CN113930198A - Oil-filled star-shaped rubber hot melt adhesive and preparation method thereof - Google Patents
Oil-filled star-shaped rubber hot melt adhesive and preparation method thereof Download PDFInfo
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- CN113930198A CN113930198A CN202111397838.5A CN202111397838A CN113930198A CN 113930198 A CN113930198 A CN 113930198A CN 202111397838 A CN202111397838 A CN 202111397838A CN 113930198 A CN113930198 A CN 113930198A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 162
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000004014 plasticizer Substances 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 238000011049 filling Methods 0.000 claims abstract description 15
- 239000002199 base oil Substances 0.000 claims abstract description 14
- 239000010690 paraffinic oil Substances 0.000 claims abstract description 10
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical class C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 241000219061 Rheum Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of hot melt adhesives, in particular to an oil-filled star-shaped rubber hot melt adhesive and a preparation method thereof. The oil-filled star-shaped rubber hot melt adhesive comprises, by mass, 20-33% of a plasticizer, 15-30% of oil-filled star-shaped rubber, 35-64.7% of tackifying resin, 0.1-1.0% of an antioxidant and 0.2-1.0% of an ultraviolet absorbent; the molecular weight of the oil-extended star rubber is 30-60 ten thousand; according to the mass percentage, the oil filling amount of the oil-filled star rubber is 20-40%; the plasticizer is a paraffinic oil. According to the invention, the oil-filled star rubber is introduced into the hot melt adhesive and is compounded with the paraffin base oil for use, and the paraffin base oil has a small molecular weight, so that the oil-filled star rubber can be softened and better melted, the oil-filled star rubber is successfully applied to the field of the hot melt adhesive, the peel strength of the oil-filled star rubber hot melt adhesive can be improved, and the problem that the existing oil-filled star rubber is difficult to apply to the field of the hot melt adhesive is solved.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to an oil-filled star-shaped rubber hot melt adhesive and a preparation method thereof.
Background
In recent years, the market environments at home and abroad are complex and changeable, hot melt adhesive enterprises face pressure in various aspects such as large price fluctuation of raw materials, excess capacity, fierce market competition and the like, and particularly the continuously fluctuating price of the raw materials brings great pressure to the production and operation of the hot melt adhesive enterprises. Therefore, how to reduce the product cost and improve the product performance becomes a problem of close attention of numerous hot melt adhesive enterprises.
The structures of all layers of the disposable sanitary product are basically bonded and compounded through hot melt adhesive. The existing hot melt adhesive generally comprises a high molecular polymer, a plasticizer, tackifying resin and an antioxidant, wherein the high molecular polymer is generally rubber, and the rubber type suitable for the hot melt adhesive is more and more difficult to meet the requirement of the market of disposable sanitary products. The oil-extended rubber is a high molecular polymer prepared from rubber and an oil softener, has low cost and excellent oil locking property and high temperature resistance, but has high viscosity, difficult melting, overlong melting time and easy aging compared with common rubber due to large molecular weight in the hot melt adhesive industry, so that the oil-extended rubber is generally used in the industries of shoe processing industry, plastic modification and the like, and is difficult to meet the production and processing technology of the hot melt adhesive, and therefore, the oil-extended rubber is difficult to be applied to the production of the hot melt adhesive.
Disclosure of Invention
Aiming at the problems brought forward by the background art, the invention aims to provide an oil-filled star-shaped rubber hot melt adhesive, which is prepared by introducing oil-filled star-shaped rubber into the hot melt adhesive and compounding the oil-filled star-shaped rubber with 20-33% of paraffin-based oil, wherein the paraffin-based oil has a small molecular weight, so that the oil-filled star-shaped rubber can be softened and better melted, and the oil-filled star-shaped rubber is successfully applied to the field of the hot melt adhesive, the peel strength of the oil-filled star-shaped rubber hot melt adhesive can be effectively improved, and the problem that the existing oil-filled star-shaped rubber is difficult to melt due to a large molecular weight and is difficult to apply to the field of the hot melt adhesive is solved.
The invention also aims to provide a preparation method of the oil-extended star-shaped rubber hot melt adhesive, which can fully melt the oil-extended star-shaped rubber, is simple and can realize industrial production.
