modified petroleum resin, EVA, a plasticizer, an SBS elastomer, a POE elastomer, isocyanate siloxane, rosin resin, a silane coupling agent, PP wax and an antioxidant in proportion, and mixing for 15min at 120 ℃ in an internal mixer;

(b) adding the nano composite filler and the absorbent fiber into an internal mixer, and stirring for 15min at 120 ℃;

(c) extruding and granulating the material obtained in the step (b) in a double-screw extruder at 180 ℃;

(d) and (c) adding the colloidal particles obtained in the step (c) into a hot melt adhesive coating machine, coating the colloidal particles on the surface of the fine cloth, and pressing the fine cloth into a specified thickness by a cooling pressing wheel.

TABLE 1 physical Properties test of examples

Examples	Tensile strength/MPa	Tensile shear strength/MPa	hardness/HA	Melt index/g.min-1
					1	7.4	7.8	92	38.6
2	7.4	7.9	93	39.5
					3	7.3	7.8	92	43.8
4	7.1	7.3	90	46.3
					5	7.5	8.1	96	19.5
6	7.9	8.4	99	6.2

Note: testing the hot melt adhesive sample according to GB/T528-2009 by adopting a universal tensile testing machine for tensile strength; testing the hot melt adhesive sample according to GB/T7124-2008 by adopting a universal electronic tensile testing machine for tensile shear strength; the hardness is measured by a Shore A hardness meter according to GB/T531-1999; the melt index is measured by a plastic melt index measuring machine according to the method of GB/T3682-2000 melt mass flow rate.

It will be understood by those skilled in the art that the foregoing is merely exemplary of the present invention, and is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.