A hot melt pressure sensitive adhesive suitable for use in heel counter products and a method of making the same

Abstract

The application discloses a hot-melt pressure-sensitive adhesive suitable for a heel anti-abrasion patch product, which comprises the following components in parts by weight: 10-35 parts of a block copolymer, 10-30 parts of a plasticizer, 40-60 parts of an adhesion resin, and 3-6 parts of an antioxidant. The prepared product has good wettability and improved polarity of the glue, is beneficial to application and wettability to a base material, has fast glue melting speed, high production efficiency, low requirements on transportation, storage and use conditions, high inclusiveness to equipment and processes, is suitable for roll coating and blade coating, has good wettability to PE foam, and has excellent peel strength and moderate holding adhesion.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hot melt pressure sensitive adhesive, in particular to a hot melt pressure sensitive adhesive suitable for heel anti-friction paste product and a preparation method thereof. BACKGROUND

[0002] In summer, whether it is a climate problem or a dressing problem, when wearing socks, some people will choose some socks or boat socks, or choose sandals, and women may wear some high heels, etc. When you walk, the shoes will rub your heel skin from time to time, and the heel will gradually turn red or break the skin, thereby affecting our daily life. The common heel anti-friction paste on the market is composed of silica gel paste, sleeve or foam adhesive paste. Generally, acrylic adhesive is used for the preparation of anti-friction paste on the market, but the product has the defect of low initial adhesion.

[0003] Patent CN102604570A discloses a hot melt pressure sensitive adhesive for HDPE self-adhesive coiled material and a preparation method thereof. The hot melt pressure sensitive adhesive has excellent adhesion and low high-temperature viscosity, which is prepared by using polystyrene-polyisoprene-polystyrene thermoplastic elastomer as the main polymer, and then adding polyisobutylene, carbon five petroleum resin and a small amount of antioxidant. However, if the product comes into contact with the skin, it is easy to leave adhesive on the surface of the skin, which is not conducive to application in heel anti-friction paste products. Therefore, it is of great significance to develop a hot melt pressure sensitive adhesive with good wettability, which can be applied to PE foam to prepare PE foam adhesive tape, and the hot melt pressure sensitive adhesive has low sensitization, is environmentally friendly and non-toxic, has excellent peel strength and moderate holding adhesion, and is not easy to leave the skin surface. SUMMARY

[0004] The present application provides a hot melt pressure sensitive adhesive suitable for heel anti-friction paste product, which comprises the following components by weight: 10-35 parts of block copolymer, 10-30 parts of plasticizer, 40-60 parts of tackifying resin and 3-6 parts of antioxidant.

[0005] As a preferred technical solution, the hot melt pressure sensitive adhesive comprises the following components by weight: 15-30 parts of block copolymer, 10-25 parts of plasticizer, 40-55 parts of tackifying resin and 3-5 parts of antioxidant.

[0006] As a preferred technical solution, the block copolymer is a compound of styrene-isoprene-styrene block copolymer (SIS) and styrene-butadiene-styrene block copolymer (SBS), and the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 6-8:2-4.

[0007] Preferably, the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 7:3.

[0008] The double block content of the styrene-isoprene-styrene block copolymer (SIS) is high, which effectively improves the initial adhesion and peeling performance of the product, but the initial adhesion and peeling performance are too large, which easily leads to glue residue on the skin surface and is not easy to remove. The present applicant finds that when the block copolymer is a combination of the styrene-isoprene-styrene block copolymer (SIS) and the styrene-butadiene-styrene block copolymer (SBS), and the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 6-8:2-4, the defect of insufficient cohesion of the styrene-isoprene-styrene block copolymer (SIS) can be compensated for, and glue residue on the skin surface can be prevented. Especially when the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 7:3, the product has better initial adhesion, holding adhesion, and peeling force.

[0009] Preferably, the double block content of the styrene-isoprene-styrene block copolymer (SIS) is 15-55wt%.

[0010] Preferably, the double block content of the styrene-isoprene-styrene block copolymer (SIS) is 17-50wt%.

[0011] Preferably, the styrene-isoprene-styrene block copolymer (SIS) is a combination of YH-1106 and YH-1126; preferably, the weight ratio of the YH-1106 to the YH-1126 is 1:1-2.