The oil-filled star-shaped rubber hot melt adhesive comprises, by mass, 20-33% of a plasticizer, 15-30% of a high polymer, 35-64.7% of tackifying resin, 0.1-1.0% of an antioxidant and 0.2-1.0% of an ultraviolet absorber;
the high molecular polymer is oil-filled star rubber, and the molecular weight of the oil-filled star rubber is 30-60 ten thousand; according to the mass percentage, the oil filling amount of the oil-filled star rubber is 20-40%;
the plasticizer is a paraffinic oil.
Further, the melt index of the oil-extended star rubber is 5-50 (g/10 min);
according to the mass percentage, the content of styrene in the oil-extended star rubber is 25-45%.
Further, the oil-extended star rubber is one or more of star SBS1475, star SBS1484, star SBS1485 and star SBS 1487.
Further, the molecular weight of the paraffinic oil is 100 to 400.
Further, the paraffinic oil is KP6010 or P-80.
Further, the tackifying resin is one or more of hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin and hydrogenated DCPD petroleum resin.
Further, the antioxidant is one or two of antioxidant 1010 and antioxidant 168.
Further, the ultraviolet absorber is UV 326.
A preparation method of an oil-filled star-shaped rubber hot melt adhesive is used for preparing the oil-filled star-shaped rubber hot melt adhesive and comprises the following steps:
(1) according to the formula ratio, adding a plasticizer and an antioxidant into a reaction kettle, heating to raise the temperature to 115-125 ℃, adding oil-filled star rubber, controlling the temperature to be 120-150 ℃, and stirring;
(2) and (2) after the oil-filled star rubber in the step (1) is completely melted, adding tackifying resin and an ultraviolet absorbent, controlling the temperature to be 120-150 ℃, and after the tackifying resin is completely melted, vacuumizing until no air bubbles exist, and discharging the glue to obtain the oil-filled star rubber hot melt adhesive.
This technical scheme has above beneficial effect: according to the technical scheme, the oil-filled star rubber is introduced into the hot melt adhesive and is compounded with 20-33% of paraffin-based oil for use, and the paraffin-based oil has a small molecular weight, so that the oil-filled star rubber can be better softened and better melted compared with the conventional naphthenic oil with a large molecular weight, and the oil-filled star rubber is successfully applied to the field of the hot melt adhesive, so that a new formula thought is provided for the hot melt adhesive, and the industrial development is promoted. Moreover, because the oil-filled star rubber has a large molecular weight and the plasticizers and the tackifying resins have small molecular weights, the micromolecular plasticizers and the tackifying resins are filled among macromolecular chains in a surrounding manner, the peel strength and the cohesive strength of the oil-filled star rubber hot melt adhesive can be effectively improved, the micromolecular precipitation resistance is improved, meanwhile, the odor is small, the comfort is better, and a new selectable main body material is provided for the disposable hygienic hot melt adhesive.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The oil-filled star-shaped rubber hot melt adhesive comprises, by mass, 20-33% of a plasticizer, 15-30% of a high polymer, 35-64.7% of tackifying resin, 0.1-1.0% of an antioxidant and 0.2-1.0% of an ultraviolet absorber;
the high molecular polymer is oil-filled star rubber, and the molecular weight of the oil-filled star rubber is 30-60 ten thousand; according to the mass percentage, the oil filling amount of the oil-filled star rubber is 20-40%;
the plasticizer is a paraffinic oil.
It is worth to be noted that the rubber is generally divided into linear rubber and star-shaped rubber, the star-shaped rubber has higher strength and better oil locking performance compared with the linear rubber, and at the later stage of the star-shaped rubber production, a proper amount of oil softener is filled to prepare the oil-filled star-shaped rubber, wherein the ratio of the mass of the filled oil softener to the total mass of the oil-filled star-shaped rubber is oil filling amount, the cost of the oil-filled star-shaped rubber is low, and the oil-filled star-shaped rubber has excellent oil locking performance and high temperature resistance, but for the hot melt adhesive industry, the oil-filled star-shaped rubber has a large molecular weight and is difficult to meet the production and processing technology of the hot melt adhesive, the molecular weight of the conventional rubber is generally less than 30 ten thousand, while the molecular weight of the oil-filled rubber is generally more than 30 thousand, and the oil-filled rubber is difficult to process due to the large molecular weight, the high temperature and the long time are required for complete melting, while the melting temperature of the hot melt adhesive is lower, if the oil-filled rubber is directly added into the raw material of the hot melt adhesive, the rubber is difficult to melt with other raw materials, so that the oil-extended star-shaped rubber is not used for producing the hot melt adhesive at present, and the oil-extended star-shaped rubber is mainly used in the industries of shoe processing, plastic modification and the like. According to the technical scheme, the oil-filled star rubber is introduced into the hot melt adhesive and is compounded with 20-33% of paraffin-based oil for use, and the paraffin-based oil has a small molecular weight, so that the oil-filled star rubber can be better softened compared with the traditional naphthenic oil with a large molecular weight, the oil-filled star rubber can be better melted, and the paraffin-based oil has a chain structure, and compared with a plasticizer with a ring structure, the paraffin-based oil with the chain structure has lower rigidity and lower hardness, and can be better softened, so that the oil-filled star rubber can be easier to soften, and therefore the oil-filled star rubber is successfully applied to the field of the hot melt adhesive, a new formula thought is provided for the hot melt adhesive, and the industrial development is promoted.
Preferably, the tackifier resin has a molecular weight of 300 to 2000, and the paraffin-based oil has a molecular weight of 50 to 400. Because the oil-filled star rubber has large molecular weight and the plasticizer and the tackifying resin have small molecular weight, and the micromolecular plasticizer and the tackifying resin are filled among macromolecular chains in a surrounding way, the peel strength and the cohesive strength of the oil-filled star rubber hot melt adhesive can be effectively improved, the micromolecular precipitation resistance is improved, meanwhile, the odor is small, the comfortableness is better, and a new selectable main body material is provided for the disposable hygienic hot melt adhesive.
Further, the oil-filled star rubber in the technical scheme is the oil-filled star rubber with the oil filling amount of 20-40%, and has the characteristics of strong plasticity and small contractibility, the oil is micromolecule and is responsible for softening the oil-filled star rubber in advance, the subsequent processing is convenient, the smaller the oil filling proportion is, the smaller the softening degree of the oil-filled star rubber is, the more difficult the subsequent processing is, and the lower the efficiency is; if the oil-extended proportion is larger, the softening degree is larger, and the subsequent processing is convenient, but the strength of the oil-extended star-shaped rubber is weakened, and the elasticity is also deteriorated.
Specifically, the plasticizer mainly adjusts the fluidity of the oil-filled star-shaped rubber hot melt adhesive, so that the oil-filled star-shaped rubber hot melt adhesive can better permeate the base material, the more the plasticizer is, the better the fluidity of the oil-filled star-shaped rubber hot melt adhesive is, and the fluidity can influence the gluing effect and the gluing mode; the plasticizer also acts as a softening rubber to allow the rubber to melt more quickly during heating. The oil-filled star rubber is a main material and mainly provides strength for the oil-filled star rubber hot melt adhesive, the more the content proportion of the oil-filled star rubber is, the higher the strength is, the better the elasticity is, and the better the low-temperature resistant effect is, but if the content of the oil-filled star rubber is too large, the difficulty in melting can be caused. The tackifying resin can increase the viscosity of the oil-filled star-shaped rubber hot melt adhesive, so that the prepared oil-filled star-shaped rubber hot melt adhesive can adhere to a bonded substrate and a bonding substrate. The antioxidant is used as a conventional auxiliary raw material and mainly provides anti-aging performance for the oil-filled star-shaped rubber hot melt adhesive. The ultraviolet absorber UV326 absorbs ultraviolet rays and prevents fluorescence from being generated by the irradiation of ultraviolet rays.
Preferably, the oil-filled star-shaped rubber hot melt adhesive is applied to the industry of disposable sanitary products, such as baby diapers, baby pull-ups, sanitary towels, medical mattresses, adult diapers, adult pull-ups and other disposable sanitary products, and the hot melt adhesive for the disposable sanitary products is required to have certain bonding performance, small smell, soft hand feeling, good low temperature resistance effect and can be used under the condition that the environmental temperature is above 5 ℃. The oil-filled star-shaped rubber hot melt adhesive of the technical scheme has the advantages of low cost, good oil locking performance and excellent high temperature resistance by introducing the oil-filled star-shaped rubber into the hot melt adhesive used in the disposable sanitary material industry, and compared with general rubber (the molecular weight is less than 30 ten thousand), the oil-filled star-shaped rubber has higher viscosity, is difficult to melt, has overlong melting time and is easy to age because the molecular weight of the oil-filled star-shaped rubber is 30-60 ten thousand, so that the oil-filled star-shaped rubber is generally used in the industries of shoe processing industry, plastic modification and the like and is difficult to be applied to the hot melt adhesive used in disposable sanitary products, the prepared oil-filled star-shaped rubber hot melt adhesive has improved overall performance, excellent peel strength and wettability, and excellent cohesive strength, increases the selectable directions of high-molecular polymers in the common hot melt adhesive, and fills the blank of the material use of the hot melt adhesive for disposable hygienic products.