[0012] Preferably, the weight ratio of the YH-1106 to the YH-1126 is 1:1.5.

[0013] Preferably, the S / B ratio of the styrene-butadiene-styrene block copolymer (SBS) is 20-32:68-80.

[0014] Preferably, the S / B ratio of the styrene-butadiene-styrene block copolymer (SBS) is 32:68 or 20:80.

[0015] Preferably, the styrene-butadiene-styrene block copolymer (SBS) is a combination of YH-188 and YH-792, and the weight ratio of the YH-188 to the YH-792 is 1:1.

[0016] Preferably, the YH-1106, YH-1126, YH-188, YH-792 are purchased from Balin Petroleum Chemical Industry Co., Ltd.

[0017] As a preferred technical solution, the plasticizer is at least one of naphthenic oil and white mineral oil.

[0018] Preferably, the plasticizer is naphthenic oil, and the pour point of the naphthenic oil is -30℃ to -15℃.

[0019] Preferably, the naphthenic oil is Karamay naphthenic oil 4010, purchased from Maoming Runhua Petroleum Chemical Co., Ltd.

[0020] As a preferred technical solution, the tackifying resin is at least one of C5 petroleum resin, C9 petroleum resin, dicyclopentadiene resin, rosin resin, and terpene resin.

[0021] Preferably, the tackifying resin is a combination of C5 petroleum resin, dicyclopentadiene resin, and rosin resin.

[0022] Preferably, the weight ratio of the C5 petroleum resin, dicyclopentadiene resin, and rosin resin is (4-6):(3-5):1.

[0023] Preferably, the weight ratio of the C5 petroleum resin, dicyclopentadiene resin, and rosin resin is 5:4:1.

[0024] In this application, by selecting the tackifying resin as a combination of C5 petroleum resin, dicyclopentadiene resin, and rosin resin, the adhesion and peeling performance of the product are ensured under the synergistic effect. By adding a small amount of rosin resin in the system, the wettability of the product and the polarity of the glue are improved, which is conducive to the application and wettability to the substrate. Especially when the weight ratio of the C5 petroleum resin, dicyclopentadiene resin, and rosin resin is 5:4:1, a synergistic effect with block copolymer is generated, the initial adhesion, peeling force, and adhesion of the product are good.

[0025] Preferably, the softening point of the C5 petroleum resin is 98-102℃.

[0026] Preferably, the softening point of the C5 petroleum resin is 100℃.

[0027] Preferably, the model of the C5 petroleum resin is A1100, purchased from Luhua Chemical Co., Ltd.; the dicyclopentadiene resin is purchased from Jinan Hui Fengda Chemical Co., Ltd.; and the rosin resin is purchased from Baolin Plastic Co., Ltd.

[0028] As a preferred technical solution, the antioxidant is at least one of antioxidant 1010, antioxidant DLTP, antioxidant 168, and antioxidant 1076.

[0029] Preferably, the antioxidant is a compound of antioxidant 1010 and antioxidant 1076, and the weight ratio of the antioxidant 1010 to the antioxidant 1076 is 1:0.6-0.8.

[0030] Preferably, the weight ratio of the antioxidant 1010 to the antioxidant 1076 is 1:0.7.

[0031] Another aspect of the present application discloses a preparation method of hot melt pressure sensitive adhesive suitable for heel anti-wear patch products, comprising the following steps: weighing each raw material according to the required weight parts, adding block copolymer and antioxidant into a stirring tank and heating and stirring to 130-140 DEG C, adding tackifying resin and plasticizer after sufficient stirring, vacuum stirring for 35 min, and then pressing out the glue to obtain the product.

[0032] Preferably, the preparation method comprises the following steps: weighing each raw material according to the required weight parts, adding block copolymer and antioxidant into a stirring tank and heating and stirring to 134 DEG C, adding tackifying resin and plasticizer after sufficient stirring, vacuum stirring for 35 min, and then pressing out the glue to obtain the product.