Further, the melt index of the oil-extended star rubber is 5-50 (g/10min, 190 ℃/5 kg);
according to the mass percentage, the content of styrene in the oil-extended star rubber is 25-45%.
The lower the melt index, the higher the reaction molecular weight, the thicker the oil-extended star-shaped rubber hot melt adhesive prepared, and vice versa. The oil-extended star rubber is a triblock copolymer, taking SBS as an example, and has the composition of S-B-S, wherein S is styrene and is a hard segment, and B is a butadiene rubber segment and is a soft segment. The more S, the harder the rubber, the harder the hot melt adhesive prepared, the poorer the elasticity, the poorer the low temperature resistance, and vice versa.
When the styrene content in the oil-filled star rubber is 25-45% and the melt index of the oil-filled star rubber is 5-50 (g/10min, 190 ℃/5kg), the prepared oil-filled star rubber hot melt adhesive has high strength and flexibility, and can improve the bonding performance and the temperature resistance effect. Too low a melt index can result in the oil-extended star rubber being difficult to melt and leading to aging; if the mass percentage of styrene in the oil-filled star rubber exceeds 45 percent, the oil-filled star rubber hot melt adhesive is hard, the quick-drying wettability is poor, and the peel strength is reduced.
Stated further, the oil-extended star rubber is one or more of star SBS1475, star SBS1484, star SBS1485 and star SBS 1487.
Specifically, star SBS1475 is produced in Taiwan plum, and its oil-filling amount is 33.3%; the star SBS1485 is produced in Taiwan plum, and the oil filling amount is 31%; the star SBS1484 is produced in Taiwan plum, and the oil filling amount is 33.3%; star SBS1487 is produced in Taiwan plum with oil filling of 28.5%.
The rubber structure has two types of linear rubber and star rubber, the linear rubber has lower strength and poor oil locking property compared with the star rubber, but the linear rubber is easier to process compared with the star rubber; the larger the molecular weight of the rubber is, the larger the intermolecular force is, and the stronger the oil locking property is, but the conventional rubber used in the hot melt adhesive industry at present is generally linear rubber, has smaller molecular weight, poor oil locking property and higher price, and a small number of star-shaped rubbers which are not filled with oil are adopted, but the traditional star-shaped rubbers which are not filled with oil are more expensive than the linear rubbers, so the production cost can be greatly increased by using the linear-structured rubber and the star-shaped rubbers which are not filled with oil. Moreover, the conventional rubber used in the hot melt adhesive industry at present has the advantages that the molecular weight of the conventional rubber, whether linear rubber or non-oil-filled star rubber is small compared with that of oil-filled star rubber, and the oil locking property is poor.
Further, the molecular weight of the paraffinic oil is 50 to 400.
The oil-filled star rubber has high molecular weight and is difficult to process, the paraffin base oil with the molecular weight less than 400 is used as the plasticizer, so that the oil-filled star rubber can be better softened, the oil-filled star rubber can be better processed, the paraffin base oil can adjust the fluidity of the oil-filled star rubber hot melt adhesive and enhance the low temperature resistance of the oil-filled star rubber hot melt adhesive, the smaller the molecular weight is, the lower the glass transition temperature (Tg) point of the obtained hot melt adhesive is, and the better the low temperature resistance effect is.
In a further aspect, the paraffinic base oil is KP6010 paraffinic base oil or P-80 paraffinic base oil.
It is to be noted that the molecular weight of the P-80 paraffinic base oil is 60, CPParaffin base proportion 67%, CNThe proportion of cycloalkyl groups is 33%; KP6010 Paraffin base oil has a molecular weight of 100, CPParaffin base proportion of 64%, CNThe proportion of cycloalkyl is 35%; because KP6010 paraffin base oil and P-80 paraffin base oil have small molecular weight, the obtained oil-extended star-shaped rubber hot melt adhesive has low glass transition temperature (Tg) point and good low temperature resistance effect. CPThe higher the paraffin base content is, the smaller the peeling force constant viscosity data of the obtained hot melt adhesive is; cNThe higher the content of cycloparaffins, the higher the peel force tack data of the hot melt adhesive obtained.
Specifically, KP6010 paraffinic oil is available from Clarity, and P-80 paraffinic oil is available from David technology.
Illustratively, the tackifying resin is one or more of a hydrogenated C9 petroleum resin, a hydrogenated C5 petroleum resin, and a hydrogenated DCPD petroleum resin.
The petroleum resins can effectively improve the adhesive property of the oil-filled star-shaped rubber hot melt adhesive to the base material.
Specifically, the hydrogenated DCPD petroleum resin is selected from one or more of gold sea JH6100, rugosity HD1100, Rassen S5100 or constant river HM 1000; hydrogenated C9 petroleum resin is selected from one or more of Qilon QH4100, Tianma AH1000, and Liansuper FM 100; the hydrogenated C5 petroleum resin is selected from one or more of Henghe HS1001 and Chinese information sources PZX-H2100.
Illustratively, the antioxidant is one or both of antioxidant 1010 and antioxidant 168.
The antioxidant can protect the oil-filled star-shaped rubber hot melt adhesive from oxidation and other aging reactions during heating and storage at normal temperature, and the stability of the oil-filled star-shaped rubber hot melt adhesive is ensured.
Illustratively, the ultraviolet absorber is UV 326.
The UV326 and the antioxidant have good synergistic effect, can effectively prevent ultraviolet rays from passing through, and enables the prepared oil-filled star-shaped rubber hot melt adhesive to have higher stability and avoid aging.
A preparation method of an oil-filled star-shaped rubber hot melt adhesive is used for preparing the oil-filled star-shaped rubber hot melt adhesive and comprises the following steps:
(1) according to the formula ratio, adding a plasticizer and an antioxidant into a reaction kettle, heating to raise the temperature to 115-125 ℃, adding oil-filled star rubber, controlling the temperature to be 120-150 ℃, and stirring;
(2) and (2) after the oil-filled star rubber in the step (1) is completely melted, adding tackifying resin and an ultraviolet absorbent, controlling the temperature to be 120-150 ℃, and after the tackifying resin is completely melted, vacuumizing until no air bubbles exist, and discharging the glue to obtain the oil-filled star rubber hot melt adhesive.
Specifically, in the step (1), the oil-extended star rubber is a porous granular material, so that the oil-extended star rubber is easy to absorb a plasticizer and thicken, and if the temperature is too low, the oil-extended star rubber is difficult to melt, so that stirring cannot be performed, and stirring cannot be performed, so that production cannot be performed. After the oil-filled star rubber is added, the temperature needs to be controlled to be 130-150 ℃, if the temperature is too low, the material is too thick, stirring cannot be easily caused, the oil-filled star rubber cannot be sheared and melted, and if the temperature is too high, the material is easily subjected to high-temperature oxidation and is aged. The preparation method of the technical scheme can fully melt the oil-extended star rubber, is simple and can realize industrial production.
The technical scheme of the invention is further illustrated by combining specific examples and comparative examples.
Example 1
An oil-extended star-shaped rubber hot melt adhesive comprises, by mass, 22% of KP6010 (Clarity), 21% of star-shaped SBS1485 (Lechangrong), 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 25% of Jinhai JH6100, 30.7% of Heng HM1000 and 0.3% of UV326, wherein the molecular weight of the star-shaped SBS1485 (Lechangrong) is 35 ten thousand, the oil-extended amount of the star-shaped SBS1485 (Lechangrong) is 31%, the melt index of the star-shaped SBS1485 (Lechangrong) is 8(g/10min, 190 ℃/5kg), the styrene content of the oil-extended star-shaped rubber is 32%, the molecular weight of the Clarity 6010 (Maryland) is 100, and the molecular weight of the Jinhai JH6100 is 511; the molecular weight of the rhesus HM1000 is 492.