[0033] The present application has the following beneficial effects: 1) by selecting the compound of specific components of block copolymer, the defect of insufficient cohesion of styrene-isoprene-styrene block copolymer (SIS) is improved, so that the product has good initial adhesion and holding adhesion, high peeling force and is not easy to remain on the skin surface; 2) by selecting specific tackifying resin and using amount, the wettability of the product is improved, and the polarity of the glue is improved, which is beneficial to the application and the wettability to the substrate; 3) the product has fast fusion speed, high production efficiency, low transportation, storage and use conditions, large inclusiveness of equipment and process, is suitable for roll coating and blade coating, has good wettability to PE foam, excellent peeling force and moderate holding adhesion. DETAILED DESCRIPTION

[0034] Example 1

[0035] The example 1 of the present application discloses a hot melt pressure sensitive adhesive suitable for heel anti-wear patch products, which comprises the following components in weight parts: 23 parts of block copolymer, 17 parts of plasticizer, 47 parts of tackifying resin, and 4 parts of antioxidant.

[0036] The block copolymer is a compound of styrene-isoprene-styrene block copolymer (SIS) and styrene-butadiene-styrene block copolymer (SBS), and the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 7:3.

[0037] The diblock content of the styrene-isoprene-styrene block copolymer (SIS) is 17-50 wt%.

[0038] The styrene-isoprene-styrene block copolymer (SIS) is a complex of YH-1106 and YH-1126, and the weight ratio of YH-1106 to YH-1126 is 1:1.5.

[0039] The diblock content of the YH-1106 is 17 wt%, and the diblock content of the YH-1126 is 50 wt%.

[0040] The S / B ratio of the styrene-butadiene-styrene block copolymer (SBS) is 32:68 and 20:80.

[0041] The styrene-butadiene-styrene block copolymer (SBS) is a complex of YH-188 and YH-792, and the weight ratio of YH-188 to YH-792 is 1:1.

[0042] The S / B ratio of the YH-188 is 32:68, and the S / B ratio of the YH-792 is 20:80.

[0043] The YH-1106, YH-1126, YH-188, and YH-792 are all purchased from Balin Petroleum Chemical Industry Co., Ltd.

[0044] The plasticizer is naphthenic oil, and the pour point of the naphthenic oil is -24℃.

[0045] The naphthenic oil is Karamay naphthenic oil 4010, purchased from Maoming Runhua Petroleum Chemical Industry Co., Ltd.

[0046] The tackifying resin is a complex of C5 petroleum resin, dicyclopentadiene resin, and rosin resin.

[0047] The weight ratio of the C5 petroleum resin, dicyclopentadiene resin, and rosin resin is 5:4:1.

[0048] The softening point of the C5 petroleum resin is 100℃.

[0049] The model of the C5 petroleum resin is A1100, purchased from Luhua Chemical Co., Ltd.; the dicyclopentadiene resin is purchased from Jinan Hui Fengda Chemical Co., Ltd.; and the rosin resin is purchased from Baolin Plastic Co., Ltd.

[0050] The antioxidant is a complex of antioxidant 1010 and antioxidant 1076, and the weight ratio of antioxidant 1010 to antioxidant 1076 is 1:0.7.

[0051] The antioxidant 1010 is purchased from Qingdao Zhen Guang Functional Material Technology Co., Ltd., and the antioxidant 1076 is purchased from Henan Ankai Chemical Technology Co., Ltd.

[0052] Another aspect of the embodiment discloses a preparation method of the hot melt pressure sensitive adhesive suitable for the heel anti-wear patch product, comprising the following steps: weighing each raw material according to the required weight part, adding the block copolymer and the antioxidant into a stirring tank and heating and stirring to 134 DEG C, adding the tackifying resin and the plasticizer after sufficient stirring, vacuumizing and stirring for 35 min, and extruding the glue under pressure to obtain the product.

[0053] Example 2

[0054] The embodiment 2 of the present application discloses a hot melt pressure sensitive adhesive suitable for the heel anti-wear patch product, comprising the following components in weight part: 15 parts of the block copolymer, 10 parts of the plasticizer, 40 parts of the tackifying resin, and 3 parts of the antioxidant.

[0055] The specific implementation method is the same as that in the example 1, except that the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 6:4.

[0056] The weight ratio of the YH-1106 to the YH-1126 is 1:1.