The preparation method of the oil-filled star-shaped rubber hot melt adhesive comprises the following steps:
uniformly mixing 22% of KP6010 (Clarity), 21% of star SBS1485 (Lecheng), 0.5% of antioxidant 1010 and 0.5% of antioxidant 168, heating to 130 ℃, and stirring while vacuumizing until all components are completely melted; then adding 25% of gold sea JH6100, 30.7% of rheum HM1000 and 0.3% of UV326 in sequence, heating to melt at 130 ℃, then vacuumizing until no bubbles exist, stirring and mixing uniformly to obtain the oil-filled star-shaped rubber hot melt adhesive.
The hot melt adhesive prepared by the embodiment is suitable for a device for spraying, roll coating or blade coating, the oil-filled star-shaped rubber hot melt adhesive is placed in a hot melt adhesive cylinder, the temperature is kept at 130 ℃ until the adhesive block is completely melted for use, the gluing surface is a non-woven fabric or a PE film, and the gluing amount is about 1.5g/m2And pressing and compounding to obtain the basic structure of the disposable hygienic product. The viscosity of the oil-filled star-shaped rubber hot melt adhesive is mainly provided by tackifying resin, star-shaped SBS1485 is selected as the oil-filled star-shaped rubber, Hoodia HM1000 and Hoodia JH6100 resin is selected as the hydrogenated DCPD resin in the embodiment, so that the peel strength and the cohesive strength of the oil-filled star-shaped rubber hot melt adhesive product are greatly improved, the adhesive force is strong, the application temperature range is relatively proper, and the universality is relatively strong.
Example 2
The oil-extended star-shaped rubber hot melt adhesive comprises, by mass, 23% of P-80, 19% of SBS1475 (Lecheng Rong company), 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 56.7% of Qilong QH4100 and 0.3% of UV326, wherein the molecular weight of SBS1475 (Lecheng Rong company) is 40 ten thousand, the oil-extended amount of SBS1475 (Lecheng Rong company) is 33.3%, the melt index of SBS1475 (Lecheng Rong company) is 5(g/10min, 190 ℃/5kg), the styrene content of SBS1475 (Lecheng Rong company) is 40%, the molecular weight of P-80 is 60, and the molecular weight of Qilong QH4100 is 707.
The preparation method of the oil-filled star-shaped rubber hot melt adhesive comprises the following steps:
uniformly mixing 23% of P-80, 19% of SBS1475 (Lechangrong company), 0.5% of antioxidant 1010 and 0.5% of antioxidant 168, heating to 130 ℃, and stirring while vacuumizing until all components are completely melted; then adding 56.7 percent of zipron QH4100 and 0.3 percent of UV326 in sequence, and heating to be molten at 130 ℃; then vacuumizing until no air bubbles exist, and stirring and mixing uniformly to obtain the oil-filled star-shaped rubber hot melt adhesive.
The oil-filled star-shaped rubber hot melt adhesive prepared by the embodiment is suitable for a device for spraying, roller coating or blade coating, the hot melt adhesive is placed in a hot melt adhesive cylinder, the temperature is kept constant at 130 ℃ until an adhesive block is completely melted for use, the gluing surface is a non-woven fabric or a PE (polyethylene) film, and the gluing amount is about 1.5g/m2After lamination and compounding, the basic structure of the disposable hygienic product is obtained, the viscosity of the oil-filled star rubber is mainly provided by tackifying resin, star SBS1475 oil-filled rubber and a large amount of Qilong QH4100 are used in the embodiment, the peel strength and the cohesive strength of the hot melt adhesive product are greatly improved, glue overflow is not easy to occur, and the obtained hot melt adhesive product has strong adhesive force and strong universality.
Stated further, the oil-extended star rubber is one or more of star SBS1475, star SBS1484, star SBS1485 and star SBS 1487.
Specifically, star SBS1475 is produced in Taiwan plum, and its oil-filling amount is 33.3%; the star SBS1485 is produced in Taiwan plum, and the oil filling amount is 31%; the star SBS1484 is produced in Taiwan plum, and the oil filling amount is 33.3%; star SBS1487 is produced in Taiwan plum with oil filling of 28.5%.
Example 3
The oil-extended star-shaped rubber hot melt adhesive is prepared from the following raw materials, by mass, 23% of P-80, 8% of star-shaped SBS1484, 11% of star-shaped SBS1475, 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 56.7% of Qilon QH4100 and 0.3% of UV326, and is prepared by adopting the raw materials and the preparation method according to the embodiment 2.
Example 4
The oil-extended star-shaped rubber hot melt adhesive is prepared from the following raw materials, by mass, 23% of P-80, 12% of star-shaped SBS1487, 7% of star-shaped SBS1485, 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 56.7% of Qilon QH4100 and 0.3% of UV326, and is prepared by adopting the raw materials and the preparation method according to the embodiment 2.
Example 5
The oil-extended star-shaped rubber hot melt adhesive is prepared from the following raw materials, by mass, 23% of P-80, 10% of star-shaped SBS1485, 9% of star-shaped SBS1475, 0.5% of antioxidant 1010, 0.5% of antioxidant 168, 56.7% of Qilon QH4100 and 0.3% of UV326, and is prepared by adopting the raw materials and the preparation method according to the embodiment 2.
Specifically, the oil-extended star-shaped rubber hot melt adhesive products obtained in examples 1 to 5 were tested according to the following methods:
softening point test method: the softening point of the oil-extended star-shaped rubber hot melt adhesive obtained in examples 1 to 5 was tested by a method for testing the softening point of the hot melt adhesive according to the standard regulation of GB/T15332-94 "determination of softening point of Hot melt adhesive Ring and ball method";
viscosity test method: according to the test standard of a rotation method in GB/T10247-2008 standard, the viscosity of the oil-filled star-shaped rubber hot melt adhesive obtained in the embodiment 1-5 is detected, and a Brookfield viscometer is selected as a test instrument;
and (3) testing the peel strength: testing according to GB/T2792-;
cohesive strength (tensile strength): the cohesive strength of the oil-extended star-shaped rubber hot melt adhesive obtained in examples 1-5 is detected according to the determination of the tensile stress strain performance of the vulcanized rubber or thermoplastic rubber of GB/T528-2009;
and (3) odor test: the blind person smells the test blindly through the fixed personnel, then judges according to self feeling, and the judgement basis is as follows: no odor was assigned a score of 0, slight odor was assigned a score of 1, odor was assigned a score of 2 but not pungent, pungent odor was assigned a score of 3, strong pungent odor was assigned a score of 4, and intolerable odor was assigned a score of 5.
The detection is carried out by adopting the method, and the detection results are shown in the following table 1:
TABLE 1 test results of examples 1 to 5
Comparative example 1
The raw materials of the hot melt adhesive comprise, by mass, 27% of a plasticizer (KN 4010 is selected), 18% of non-oil-extended rubber (10% of SIS1209 and 8% of SIS1105 are selected), 53.7% of tackifying resin (32.5% of rosin resin and 21.2% of rhesus HS1001 are selected), 1% of an antioxidant (0.5% of antioxidant 1010 and 0.5% of antioxidant 168 are selected), and 0.3% of UV 326.
The preparation method of the thermosol comprises the following steps:
uniformly mixing 27% of plasticizer, 18% of non-oil-filled rubber and 1% of antioxidant, heating to 130 ℃, vacuumizing and stirring until all components are completely melted; and then adding 53.7% of tackifying resin and 0.3% of UV326 in sequence, heating to melt at 130 ℃, then vacuumizing until no bubbles exist, and stirring and mixing uniformly to obtain the hot melt adhesive.
Comparative example 2
The hot melt adhesive of the comparative example and the raw materials and the preparation method of the example 2 are basically the same, except that the plasticizer in the comparative example is naphthenic oil, and the oil-extended star-shaped rubber hot melt adhesive is prepared according to the raw materials and the preparation method.
The hot melt adhesive products obtained in comparative examples 1-2 were tested according to the conventional test methods for hot melt adhesives, and the test results are shown in table 1 below:
TABLE 1 test results
As can be seen from the test results in Table 1 above, in comparison with comparative example 1, the cohesive strength of the oil-extended star-shaped rubber hot melt adhesive prepared in example 1 is significantly greater than that of the hot melt adhesive in comparative example 1, and the peel strength was also higher than that of comparative example 1, and example 1 also had the advantages of low softening point, small viscosity at high temperature (150 c/cps), and small odor, compared to comparative example 1, and at the same time, in the preparation process, the oil-filled star rubber can be completely melted after being heated for 45 minutes at the temperature of 130 ℃ without long-time heating, therefore, the technical proposal successfully applies the oil-filled star-shaped rubber to the field of hot melt adhesive, overcomes the difficulty that the prior oil-filled star-shaped rubber is difficult to be applied to the hot melt adhesive, and the oil-filled star-shaped rubber hot melt adhesive prepared by adopting the oil-filled star-shaped rubber has better performance in all aspects than the existing common hot melt adhesive.