[0057] The weight ratio of the C5 petroleum resin, the dicyclopentadiene resin and the rosin resin is 4:3:1.

[0058] Example 3

[0059] The embodiment 3 of the present application discloses a hot melt pressure sensitive adhesive suitable for the heel anti-wear patch product, comprising the following components in weight part: 30 parts of the block copolymer, 25 parts of the plasticizer, 55 parts of the tackifying resin, and 5 parts of the antioxidant.

[0060] The specific implementation method is the same as that in the example 1, except that the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) to the styrene-butadiene-styrene block copolymer (SBS) is 8:2.

[0061] The weight ratio of the YH-1106 to the YH-1126 is 1:2.

[0062] The weight ratio of the C5 petroleum resin, the dicyclopentadiene resin and the rosin resin is 6:5:1.

[0063] Comparative Example 1

[0064] Comparative Example 1 of the present application discloses a hot melt pressure sensitive adhesive suitable for heel anti-friction tape product, the specific implementation is the same as Example 1, the difference is that the weight ratio of the styrene-isoprene-styrene block copolymer (SIS) and the styrene-butadiene-styrene block copolymer (SBS) is 3:7.

[0065] Comparative Example 2

[0066] Comparative Example 1 of the present application discloses a hot melt pressure sensitive adhesive suitable for heel anti-friction tape product, the specific implementation is the same as Example 1, the difference is that the weight ratio of the C5 petroleum resin, dicyclopentadiene resin, and rosin resin is 1:1:1.

[0067] Comparative Example 3

[0068] Comparative Example 3 of the present application is a PE foam anti-friction tape made of acrylic glue commonly used on the market.

[0069] Performance test

[0070] The products obtained in Examples 1-3 and Comparative Examples 1-2 are prepared into PE foam anti-friction tapes, which have the same grammage of the substrate and the added glue as Comparative Example 3. The peel strength, loop initial adhesion, and holding adhesion of the obtained PE foam anti-friction tapes are tested.

[0071] 1. Peel strength: test the peel strength under 180° condition according to the reference standard GB / T 2792;

[0072] 2. Loop initial adhesion: test the loop initial adhesion according to the reference standard GB / T 31125;

[0073] 3. Holding adhesion: test the holding adhesion according to the reference standard GB / T 4851.

[0074] The test results are shown in Table 1.

[0075] Table 1

[0076]

Claims

1. A hot melt pressure sensitive adhesive suitable for use in a heel counter product, characterized in that, By weight parts, including the following components: block copolymer is 15-30 parts, plasticizer is 10-25 parts, tackifying resin is 40-55 parts, antioxidant 3-5 parts; The block copolymer is a complex of styrene-isoprene-styrene block copolymer and styrene-butadiene-styrene block copolymer, and the weight ratio of the styrene-isoprene-styrene block copolymer to the styrene-butadiene-styrene block copolymer is 7:3, 6:4 or 8:2; The styrene-isoprene-styrene block copolymer is a complex of YH-1106 and YH-1126, and the weight ratio of the YH-1106 to the YH-1126 is 1:1-2; the styrene-butadiene-styrene block copolymer is a complex of YH-188 and YH-792, and the weight ratio of the YH-188 to the YH-792 is 1:1; The tackifying resin is a complex of C5 petroleum resin, dicyclopentadiene resin and rosin resin, and the weight ratio of the C5 petroleum resin, dicyclopentadiene resin and rosin resin is 5:4:1, 4:3:1 or 6:5:

1.

2. A hot melt pressure sensitive adhesive suitable for use in a heel guard product according to claim 1, wherein, The antioxidant is at least one of antioxidant 1010, antioxidant DLTP, antioxidant 168 and antioxidant 1076.

3. A process for the preparation of a hot-melt pressure sensitive adhesive suitable for use in a heel counter product according to any one of claims 1-2, characterized in that, The method comprises the following steps: weighing each raw material according to the required weight parts, adding the block copolymer and the antioxidant into a stirring tank and heating and stirring to 130-140℃, adding the tackifying resin and the plasticizer after sufficient stirring, vacuum stirring for 35min, and then pressing out the glue to obtain the product.

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