According to the detection result of the comparative example 2, if the plasticizer is naphthenic oil, although the cohesive strength and the peel strength of the prepared hot melt adhesive are high, the viscosity of the hot melt adhesive prepared in the comparative example 2 at 150 ℃ is very high, the use of the hot melt adhesive at high temperature and the service life of the hot melt adhesive are influenced, and in the preparation process, the oil-filled star-shaped rubber can be completely melted only after being heated for 110 minutes at 130 ℃, so that the preparation efficiency is greatly reduced, and the energy consumption is greatly increased.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. The oil-filled star-shaped rubber hot melt adhesive is characterized by comprising the following raw materials, by mass, 20-33% of a plasticizer, 15-30% of a high polymer, 35-64.7% of tackifying resin, 0.1-1.0% of an antioxidant and 0.2-1.0% of an ultraviolet absorber;
the high molecular polymer is oil-filled star rubber, and the molecular weight of the oil-filled star rubber is 30-60 ten thousand; according to the mass percentage, the oil filling amount of the oil-filled star rubber is 20-40%;
the plasticizer is a paraffinic oil.
2. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 1, wherein the melt index of the oil-extended star-shaped rubber is 5-50 (g/10min, 190 ℃/5 kg);
according to the mass percentage, the content of styrene in the oil-extended star rubber is 25-45%.
3. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 2, wherein the oil-extended star-shaped rubber is one or more of star-shaped SBS1475, star-shaped SBS1484, star-shaped SBS1485 and star-shaped SBS 1487.
4. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 1, wherein the molecular weight of the paraffinic oil is 50-400; the molecular weight of the tackifying resin is 300-2000.
5. The oil-extended star-shaped rubber hot melt adhesive according to claim 1, wherein the paraffinic base oil is KP6010 paraffinic base oil or P-80 paraffinic base oil.
6. The oil-extended star-shaped rubber hot melt adhesive according to claim 1, wherein the tackifying resin is one or more of hydrogenated C9 petroleum resin, hydrogenated C5 petroleum resin and hydrogenated DCPD petroleum resin.
7. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 1, wherein the antioxidant is one or both of an antioxidant 1010 and an antioxidant 168.
8. The oil-extended star-shaped rubber hot melt adhesive as claimed in claim 1, wherein the ultraviolet absorber is UV 326.
9. A preparation method of the oil-extended star-shaped rubber hot melt adhesive is characterized by being used for preparing the oil-extended star-shaped rubber hot melt adhesive as claimed in any one of claims 1 to 7, and comprising the following steps:
(1) according to the formula ratio, adding a plasticizer and an antioxidant into a reaction kettle, heating to raise the temperature to 115-125 ℃, adding oil-filled star rubber, controlling the temperature to be 120-150 ℃, and stirring;
(2) and (2) after the oil-filled star rubber in the step (1) is completely melted, adding tackifying resin and an ultraviolet absorbent, controlling the temperature to be 120-150 ℃, and after the tackifying resin is completely melted, vacuumizing until no air bubbles exist, and discharging the glue to obtain the oil-filled star rubber hot melt adhesive.
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| CN115838578A (en) * | 2022-10-14 | 2023-03-24 | 江苏嘉好热熔胶股份有限公司 | Wet strength structural adhesive for disposable hygienic products and preparation method thereof |
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| EP0700978A1 (en) * | 1994-08-18 | 1996-03-13 | National Starch and Chemical Investment Holding Corporation | Hot melt adhesive compositions |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115838578A (en) * | 2022-10-14 | 2023-03-24 | 江苏嘉好热熔胶股份有限公司 | Wet strength structural adhesive for disposable hygienic products and preparation method thereof |
| CN115838578B (en) * | 2022-10-14 | 2024-04-19 | 江苏嘉好热熔胶股份有限公司 | Wet strength structural adhesive for disposable sanitary products and preparation method thereof |
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